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CN105308009A - Method for producing unsaturated hydrocarbon using metal-containing zeolite catalyst - Google Patents

Method for producing unsaturated hydrocarbon using metal-containing zeolite catalyst Download PDF

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Publication number
CN105308009A
CN105308009A CN201480032497.3A CN201480032497A CN105308009A CN 105308009 A CN105308009 A CN 105308009A CN 201480032497 A CN201480032497 A CN 201480032497A CN 105308009 A CN105308009 A CN 105308009A
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China
Prior art keywords
zeolite
manufacture method
catalyzer
reaction
zsm5
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CN201480032497.3A
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CN105308009B (en
Inventor
冈部晃博
秋山聪
梅野道明
水津宏
村上昌义
宫路淳幸
辰巳敬
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Mitsui Chemical Industry Co Ltd
Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Mitsui Chemical Industry Co Ltd
Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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Publication of CN105308009A publication Critical patent/CN105308009A/en
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Publication of CN105308009B publication Critical patent/CN105308009B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
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    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7276—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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  • Chemical & Material Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A method for producing a low-grade olefin having ethylene and propylene as the principal components thereof according to an embodiment of the present invention is characterized by contacting: a metal-containing zeolite catalyst having, as constituent elements thereof, a metal (X) selected from the group 8-10 metals of the periodic table, and a medium-pore zeolite (Z1) having a 10-membered ring structure comprising ten of a tetrahedral TO4 (T=Si or Al) unit; a material (O) having, as the principal component thereof, a saturated hydrocarbon having a boiling point in the range of 35-180 DEG C at 1 atm; and an acidic gas (S).

Description

Employ the manufacture method of the unsaturated hydro carbons of containing metal zeolite catalyst
Technical field
The present invention relates to the method using zeolite catalyst to be manufactured unsaturated hydro carbons by the raw material taking saturated hydrocarbons as principal constituent.
Background technology
The mono-cyclic aromatic same clans such as light alkene class and benzene, toluene, ethylbenzene and xylene such as ethene, propylene, butylene and divinyl are the important foundation chemical feedstockss of the backbone forming petrochemical industry.Manufacture the raw material of these basic chemical feedstock mainly as the petroleum naphtha of the straight run light ends of crude oil.
In these basic chemical feedstock, about light alkene classes such as ethene, propylene, butylene and divinyl, following manufacture: the light naphtha of the lower composition of boiling point will be belonged to as raw material in petroleum naphtha, by in naphtha cracker complex, carry out thermolysis (steam cracking) when steam coexist with the high temperature of more than 800 DEG C.In addition, in the thermolysis of light naphtha, except light alkene class, the fragrant same clans such as coproduction benzene, toluene, ethylbenzene, xylene are gone back.But to these fragrant same clans, the manufacture method that known general employing is raw material with the cut corresponding to the heavy naphtha being rich in high boiling point composition than light naphtha, this is compared with the method manufactured by light naphtha, is more efficient manufacture method.From this viewpoint, the decomposition product to light naphtha can be said, it is desirable to reduce aromatic component and improve the ratio of light alkene class as far as possible.
If pay close attention to the Demand trend in recent years of light alkene class, then, headed by polypropylene, the demand of the acryloyl derivative such as isopropyl benzene, propylene oxide expands.At present, the growth growing beyond ethylene requirements of propylene demand, can think that the difference of the demand growth of this propylene and ethene from now on will be accelerated further.
On the other hand, as the rudimentary saturated hydrocarbons of the principal constituent of petroleum naphtha, because its reactivity is low, therefore as the decomposition temperature of naphtha cracking, need the high temperature of more than 800 DEG C, the decomposition temperature that can obtain the output of good economy performance is limited in scope.Generally speaking, more carry out naphtha cracking at high temperature, higher compared to the yield of the ethene of propylene, the high-temperature zone more than 800 DEG C, the propylene/ethylene ratio in resultant is about 0.6 ~ 0.7.In this temperature range, cannot change propylene/ethylene ratio significantly, therefore can say, with existing naphtha cracker complex, it is very difficult that the selectivity of propylene is produced.
In sum, decomposition temperature is depended in the resultant distribution in thermolysis, therefore thinks that existing naphtha cracker complex is difficult to the variation of the equilibrium of supply and demand tackling each composition neatly.In addition, centered by the natural gas producing nation such as the Middle East, advance raw material conversion rapidly, that be raw material with price low-down ethane compared with petroleum naphtha, that cost competitiveness is high ethene comes into the market.Therefore, the naphtha cracker complex in the Asia headed by domestic is had to carry out that production regulates etc. and is dealt with these situations.When so forcing, looking forward to the petroleum naphtha decomposition technique that can control resultant distribution according to supply and demand, for this reason, as promising technology, disclosing the contact decomposition technique (such as, patent documentation 1) using acid form catalyzer.This technology, compared with the existing naphtha cracker complex belonging to many energy-dissipating types equipment, can reduce consumed energy, and then can reduce the carbonic acid gas (non-patent literature 1) discharged in a large number with petroleum naphtha decomposes.
In the contact decomposition technique of the rudimentary saturated hydrocarbons such as disclosed petroleum naphtha, mesopore zeolite, the MFI zeolite wherein particularly representated by ZSM5, has excellent performance when generating light alkene class and aromatics class.Utilize these technology, temperature of reaction can be reduced to less than 700 DEG C, can improve the selectivity of propylene and the ratio of propylene/ethylene significantly.In addition, by reducing temperature of reaction, the growing amount as the lower methane of the value of chemical feedstocks can also be suppressed.But these public technologies also cannot be called the technology of the ripe degree to replaceable thermolysis of both having deposited.
In order to make to utilize the contact decomposition technique of the rudimentary saturated hydrocarbons such as the petroleum naphtha of zeolite reach can be practical level, need the extending catalyst life-span significantly.In addition, catalyst life is using huge problem common in the reaction process of zeolite catalyst, and especially, reaction conditions is harsher, more can cause the remarkable reduction of catalyst performance.The reduction of catalyst performance causes the production declining of object resultant, cause because of the change of resultant distribution problems such as the load increases of refining step.The major cause of the performance reduction of zeolite catalyst, the carbonaceous aluminium component piled up in the pore obturation caused and the crystallization of zeolites skeleton caused by the contact etc. with high-temperature steam thinking to be called as coke (coke) departs from the disappearance of the Acidity caused.
The generation of coke, thinks under harsh reaction conditions, carries out in proper order causing by the side reaction as the polymerization of light alkene, cyclisation, aromatic series.On the other hand, the feature of zeolite catalyst is, have the pore that the size that derives from crystalline texture is clear and definite, the reaction of shape selective is carried out in the acid site in pore.Therefore, particularly, if use the zeolite catalyst without the large pore of more than 12 rings, then, due to the restriction of aspect, space, in pore, the gradualness side reaction that coke can be caused to generate also is restricted.But, in zeolite, at the pore outside surface of restriction not by pore shape, also there is acid site in certain proportion, think the generation (non-patent literature 2) that can cause coke thus because of the carrying out of non-selective reaction.It is the reaction at high temperature carried out that contact due to lower hydrocarbon such as petroleum naphthas is decomposed, thus such because of coking (コ ー キ Application グ) and the performance of zeolite catalyst that causes to reduce be serious problem, in practical, the technology of coking is suppressed to become key point.
In the contact converting reaction process of the saturated hydrocarbons at high temperature carried out, generally speaking, catalyzer is due to coking, and its activity reduces, but known to adding oxidizing gas in the feed, coke can be suppressed to generate, the extending catalyst life-span.As oxidizing gas, use water vapour, carbonic anhydride etc.
Such as, use Pt catalyzer carry out dehydrogenating propane reaction propylene manufacture (non-patent literature 3), use Fe catalyzer to carry out, in the techniques such as the vinylbenzene manufacture (non-patent literature 4) of ethylbenzene dehydrogenation reaction, using water vapour by adding in the feed.Water vapour plays the effect as oxidizing gas under the high temperature conditions, can think in catalyst layer, except principal reaction, promotes the removal of coke and the precursors of coke produced because of steam reforming reaction, suppresses coking.
On the other hand, known zeolites catalyzer generally contacts with steam under the high temperature conditions, is therefore absorbed in permanent active deterioration.This permanent active deterioration combines hydrolysis by the Al-O-Si in zeolite framework under the high temperature conditions, and Al composition departs from, and Acidity disappears and produces.Therefore, in order to adopt water vapour as oxidizing gas in the pyroreaction technique using zeolite catalyst, need to use the zeolite catalyst being applied with the process improving steam patience.
In the contact decomposition technique of the rudimentary stable hydrocarbon such as disclosed petroleum naphtha so far, as the technique using common zeolite catalyst, need the so-called harsh high temperature of more than 600 DEG C.But, due to the significant coking being difficult to suppress can be produced under this condition, therefore water vapour is made an addition in raw material, coking is relaxed.On the other hand, in the contact decomposition reaction technique of the rudimentary stable hydrocarbon such as petroleum naphtha, catalyzer needs repeatedly to carry out reacting, regenerating in life-time service, and due to the interpolation of water vapour, catalyzer can be exposed to high-temperature vapor for a long time, therefore easily causes active deterioration.In addition, the reason that the specific energy consumption that the energy consumption required for manufacture of high-temperature vapor becomes technique entirety is deteriorated.In sum, it seems from practicality and Eco-power viewpoint, need the addition of water vapour to suppress as far as possible low.
Open use improves the zeolite catalyst of steam patience, adds water vapour in the feed, the example that the contact implementing the rudimentary stable hydrocarbon such as petroleum naphtha is decomposed.In patent documentation 2, employ the ZSM5 catalyzer containing P, in patent documentation 3, employ the ZSM5 catalyzer containing P, Ca, La, about normal hexane decomposition reaction, implement the continuous operation of more than 48 hours.But to any example, it seems from the viewpoint of practicality and economy, not talkative is the continuous operation under reality condition.
In addition, also disclose and add water vapour in the feed to carry out the example (patent documentation 4 and 5, non-patent literature 5) of the contact decomposition reaction of the rudimentary stable hydrocarbon such as petroleum naphtha, but to any example, there is no the continuous operation implementing the feasibility considered from practical face.
Be disclosed in steam reforming reaction, used the zeolite catalyst being added with the activated metal species of tool, under water vapour adding conditional, implement the technology of the contact decomposition reaction of the rudimentary stable hydrocarbon such as petroleum naphtha.In non-patent literature 6, in steam reforming reaction, adopt the ZSM5 that with the addition of activated Ni and Ru of tool as catalyzer, to the light naphtha contact decomposition reaction under water vapour adding conditional, carry out the continuous operation of 10 hours.But it seems from practicality and Eco-power viewpoint, not talkative is the continuous operation under reality condition.
In non-patent literature 7, in steam reforming reaction, adopt the ZSM5 being added with the activated Pd of tool as catalyzer, under water vapour adding conditional, implement petroleum naphtha contact decompose.In the prior art document, in order to improve reactivity, except water vapour, in raw material petroleum naphtha, also adding methyl alcohol, at catalyst layer temperature 635 DEG C, implementing reaction, but transformation efficiency, when maximum, also stop at 52.2%, decomposition reaction cannot be carried out fully.
In non-patent literature 5, will the ZSM5 of Mo and Ce be added with as catalyzer, under water vapour adding conditional, implement petroleum naphtha contact decompose.But transformation efficiency, also stops at 55.3% when maximum, decomposition reaction cannot be carried out fully.In addition, the reaction times is as short as 5 hours, does not carry out the continuous operation from the viewpoint of practical feasibility.
In the embodiment 11 of patent documentation 4, as catalyst layer, Pt catalyzer is divided into leading portion, the ZSM5 catalyzer being carried with Pr is divided into back segment, under water vapour adding conditional, implement normal butane contact decomposition reaction.But in this reaction system measurable, Pt catalyzer is difficult to remove efficiently the coke and precursors of coke piled up on ZSM5.
In the same manner as water vapour, to carbonic anhydride also known its, there is coking inhibition.Can think by the mechanism same with water vapour, utilize dry type reforming reaction to promote the removal of coke and precursors of coke, suppress coking.In addition, to carbonic anhydride, known except dry type reforming reaction, go back accelerating oxidation dehydrogenation reaction.
As the technique that carbonic anhydride is added in stable hydrocarbon raw material as oxidizing gas, the benzene manufacture such as utilizing the aromatic seriesization of the rudimentary saturated hydrocarbons such as methane, ethane, propane to react can be enumerated, utilize the rudimentary unsaturated hydro carbons manufacture of the dehydrogenation reaction of the rudimentary saturated hydrocarbons such as ethane, propane, butane, utilize the vinylbenzene manufacture etc. of ethylbenzene dehydrogenation reaction, utilize the reaction process (non-patent literature 8) of oxidative dehydrogenation.Wherein, about aromatic series manufacturing process, under being disclosed in the condition being added with carbonic anhydride, use the example (non-patent literature 9 and 10) of containing metal zeolite catalyst suitably.On the other hand, utilize the contact decomposition reaction of the rudimentary stable hydrocarbon such as petroleum naphtha in the technique manufacturing rudimentary unsaturated hydro carbons, need to suppress the carrying out of excessive dehydrogenation reaction, but the not yet open example applied carbonic anhydride in order to this suppression and add.
In patent documentation 2, as using the form implementing the contact decomposition technique of the rudimentary stable hydrocarbon such as petroleum naphtha containing the zeolite catalyst of P, describing and carbonic anhydride can be used as the such content of diluent gas.But, in the prior art document, carbonic anhydride is recited as only to dilute the gas for the purpose of raw material, and the intention do not used as oxidizing gas completely, do not imagine coking inhibition on a catalyst completely yet.In addition, in this look-ahead technique document, also openly do not add the embodiment of the contact decomposition reaction of carbonic anhydride, about the contact decomposition technique of the rudimentary stable hydrocarbon such as petroleum naphtha, make us cannot expecting completely adding by carbonic anhydride the effect that the catalyst life that causes improves.
In the embodiment of patent documentation 4, disclose in normal butane contact decomposition reaction, containing the reaction result that the carbonic anhydride generated by the oxidation of raw material is such in resultant.But the impact that carbonic anhydride contained in resultant brings catalyst life is indefinite, from practicality and Eco-power viewpoint, do not implement to run continuously under reality condition yet.
Generally speaking, known in reforming reaction, waste gas in the oxidizing reaction such as VOC decomposition reaction, purifying vehicle exhaust reaction, by using oxygen ion conduction body that the lattice oxygen such as perofskite type oxide and cerium oxide supply capacity is high as carrier, improve the activity (such as non-patent literature 11 ~ 17 etc.) of metal catalyst.But, in the contact decomposition reaction of the rudimentary stable hydrocarbon such as petroleum naphtha, not yet openly pay close attention to this series of prior art and be used for the lattice oxygen supply capacity of support of the catalyst to improve the example of catalyst life.
In sum, if consider the contact decomposition reaction of the rudimentary saturated hydrocarbons such as petroleum naphtha, then studying by adding oxidizing gas in the feed to suppress the technology causing the coking that catalyst life shortens hardly, also cannot say that it reaches practical level.In view of such circumstances, to the contact decomposition reaction of the rudimentary saturated hydrocarbons such as petroleum naphtha, expect a kind ofly to suppress the generation of coke by oxidizing gas and can the containing metal zeolite catalyst of long-term continuous seepage light alkene class efficiently.
[at first technical literature]
[patent documentation]
Patent documentation 1: Japanese Unexamined Patent Publication 6-192135 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-193127 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2010-104878 publication
Patent documentation 4: Japanese Unexamined Patent Publication 11-180902 publication
Patent documentation 5: Japanese Unexamined Patent Application Publication 2011-523584 publication
[non-patent literature]
Non-patent literature 1: the energy (Energy), the 31st volume, 425-451 page (2006)
Non-patent literature 2: Japanese chemical engineering magazine (JournalofChemicalEngineeringofJapan) the 42nd volume, S162-S167 page (2009)
Non-patent literature 3: applied catalysis (AppliedCatalysis) A: general (General), the 221st volume, 397-419 page (2001)
Non-patent literature 4: catalysis comment (CatalysisReviews), the 8th volume, 285-305 page (1974)
Non-patent literature 5: catalysis bulletin (CatalysisLetters), the 100th volume, 1-6 page (2005)
Non-patent literature 6: technical chemistry and engineering chemistry are studied (Industrial & EngineeringChemistryResearch), the 47th volume, 2963-2969 page (2008)
Non-patent literature 7: catalysis bulletin (CatalysisLetters), the 142nd volume, 60-70 page (2012)
Non-patent literature 8: the energy and fuel (Energy & Fuels), the 18th volume, 1126-1139 page (2004)
Non-patent literature 9: catalysis (JournalofCatalysis), the 182nd volume, 92-103 page (1999)
Non-patent literature 10: application organometallic chemistry (AppliedOrganometallicChemistry), the 14th volume, 778-782 page (2000)
Non-patent literature 11: chemical engineering magazine (ChemicalEngineeringJournal), the 112nd volume, 13-22 page (2005)
Non-patent literature 12: catalysis (JournalofCatalysis), the 234th volume, 496-508 page (2005)
Non-patent literature 13: catalysis bulletin (CatalysisLetters), the 105th volume, 239-247 page (2005)
Non-patent literature 14: applied catalysis (AppliedCatalysis) A: general (General), the 286th volume, 23-29 page (2005)
Non-patent literature 15: Surface Science and catalyticing research (StudiesinSurfaceScienceandCatalysis), the 119th volume, 843-848 page (1998)
Non-patent literature 16: hazardous material magazine (JournalofHazardousMaterials), 244-245 rolls up, 613-620 page (2013)
Non-patent literature 17: Asia catalysis outline (CatalysisSurveysfromAsia), the 9th volume, 63-67 page (2005)
Summary of the invention
[inventing problem to be solved]
Problem of the present invention is, provides a kind of manufacture method employing the light alkene class of containing metal zeolite catalyst, and its contact by rudimentary saturated hydrocarbons such as petroleum naphthas is decomposed, and can supply light alkene class continuously for a long time with high yield.
[for solving the method for problem]
The present inventor etc. further investigate in view of the above problems, result is for above-mentioned problem, by using the containing metal zeolite catalyst being integrant with periodictable 8th ~ 10 race's metal and mesopore zeolite, in the rudimentary saturated hydrocarbons such as the petroleum naphtha as raw material, add oxidizing gas to carry out contact decompose, thus make this skill upgrading to industrial level, so that complete the present invention.
That is, the present invention contains following item.
(1) a kind of manufacture method of light alkene class, the manufacture method of the light alkene class of 2 ~ 4 that to be the carbonatoms being principal constituent with ethene, propylene be, it is characterized in that, the raw material (O) that to make with the boiling point under 1 air pressure be the saturated hydrocarbons within the scope of 35 ~ 180 DEG C be principal constituent contacts with containing metal zeolite catalyst with oxidizing gas (S), and described containing metal zeolite catalyst contains periodictable 8th ~ 10 race metal (X) and by ten tetrahedral TO 4the mesopore zeolite (Z1) of the ten-ring structure that (T represents Si atom or Al atom, and O represents Sauerstoffatom) unit is formed is as integrant.
The manufacture method of the light alkene class (2) as described in (1), more than one for being selected from water vapour and carbonic anhydride of described oxidizing gas (S).
The manufacture method of the light alkene class (3) as described in (1) or (2), under catalyst temperature when making described containing metal zeolite catalyst contact with described raw material (O) and described oxidizing gas (S), namely under the temperature of reaction in the contact decomposition reaction of described raw material (O), in other words, at the temperature of the catalyst layer in contact decomposition reaction, the volume (V shared by gas of described oxidizing gas (S) s) relative to described raw material (O) gas shared by volume (V o) ratio (V s/ V o) be 0.01 ~ 2 scope.
The manufacture method of the light alkene class (4) according to any one of (1) ~ (3), the temperature of reaction of the contact decomposition reaction of described raw material (O) is 500 ~ 750 DEG C of scopes.
The manufacture method of the light alkene class (5) according to any one of (1) ~ (4), mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 ').
The manufacture method of the light alkene class (6) according to any one of (1) ~ (5), described containing metal zeolite catalyst further containing more than one the element be selected from the group that is made up of periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) as integrant, described element (Y2) is for being selected from more than one the element in P, As, Sb and Bi.
The manufacture method of the light alkene class (7) as described in (6), described containing metal zeolite catalyst contains described element (Y2), and described element (Y2) is P.
The manufacture method of the light alkene class (8) as described in (6) or (7), described containing metal zeolite catalyst contains described element (Y1), and described element (Y1) is Ce.
The manufacture method of the light alkene class (9) according to any one of (5) ~ (8), described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), and described mesopore zeolite (Z1 ') is carried with described metal (X).
The manufacture method of the light alkene class (10) as described in (9), described mesopore zeolite (Z1 ') holds more than one element in the group being selected from and being made up of periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) further, and described element (Y2) is for being selected from more than one the element in P, As, Sb and Bi.
The manufacture method of the light alkene class (11) according to any one of (6) ~ (8), described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), containing metal zeolite catalyst is, is supported at the described metal (X) on the oxide compound (Z2) of described element (Y1) or is supported at described metal (X) in the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described mesopore zeolite (Z1 '), physical mixed body with described mesopore zeolite (Z1 ').
The manufacture method of the light alkene class (12) according to any one of (6) ~ (8), described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), containing metal zeolite catalyst is the described metal (X) that is supported on the oxide compound (Z2) of described element (Y1) or the described metal (X) be supported in the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described mesopore zeolite (Z1 '), with the physical mixed body of described mesopore zeolite (Z1 ') being carried with described element (Y2).
The manufacture method of the light alkene class (13) as described in (12), described mesopore zeolite (Z1 ') holds Al further.
The manufacture method of the light alkene class (14) as described in (13), containing metal zeolite catalyst contains P as described element (Y2) as must element, and the Al that described mesopore zeolite (Z1 ') holds derives from and is selected from boehmite, at least one aluminum contained compound (A) intended in boehmite, aluminum oxide, aluminium salt and amorphous silica-aluminum oxide.
The manufacture method of the light alkene class (15) as described in (14), described aluminum contained compound (A) is any one in boehmite or plan boehmite.
The manufacture method of the light alkene class (16) according to any one of (13) ~ (15), the composition of Si and Al contained by described mesopore zeolite (Z1 '), by the mol ratio (SiO being converted into silicon-dioxide and aluminum oxide 2/ Al 2o 3) count 30 ~ 100 scope, and the total of the Al composition contained by described containing metal zeolite catalyst counts the scope of 1 ~ 10 quality % with Al atom.
The manufacture method of the light alkene class (17) according to any one of (14) ~ (16), the composition of P and Al contained by described containing metal zeolite catalyst, counts the scope of 0.1 ~ 1.0 with atomic molar ratio (P/Al).
The manufacture method of the light alkene class (18) according to any one of (11) ~ (17), described oxide compound (Z2) is cerium oxide.
The manufacture method of the light alkene class (19) according to any one of (11) ~ (18), described inorganic solid compounds (Z3) is perovskite compound.
The manufacture method of the light alkene class (20) according to any one of (6) ~ (8), described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), containing metal zeolite catalyst is, be supported at the described metal (X) on the oxide compound (Z2) of described element (Y1) or be supported at the described metal (X) in the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described mesopore zeolite (Z1 '), the physical mixed body of the described metal (X) held with described mesopore zeolite (Z1 ').
The manufacture method of the light alkene class (21) as described in (20), described mesopore zeolite (Z1 ') holds more than one the element be selected from described element (Y1) and described element (Y2) further.
The manufacture method of the light alkene class (22) as described in (10), described mesopore zeolite (Z1 ') holds Al further.
The manufacture method of the light alkene class (23) according to any one of (1) ~ (22), described metal (X) is for being selected from the metal in Ru, Rh, Ir, Ni, Pd and Pt.
[invention effect]
According to the present invention, in the contact decomposition reaction of the rudimentary saturated hydrocarbons such as petroleum naphtha, light alkene class can be manufactured continuously for a long time with high yield.
Embodiment
Below, describe a kind of method being manufactured light alkene class by rudimentary saturated hydrocarbons such as petroleum naphthas in detail, it use the containing metal zeolite catalyst involved by embodiment.
The manufacture method of the light alkene class involved by embodiment is as follows: use above-mentioned containing metal zeolite catalyst, the raw material that to make with the saturated hydrocarbons that is 35 ~ 180 DEG C of scopes of the boiling point under 1 air pressure be principal constituent produces contact decomposition reaction, the light alkene class that to manufacture with ethene, propylene be principal constituent.At this, " light alkene " refers to that carbonatoms is the alkene of 2 ~ 4, and what " principal constituent " to refer in light alkene contained ethene, propylene adds up to more than 50 quality %.Below, successively the modulator approach of raw material (O), oxidizing gas (S), mesopore zeolite (Z1), containing metal zeolite catalyst, this catalyzer and reactive mode and other guide are described in detail.
(raw material)
As the raw material of saturated hydrocarbons for principal constituent taking the boiling point under 1 air pressure as 35 ~ 180 DEG C of scope To, be not particularly limited, can enumerate with carbonatoms be 3 ~ 10 sturated aliphatic hydrocarbon and the ester ring type hydrocarbon raw material etc. that is principal constituent.Particularly, light naphtha, heavy naphtha, full fraction naphtha, FCC gasoline and pyrolysis gasoline etc. can be enumerated.In addition, in petroleum refining process, decomposing by flowing contact the heavy ends such as decompression light oil, Residual oil carrying out lighting does not become object.At this, principal constituent refers to containing the boiling point under 1 air pressure to be more than the saturated hydrocarbons 70 quality % of 35 ~ 180 DEG C of scopes, in addition also can contain the heterogeneous ring compounds such as sulfocompound, nitrogenous compound and oxygenatedchemicals.Particularly, about sulfocompound, generally speaking, because it becomes the poisoning constituents of metal catalyst, therefore think to contain the unsuitable composition of catalyzer to metal.But the manufacture method of the light alkene class in the present invention does not produce special impact to catalyst performance.When contact described later is decomposed, except above-mentioned raw materials, also can as required the gases such as nitrogen low for reactivity and helium be supplied in reactor.
(oxidizing gas)
In the contact decomposition reaction of the rudimentary stable hydrocarbon such as petroleum naphtha, as the oxidizing gas with catalyst layer contacts, be not particularly limited, particularly, water vapour, carbonic anhydride, Nitrous Oxide, air, oxygen, ozone etc. can be enumerated.Wherein, water vapour and carbonic anhydride can be used especially suitably.
(mesopore zeolite (Z1))
The matrix of the containing metal zeolite catalyst of mesopore zeolite (Z1) involved by present embodiment has by ten tetrahedral TO 4the zeolite of the ten-ring structure that (T represents Si atom or Al atom, and O represents Sauerstoffatom) unit is formed.In this zeolite, preferred fine pore is the volume that the pore of 0.50 ~ 0.65nm scope accounts for more than 10% of the full pore deriving from crystallization of zeolites structure, more preferably accounts for the volume of more than 20%, preferably accounts for the volume of more than 50% further.In addition, the pore deriving from crystallization of zeolites structure represents that fine pore is the pore of 0.20 ~ 1.0nm scope.In addition, about the fine pore of pore deriving from crystallization of zeolites structure, calculated by the Adsorption and desorption isotherms measured by nitrogen adsorption methods by temperature variation curve (t-plot) method.
The preferable range with the fine pore of the pore of ten-ring structure of above-mentioned mesopore zeolite (Z1) is 0.50 ~ 0.65nm, and preferred scope is 0.50 ~ 0.60nm.Fine pore is less than to the pore of 0.50nm, due to restriction spatially, as raw material naphtha fraction contained by stable hydrocarbon be difficult at pore internal diffusion, thus likely hinder the carrying out of decomposition reaction.In addition, to the pore of fine pore more than 0.65nm, because system limit is spatially few, the carrying out of the coke formation reaction in pore is likely promoted.Therefore, fine pore be the pore of 0.50 ~ 0.65nm scope account for the full pore deriving from crystallization of zeolites structure be less than 10% when, the contact decomposition reaction of the saturated hydrocarbons such as petroleum naphtha cannot be controlled fully.
The crystalline texture of above-mentioned mesopore zeolite (Z1) is preferably MFI type, MWW type or FER type, is more preferably MFI type or MWW type, is particularly preferably MFI type.In addition, in below illustrating, sometimes the mesopore zeolite of the crystalline texture with MFI type, MWW type or FER type is called mesopore zeolite (Z1 ').
Element silicon (Si) contained by above-mentioned mesopore zeolite (Z1) and the content ratio of aluminium element (Al), be converted into SiO 2/ Al 2o 3mol ratio, is preferably 25 ~ 1000 scopes, is more preferably 25 ~ 300 scopes.
Above-mentioned mesopore zeolite (Z1) can use always known method manufacture, also can use commercially available product.As commercially available product, such as NH can be enumerated 4 +type ZSM5 (molecular sieve catalyst international corporation system) etc.
The particle diameter of above-mentioned mesopore zeolite (Z1) is not particularly limited.But if particle diameter is too small, then crystalline reduction is troubling, if excessive on the contrary, then the pore length in crystallization becomes long, brings out the pore caused because of coking inaccessible.The particle diameter of zeolite is preferably 10nm ~ 5000nm, is more preferably 50nm ~ 1000nm.
To above-mentioned mesopore zeolite (Z1), in order to the acid site being positioned at the existence of pore outside surface of the non-selective reactions such as coating promotion coke generation, silylation process can be applied as required.As silylation process, be not particularly limited, the known method usually carried out can be used.Particularly, oxyalkyl silicane such as utilizing tetramethoxy-silicane, tetraethoxysilane and aminopropyl triethoxysilane can be enumerated; The Silicon Containing Hydrogen alkanes such as Trimethoxy silane, triethoxyl silane, 1,3,5,7-tetramethyl-ring tetrasiloxane; The silazane classes such as hexamethyldisilazane and nine methyl three silazane; The silicates such as water glass and potassium silicate; And the process of the halogenated silicon compound class such as ammonium hexafluorosilicate, silicon tetrachloride and trimethylchlorosilane etc.
To above-mentioned mesopore zeolite (Z1), in order to control acid amount, dealumination treatment can be applied as required.As dealumination treatment, be not particularly limited, the known method usually carried out can be used.Particularly, high temperature steam treatment can be enumerated; The mineral acid process such as hydrochloric acid, nitric acid and sulfuric acid; The process of tetraacethyl diamino-vinyl; Hexafluorosilicic acid Ficus caricaL; And silicon tetrachloride process etc.
(containing metal zeolite catalyst)
Containing metal zeolite catalyst involved by present embodiment is containing above-mentioned mesopore zeolite (Z1) and periodictable 8th ~ 10 race metal (X) catalyzer as integrant.Containing metal zeolite catalyst, as long as the metal (X) containing more than one just manifests effect, but also can be made up of two or more metals (X).Metal (X) is preferably selected from Ru, Rh, Ir, Ni, Pd and Pt, is more preferably selected from Ru, Rh, Ir, Pd and Pt, is preferably selected from Ru, Rh, Pd and Pt further.In addition, as the example be made up of two or more metals (X), the combination of Pt and Pd, the combination of Pd and Ru, the combination etc. of Pt and Ru can be enumerated, but be not limited thereto.
The metal (X) of the integrant as above-mentioned containing metal zeolite catalyst is accounted for the content of monolith, be not particularly limited, as element, be preferably 0.01 ~ 30 quality %, be more preferably 0.01 ~ 3 quality %, more preferably 0.01 ~ 1 quality %, most preferably is 0.05 ~ 1 quality %.
In addition, as the integrant of containing metal zeolite catalyst, the chemical form of metal (X) is not particularly limited.Particularly, elemental metals, alloy, oxide compound, sulfide, nitride, carbide, boride, halogenide, hydride, the Proton in Water acids (ア Network ア acid Class), the Proton in Water Barbiturates (ア Network ア acid salt Class), the Proton in Water acid ion (ア Network ア acid イ オ Application), hydroxyl acids, alcohol acid salt, alcohol acid ion, oxygen acid class, oxygen acid salt, oxygen acid ion, metal ion etc. can be enumerated, to any compound, as long as containing at least one in periodictable 8th ~ 10 race metal, just can also contain other elements simultaneously.Now, being not particularly limited containing mode to other elements.As the combination of periodictable 8th ~ 10 race metal with other elements, the combination of platinum-Xi, the combination of platinum-indium, the combination as platinum-zinc disclosed in aftermentioned catalyzer modulation example 11, the combination of platinum-germanium, the combination of platinum-Xi-indium, the combination of platinum-palladium-Xi, the combination of palladium-Xi, the combination of palladium-zinc, the combination of palladium-indium, the combination of palladium-germanium, the combination etc. of palladium-ruthenium can be enumerated.Like this when containing other elements except periodictable 8th ~ 10 race metal, relative to periodictable 8th ~ 10 race metal, the content of other metals is generally 0.1 ~ 2.0 with atomic ratio measuring, is preferably 0.3 ~ 1.5 scope.In addition, can think that these various metals form alloy state on carrier usually.In addition, to the scientific form of metal (X), platinum (II) ion exchanged zeolite, palladium (II) ion exchanged zeolite etc. can during metal ion, be enumerated.
As forming the mesopore zeolite (Z1) of above-mentioned containing metal zeolite catalyst, preferably its crystalline texture is the mesopore zeolite (Z1 ') of MFI type, MWW type or FER type.In addition, this containing metal zeolite catalyst, can except metal (X) containing more than one the element be selected from periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) as integrant, preferably containing more than one the element be selected from periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) as integrant, more preferably containing being selected from more than one element of periodictable the 3rd race's element (Y1) and being selected from more than one element both sides in periodictable the 15th race's element (Y2) as integrant.In addition, in the following description, sometimes more than one the element be selected from periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) is generically and collectively referred to as element (Y).At this, as above-mentioned periodictable the 3rd race's element (Y1), be preferably Sc, Y, La, Ce, Pr, Sm, most preferably be Ce.As above-mentioned periodictable the 15th race's element (Y2), be preferably P, As, Sb and Bi, most preferably be P.
When above-mentioned containing metal zeolite catalyst contains element (Y) as integrant, the content of element (Y) is not particularly limited, but as preferred composition, following composition can be enumerated.To periodictable the 3rd race's element (Y1), the concentration that the total of contained 3 whole race's elements accounts for catalyzer is preferably 0.01 ~ 50 quality %, more elect 0.01 ~ 10 quality % as, more preferably 0.01 ~ 3 quality %, most preferably be 0.05 ~ 1 quality %.In addition, to periodictable the 15th race's element (Y2), the concentration that the total of contained 15 whole race's elements accounts for catalyzer is preferably 0.01 ~ 30 quality %, more elects 0.01 ~ 10 quality % as, more preferably 0.01 ~ 5 quality %, most preferably is 0.05 ~ 5 quality %.
When containing metal zeolite catalyst contains element (Y) as integrant, the chemical form of element (Y) is not particularly limited.Particularly, monomer, oxide compound, sulfide, nitride, carbide, boride, halogenide, hydride, the Proton in Water acids, the Proton in Water Barbiturates, the Proton in Water acid ion, hydroxyl acids, alcohol acid salt, alcohol acid ion, oxygen acid class, oxygen acid salt, oxygen acid ion, metal ion etc. can be enumerated.In addition, when element (Y) is containing two or more elements, the chemical form of respective element can be different, also can be the forms of the Composites such as composite oxides.
When above-mentioned containing metal zeolite catalyst contains element (Y) as integrant, to the combination [(X), (Y)] of metal (X) and element (Y), be not particularly limited, as preferred combination, can enumerate [(X), (Y1)] and [(X), (Y1), (Y2)].More specifically, as [(X), (Y1)], [(Pt can be enumerated; Pd), (Ce)], [(Pd), (Ce)], [(Pd; Ru), (Ce)] etc., [(Pt), (Ce), (P)], [(Pt in addition, as [(X), (Y1), (Y2)], can be enumerated; Pd), (Ce), (P)], [(Pd), (Ce), (P)], [(Pd; Ru), (Ce), (P)] etc.Wherein, as particularly preferred combination, [(Pt), (Ce), (P)], [(Pd), (Ce)], [(Pd), (Ce), (P)], [(Pd can be enumerated; Ru), (Ce), (P)].In addition, in above-mentioned explanation, such as (Pt; Pd) be represent that Pt is independent, any one separately or in the mixing of Pt and Pd of Pd.
In addition, about above-mentioned preferred [(X), (Y)] combination, to the content of metal (X) and element (Y), be not particularly limited, as preferred content, following content can be enumerated.When [(X), (Y1), (Y2)] is [(Pt), (Ce), (P)], preferred Pt content is 0.01 ~ 3 quality %, Ce content is 0.01 ~ 3 quality %, P content is 0.1 ~ 3 quality %, and more preferably Pt content is 0.05 ~ 1 quality %, Ce content is 0.05 ~ 1 quality %, P content is 0.1 ~ 3 quality %.[(X), (Y1), (Y2)] is [(Pt; Pd), (Ce), (P)] when, preferred Pt content is 0.01 ~ 3 quality %, Pd content is 0.01 ~ 3 quality %, Ce content is 0.01 ~ 10 quality %, P content is 0.1 ~ 3 quality %, and more preferably Pt content is 0.05 ~ 1 quality %, Pd content is 0.05 ~ 1 quality %, Ce content is 0.05 ~ 1 quality %, P content is 0.1 ~ 3 quality %.When [(X), (Y)] is [(Pd), (Ce)], preferred Pd content is 0.01 ~ 1 quality %, Ce content is 0.01 ~ 10 quality %.When [(X), (Y1), (Y2)] is [(Pd), (Ce), (P)], preferred Pd content is 0.01 ~ 1 quality %, Ce content is 0.01 ~ 10 quality %, P content is 0.1 ~ 10 quality %.[(X), (Y1), (Y2)] is [(Pd; Ru), (Ce), (P)] when, preferred Pd content is 0.01 ~ 1 quality %, Ru content is 0.01 ~ 1 quality %, Ce content is 0.01 ~ 10 quality %, P content is 0.1 ~ 10 quality %.
When containing metal zeolite catalyst contains periodictable the 15th race's element (Y2), containing metal zeolite catalyst is preferably simultaneously containing Al.Now, the total of the Al composition contained by this catalyzer, by the worthwhile gauge of the Al atom intrinsic with zeolite, is preferably 1 ~ 10 quality %, is preferably 1 ~ 5 quality %.In addition, to the composition of Si and Al contained by the mesopore zeolite (Z1) forming this catalyzer, to be converted into the mol ratio (SiO of silicon-dioxide and aluminum oxide 2/ Al 2o 3) meter, be preferably the scope of 30 ~ 100.In addition, when this catalyzer contains P as periodictable the 15th race's element (Y2), to the composition of P and Al contained by this catalyzer, the scope of 0.1 ~ 1.0 is preferably in atomic molar ratio (P/Al).
Above-mentioned containing metal zeolite catalyst, except metal (X) and element (Y), can also contain basic metal (W).As basic metal (W), Li, Na, K, Rb, Cs can be illustrated.When containing basic metal (W), the amount of (W) is not particularly limited, but by the mol ratio (W/Al) relative to the Al in mesopore zeolite (Z1), is preferably the scope of 0.001 ~ 0.5.If this mol ratio (W/Al) is less than 0.001, then the acid amount of uncontrollable mesopore zeolite (Z1), can do nothing to help the side reaction suppressing gradualness.In addition, if this mol ratio (W/Al) is more than 0.5, then the sour quantitative change of mesopore zeolite (Z1) is few sometimes, and excessive activity reduces.
To the amount of the strong acid center that above-mentioned containing metal zeolite catalyst is held, be not particularly limited, but be preferably the scope of 10 ~ 1500 μm of ol relative to the every 1g of containing metal zeolite.In addition, to the amount of strong acid center, by ammonia desorption by heating method (NH 3-TPD) evaluate.About NH 3the measurement result of-TPD, transverse axis is set to desorption temperature, the longitudinal axis is set to ammonia desorption rate, point is painted desorption by heating curve as strength of acid and is distributed, only using meet on desorption by heating curve, appear at the peak within the scope of 250 DEG C ~ 800 DEG C acid site group as strong acid center, carry out quantitatively.
The form of above-mentioned containing metal zeolite catalyst is not particularly limited, powder directly can be used as catalyzer, also can adds tackiness agent etc. as required and make preformed catalyst.As preformed catalyst, can enumerate: aggegation block powder catalyzer is pressurizeed, compressed; Maybe this aggegation block is ground into the compressed moulding body of suitable particle diameter; By tabletting machine, compression solid is carried out to form the compression molding body of specific shape to powder catalyzer; In powder catalyzer, add tackiness agent, stabilizing agent, water etc. modulate mixing thing and the extrusion moulding body etc. extruded by described mixing thing by mould and obtain, but be not limited to these.
(modulator approach of containing metal zeolite catalyst)
Containing metal zeolite catalyst involved in the present invention, as long as meet described proterties, is not particularly limited the modulator approach of this catalyzer.The modulator approach of catalyzer involved in the present invention is roughly divided into following method (1), (2) and (3).
(1) on mesopore zeolite (Z1 '), metal (X) is held and as required from more than one the method that element (Y1) and element (Y2) are selected.
(2) by the oxide compound (Z2) being carried with the described element (Y1) of metal (X) or the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described zeolite (Z1 ') being carried with metal (X), carry out the method for physical mixed with mesopore zeolite (Z1 ').
(3) by the oxide compound (Z2) being carried with the element (Y1) of metal (X) or the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described zeolite (Z1 ') being carried with metal (X), carry out the method for physical mixed with the mesopore zeolite (Z1 ') being carried with element (Y2).
In addition, in method (2) and method (3), the part of metal (X) can hold on mesopore zeolite (Z1 ').In below illustrating, sometimes (Z1 '), (Z2) or (Z3) are called " carrier ".In addition, sometimes the catalyzer obtained by method (1) is called single supported catalyst, the catalyzer obtained by method (2) or method (3) is called overloading build catalyzer.
The present inventor confirms, in present embodiment, when being used in the containing metal zeolite catalyst of modulation in method (1), although be only carried with the catalyzer of metal (X) on mesopore zeolite (Z1 '), as long as use carbonic acid gas as oxidizing gas, just show the effect of present embodiment.In the catalyzer of modulation in method (1), preferably, mesopore zeolite (Z1 ') holds metal (X) and is selected from more than one containing metal zeolite catalyst of element (Y1) and element (Y2), be more preferably the containing metal zeolite catalyst being simultaneously carried with metal (X), element (Y1) and element (Y2) on mesopore zeolite (Z1 ').
As method (2) or the middle oxide compound (Z2) that use, element (Y1) of method (3), cerium oxide (IV), lanthanum trioxide, aluminium-cerium composite oxides etc. can be enumerated.In addition, as the inorganic solid compounds (Z3) used in method (2) or method (3), strontium titanate, lanthanum manganate, LaFe can be enumerated 0.57co 0.38pd 0.05o 3deng perovskite compound class; The phosphoric acid salts such as aluminum phosphate class, Cerium monophosphate class, lanthanum orthophosphate class; And silicon-dioxide, aluminum oxide, boehmite, plan boehmite, zirconium white, titanium oxide, magnesium oxide, amorphous silica-aluminum oxide, carbon, silicon carbide etc.In addition, the oxide compound (Z2) of the element (Y1) in method (2) and method (3) and inorganic solid compounds (Z3) also can have both the function as tackiness agent time shaping.When the oxide compound (Z2) or inorganic solid compounds (Z3) of element (Y1) hold metal (X), the carrier that preferred use lattice oxygen supply capacity is high, all if promote that metal (X) is to the carrier of the catalytic effect that the reforming reaction caused by oxidizing gas produces.As the solid that such lattice oxygen supply capacity is high, the perovskite compound such as strontium titanate, lanthanum manganate class, cerium oxide (IV), aluminium-cerium composite oxides etc. can be enumerated particularly, in them, be preferably as the cerium oxide (IV) of oxide compound (Z2) of element (Y1) and the perovskite compound as inorganic solid compounds (Z3).
In addition, the usage quantity of the oxide compound (Z2) of element (Y1) is not particularly limited, but in order to reduce the impact of rudimentary saturated hydrocarbons on contact decomposition reaction, relative to mesopore zeolite (Z1) 100 Quality Mgmt Dept, be preferably the scope of 0.1 ~ 20 Quality Mgmt Dept, more elect 1 ~ 10 Quality Mgmt Dept as.
In method (3), if be added with aluminum contained compound (A) in mesopore zeolite (Z1), then for a long time give light alkene class with high yield, therefore preferably.As the preferred addition manner of aluminum contained compound (A), the mode holding aluminum contained compound (A) on mesopore zeolite (Z1) except element (Y2) further or the mode etc. using aluminum contained compound (A) as oxide compound (Z2) or inorganic solid compounds (Z3) can be enumerated.About the addition of aluminum contained compound (A), using the total of aluminium component contained in containing metal zeolite catalyst as Al atom, be preferably the scope of 1 ~ 10 quality %, more have the scope electing 1 ~ 5 quality % as.As aluminum contained compound (A), only otherwise belong to the material of mesopore zeolite (Z1), then be not particularly limited, preferred use, for being selected from least one aluminum contained compound in boehmite, plan boehmite, aluminum oxide, aluminium salt and amorphous silica-aluminum oxide, is more preferably at least one compound being selected from boehmite and intending in boehmite.When such compound (A) is supported at mesopore zeolite (Z1), only hold a part of aluminum contained compound (A) sometimes, and do not hold other compositions, thus in the physical mixed body as mesopore zeolite (Z1) and aluminum contained compound situation.But present inventor confirms, although the amount of aluminum contained compound (A) is few, as long as be supported on mesopore zeolite (Z1), the effect of present embodiment will be played.In addition, in method (3), when adding aluminum contained compound (A), element (Y2) is preferably phosphorus (P).Described " physical mixed body " refers to the material modulated by the method for physical mixed.As described " method of physical mixed ", such as following physical mixed method (a) ~ (e) illustrated can be enumerated.
(holding)
Carrier holds metal (X), element (Y) and other elements, carrier is: the oxide compound (Z2) of mesopore zeolite (Z1), element (Y1), the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described zeolite (Z1) and their mixture.As the method for carrying out holding, known method can be used, be not particularly limited.Such as, known following method: make the solution containing the metal (X) of desired amount, element (Y) and other elements with the form of monomer or compound, and make the impregnation method that it contacts with oxide compound (Z2) or the inorganic solid compounds (Z3) of mesopore zeolite (Z1), element (Y1); Metal (X), element (Y) and other element gasification is made, as the vapour deposition method etc. that gas contacts with oxide compound (Z2) or the inorganic solid compounds (Z3) of mesopore zeolite (Z1), element (Y1) with the form of monomer or compound.More specifically, as impregnation method, filling perforation method, just wet impregnation (incipientwetness) method, Equilibrium Adsorption Method, evaporation drying method, spray-drying process, sedimentation and ion exchange method etc. can be enumerated, as vapour deposition method, chemical vapor deposition method, physical vapor deposition etc. can be enumerated.As preferred method, it is easier and without the need to the impregnation method of special device to enumerate operation.
As containing by the raw material of the compound of metal (X), element (Y) and other elements held, any compound that elemental metals, alloy, oxide compound, sulfide, nitride, carbide, boride, acid and salt etc. can obtain can be used.
As the raw material of metal (X), particularly, metal (X) is for enumerating palladous oxide (II) during Pd, acid chloride (II), Palladous chloride (II), Palladous nitrate (II), tetramminepalladous chloride (II), four ammonia palladium (II) nitrate etc., metal (X) is for enumerating platinum oxide (IV) during Pt, chlorine platinum (IV) acid, chlorination four ammonia platinum (II), platinum chloride (II), platinum chloride (IV) etc., metal (X) is for enumerating chlordene iridium (IV) acid during Ir, oxidation (IV) iridium, iridium chloride (III), iridium chloride (IV) etc., metal (X) is for enumerating ruthenium chloride (III) during Ru, ruthenium oxide (IV), ruthenium oxide (VIII), chlordene ruthenium (IV) sour potassium, chlordene ruthenium (IV) sour sodium, chlordene ruthenium (IV) sour ammonium, chlorination six ammonia ruthenium (III) etc., metal (X) is for enumerating rhodium acetate (II) during Rh, rhodium chloride (III), rhodium nitrate (III), rhodium oxide (III) etc., metal (X) is for enumerating nickel oxide (II) during Ni, nickelous nitrate (II), nickelous chloride (II), nickelous acetate (II) etc.
As containing by hold element (Y1), element (Y2) raw material, any compound that elemental metals, alloy, oxide compound, sulfide, nitride, carbide, boride, acid and salt etc. can obtain can be used.Particularly, element (Y1) is for enumerating cerium oxide (III), cerium oxide (IV), cerous acetate (III), cerous nitrate (III), Cerium II Chloride (III), cerous carbonate (III) etc. during Ce, element (Y2) is for enumerating ortho-phosphoric acid, metaphosphoric acid, Tripyrophosphoric acid, tetra-sodium, Secondary ammonium phosphate etc. during P.
Hold in operation about metal (X), element (Y) and other integrants, when needing the solution of the raw material made containing metal (X), groups of elements (Y) and other elements, the form of solution is not particularly limited.Particularly, can enumerate the solution of material dissolution in solvent, raw material is scattered in colloidal solution, suspension etc. in solvent equably, if stock dispersion in solvent and leave standstill, the slurry soln etc. that Shen falls, and their mixture etc.In addition, the solution of the multiple raw materials in the raw material containing metal (X), element (Y) and other elements can also be made.
To making metal (X), element (Y) and the material dissolution of other elements or the solvent of dispersion, be not particularly limited.Particularly, water can be enumerated, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, the water-soluble solvent classes such as acetic acid, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, the alcohols such as ethylene glycol, acetone, methylethylketone, the ketones such as mibk, Anaesthetie Ether, dimethyl ether, tetrahydrofuran (THF), 1, 3-diox, 1, the ethers such as 4-diox, ethyl acetate, the ester classes such as propyl acetate, methylene dichloride, chloroform, tetracol phenixin, 1, 1-ethylene dichloride, 1, 2-ethylene dichloride, 1, 1, 2, 2-tetrachloroethane, the halogenated hydrocarbons such as orthodichlorobenzene, benzene, toluene, xylene, sym-trimethylbenzene, naphthanes etc. are aromatic hydrocarbon based, acetonitrile, dimethyl sulfoxide (DMSO), dimethyl formamide etc., and their mixture.
In order to use metal (X), element (Y) and other integrants and in the above-mentioned solution made holding in operation, about the solution of the raw material containing metal (X), holding of utilizing impregnation method to carry out can be directly used in, also can carry out liquid-phase reduction process to metal (X) in the solution, the colloidal solution made containing metal (X) uses.The method of liquid-phase reduction process is not particularly limited, following method can be enumerated: add in the solution of the raw material containing metal (X) triethyl silicane, etc. Silicon Containing Hydrogen alkanes, the carboxylic-acids such as citric acid, Trisodium Citrate, xitix, the reductive agent such as sodium borohydride, hydrazine, and carry out the method that heats as required; The solution of the solvent of modulation containing reductibilities such as alcohols, carries out the method etc. heated as required.In addition, when carrying out liquid-phase reduction process, the protective materials such as polyvinylpyrrolidone, Dodecyl Mercaptan, sodium polyacrylate, methylcellulose gum, polyoxyethylene glycol can be added as required.
Can directly use as described above be carried with metal (X), element (Y) and other elements hold thing as catalyzer, or carry out modulation catalyst by carrying out physical mixed with other integrants, also can apply to burn till process, reduction treatment or apply these the two kinds rear uses of process.About burning till process, be not particularly limited, preferably can enumerate in atmosphere, carry out burning till process at the temperature of 250 ~ 800 DEG C, more preferably enumerate in atmosphere, carry out burning till process at the temperature of 350 ~ 600 DEG C, particularly preferably to enumerate in air, carry out burning till process at the temperature of 450 ~ 550 DEG C.About reduction treatment, be also not particularly limited, particularly, nitrogen atmosphere process, reductant solution spraying process etc. can be enumerated.Nitrogen atmosphere process is carried out as follows: by under the hydrogen atmosphere with hydrogen or inert gas dilution, heat as required.Reductant solution spraying process is carried out as follows: be dissolved in suitable solvent by reductive agents such as the carboxylic-acids such as Silicon Containing Hydrogen alkanes, citric acid, Trisodium Citrate, xitix, sodium borohydride, hydrazine such as triethyl silicanes as required, make solution, to holding thing spraying or dripping.
To the number of times holding operation, be not particularly limited, can be only once hold operation, also can be divided into more than twice repeatedly implement hold operation to modulate.When holding multiple integrant more than at twice, to the amount of the integrant held in each time, the order that combines and hold, be also not particularly limited.
(physical mixed)
When modulating overloading build catalyzer by described catalyzer modulator approach (2) and (3) middle physical mixed implemented, the method of physical mixed is not particularly limited, as preferred method, particularly, following method can be enumerated: the method that (a) all will carry out with the state of powder mixing as the solids component of blending objects each other, b () makes the solids component as blending objects be scattered in same solvent, after forming paste-like, carry out the method for evaporation drying, c solids component as blending objects is made formed body by (), the method that formed body is mixed with each other, d () makes as other layer the method that each key element as blending objects coexists separately, (e) the mixing undertaken by the method for described (a) ~ (c).About (b), also can modulate the formed body containing multiple solids component as blending objects, mix with other formed bodys.As the example of (d), can enumerate and pile up each composition successively on the reactor of fixed bed, form the method for the catalyst layer be made up of multilayer.Wherein, more there is the method electing (a), (b), (c) and (e) as, most preferably be the method for (a) and (b).
About the solvent used in the physical mixed method of described (b), be not particularly limited, can enumerate and such as carry out illustrative solvent as by metal (X), element (Y) and the material dissolution of other elements or the solvent of dispersion.
About the catalyzer utilizing aforesaid method to carry out physical mixed, directly can use as catalyzer, also can use after process, reduction treatment or these two kinds process are burnt till in applying.To burning till process, be not particularly limited, can preferably enumerate in atmosphere, carry out at the temperature of 250 ~ 800 DEG C burn till process, more preferably enumerate in atmosphere, carry out at the temperature of 350 ~ 600 DEG C burn till process, particularly preferably enumerate in atmosphere, carry out at the temperature of 450 ~ 550 DEG C burn till process.Reduction treatment is also not particularly limited, particularly, nitrogen atmosphere process, reductant solution spraying process etc. can be enumerated.Nitrogen atmosphere process is carried out as follows: by under the hydrogen atmosphere with hydrogen or inert gas dilution, heat as required.Reductant solution spraying process is carried out as follows: make the reductive agents such as the carboxylic-acids such as Silicon Containing Hydrogen alkanes, citric acid, Trisodium Citrate, xitix, sodium borohydride, hydrazine such as triethyl silicane be dissolved in suitable solvent as required, make solution, to holding thing spraying or dripping.
As the reactive mode for implementing manufacture method of the present invention, there are fixed-bed type, fluidized bed-type and moving-bed type etc., are not particularly limited, it is suitable that, easily replace the fixed-bed type of existing naphtha steam cracking.
(contact decomposition reaction)
(catalyst pretreatment)
To the containing metal zeolite catalyst for reacting, pre-treatment can be applied before the reaction as required.As pre-treatment, particularly, (1) can be enumerated for the purpose of the adsorbent removing catalyst surface, the non-active gas such as nitrogen and helium is circulated on one side carry out pyroprocessing, (2) are reduced to object with the metal ingredient of catalyzer, make hydrogen or dilute hydrogen circulation to carry out high temperature reduction process etc.Pretreated kind, number of times, order are not particularly limited, preferably apply the pre-treatment containing above-mentioned (2).
(supply of raw material and oxidizing gas)
The method of subtend catalyst layer base feed and oxidizing gas, be not particularly limited, contact equably with catalyst layer entirety with oxidizing gas to make raw material, the composition under all making normal temperature preferably by heating etc. to any method being liquid gasifies in advance, is all supplied to catalyst layer with the form of gas.In addition, to the admixture of raw material and oxidizing gas, be also not particularly limited, but be supplied to catalyst layer after preferably both being mixed.In addition, oxidizing gas also can generate as the reaction product of catalyst layer, and thus with catalyst layer contacts, but wish make a part at least oxidizing gas be supplied to catalyst layer after mixing with raw material.In addition, unstripped gas and oxidizing gas can supply respectively continuously, also can discontinuously supply.Such as, Ke Yishi, suspends the supply of unstripped gas, only oxidizing gas is supplied to catalyst layer, again unstripped gas is supplied to the method for catalyst layer.As the method for discontinuous supply gas, the first method and second method of following explanation can be enumerated.First method is, to the both sides of catalyst layer base feed gas and oxidizing gas, in this condition, suspends the supply of unstripped gas, and to catalyst layer supply oxidizing gas, and then unstripped gas is supplied to the method for catalyst layer.Second method is, to catalyst layer only base feed gas, in this condition, suspends the supply of unstripped gas, and supplies oxidizing gas, then, again unstripped gas is supplied to the method for catalyst layer.In second method, when again unstripped gas being supplied to catalyst layer, can together with oxidizing gas base feed gas, also can only base feed gas.
(temperature of reaction)
Contact decomposition reaction is generally thermo-negative reaction, therefore temperature of reaction is higher, thermodynamically more favourable to the carrying out of reaction, but the high temperature of more than 800 DEG C general in petroleum naphtha thermolysis is harsh condition to zeolite catalyst, and its activity can reduce at short notice.On the other hand, need do not hindering the generation of unsaturated hydrocarbons class and reacted by the high temperature that oxidizing gas can remove coke and the such degree of precursors of coke.Owing to restricting by these, the temperature of catalyst layer during contact decomposition reaction, is preferably the scope of 500 ~ 750 DEG C, more has the scope electing 600 ~ 700 DEG C as.In addition, the temperature of reaction during contact decomposition reaction of the rudimentary saturated hydrocarbons such as petroleum naphtha of the present invention refers to the temperature of catalyst layer, and the temperature of catalyst layer refers to the medial temperature of catalyst layer entirety.But, owing to heating from outside, near the reactor wall that local temperature is high, be subject to the impact of the heat absorption produced by decomposition reaction large and cause the position that temperature is low especially, departing from the medial temperature of catalyst layer entirety sometimes significantly.Therefore, in order to measure the medial temperature of catalyst layer entirety, need the position selecting not to be in particular surroundings to measure.As concrete measuring method, can enumerate, such as, when with fixed bed type reactor, the immediate vicinity in reaction tubes cross section measures the axial two ends of reaction tubes of catalyst layer and the temperature of central part, the method etc. that the temperature of getting 3 places is averaged.
(reaction pressure)
In manufacture method of the present invention, saturated hydrocarbons is converted to decomposition reaction to unsaturated hydro carbons, therefore, can say that the dividing potential drop of raw material is higher, thermodynamically more unfavorable to the carrying out of reaction.And if the dividing potential drop of raw material is too low, then it seems from the viewpoint of economy, and not preferred.Therefore, the dividing potential drop (referring to the total of the dividing potential drop of total overall reaction resultant when raw material is mixture) of raw material is preferably in the scope of 0.01 ~ 0.20MPa.Total head in reactor is not particularly limited, but is preferably in the scope of 0.1 ~ 1.0MPa.
(feed rate of raw material and oxidizing gas)
To the feed rate of raw material and oxidizing gas, be not particularly limited, but in order to the coke being come above to a certain extent by oxidizing gas generates inhibition, make the deterioration of the catalyzer caused by oxidizing gas simultaneously, the brought impact of excessively carrying out of reaction minimizes, it is desirable to the ratio of the feed rate of oxidizing gas relative to raw material supplying amount to suppress in specific scope.As embodiment, the volume (V shared by gas of described oxidizing gas (S) at the reaction temperatures s) relative to raw material under temperature of reaction (O) gas shared by volume (V o) ratio (V s/ V o) be preferably 0.01 ~ 2 scope, more have the scope electing 0.01 ~ 1 as, most preferably be the scope of 0.1 ~ 1.In addition, when the mixtures such as petroleum naphtha are raw material, molecular weight is indefinite, therefore, molecular-weight average is assumed to be identical with the molecular weight of normal hexane 86 to calculate V o, and V oand V sall with catalyst layer contacts before gas volume calculate.
(duration of contact)
To the duration of contact of raw material and catalyzer, be not particularly limited, but be preferably the duration of contact of following degree: sufficient reacting carries out and do not produce the coking hindering reaction to carry out degree.Particularly, what preferably define in following formula (1) is 0.1 ~ 30h relative to the weight-space velocity (WHSV) of mesopore zeolite (Z1) composition quality -1scope carry out, more preferably at 0.1 ~ 15h -1scope carry out.
(WHSV [h -1])=(raw material supplying amount [g/h])/(quality [g] of mesopore zeolite (Z1) composition) ... (1)
Embodiment
Below, by embodiment, the present invention is further elaborated, but the present invention is not by any restriction of these embodiments.
[catalyzer modulation example 1] containing metal zeolite catalyst (Ru/CeO 2+ P/ZSM5) modulation
Cerium oxide (IV) (StremChemicals Inc.) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this cerium oxide (IV)/water, distilled water chlorination six ammino ruthenium (III) (Sigma-Aldrich's system) of 1.0g being dissolved in 100ml is added gradually and the solution obtained in room temperature, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, use 50 DEG C of water-baths to carry out heating to obtained mixed solution and under reduced pressure carry out evaporation drying.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate the Ru/CeO containing the Ru of 330 μm of ol relative to the every 1.0g of cerium oxide (IV) 2.
By using the SiO as mesopore zeolite 2/ Al 2o 3mol ratio is the NH of 30 4 +type MFI zeolite (ZeolystInternational Inc.) in atmosphere, burn till 4 hours, modulation SiO at the temperature of 500 DEG C 2/ Al 2o 3mol ratio is the H of 30 +the MFI zeolite catalyst (H-ZSM5) of type.By SiO 2/ Al 2o 3mol ratio be 30 H-ZSM5 (10g) impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this H-ZSM5/ water, add the distilled water Secondary ammonium phosphate of 0.85g (with Guang Chun medicine Inc.) being dissolved in 100ml and the solution obtained gradually in room temperature, after stirring 2 hours at 50 DEG C, at room temperature stir 2 hours further.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours, modulation P/ZSM5 at the temperature of 500 DEG C.
Use mortar, with the state of powder directly by P/ZSM5 (2.5g) and Ru/CeO 20.24g fully carries out physical mixed, modulation Ru/CeO 2+ P/ZSM5.
[catalyzer modulation example 2] containing metal zeolite catalyst (Pd/CeO 2+ P/ZSM5) modulation
Cerium oxide (IV) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this cerium oxide (IV)/water, at room temperature add the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g being dissolved in 100ml gradually and the solution obtained, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate the Pd/CeO relative to the Pd containing 330 μm of ol in the every 1.0g of cerium oxide (IV) 2.
Use mortar, with the state of powder directly by P/ZSM5 (2.5g) and Pd/CeO 20.24g carries out physical mixed fully, modulation Pd/CeO 2+ P/ZSM5.
[catalyzer modulation example 3] containing metal zeolite catalyst (Ni/CeO 2+ P/ZSM5) modulation
Cerium oxide (IV) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this cerium oxide (IV)/water, the distilled water nickelous nitrate of 0.96g (II) muriate hexahydrate (with light pure pharmaceutical worker's industry Inc.) being dissolved in 100ml is added gradually and the solution obtained in room temperature, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate the Ni/CeO containing the Ni of 330 μm of ol relative to the every 1.0g of cerium oxide (IV) 2.
Use mortar, with the state of powder directly by P/ZSM5 (2.5g) and Ni/CeO 20.24g carries out physical mixed fully, modulation Ni/CeO 2+ P/ZSM5.
[catalyzer modulation example 4] containing metal zeolite catalyst (Pd/CeAlO 3+ P/ZSM5) modulation
By aluminium cerium oxide (AluminumCeriumOxide) (CeAlO 3, Sigma-Aldrich's system) 10g impregnated in the distilled water of 100ml, under reduced pressure, carries out degassed in room temperature.To this CeAlO 3(IV) mixed solution of/water, adds the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g being dissolved in 100ml and the solution obtained gradually in room temperature, after stirring 2 hours, stirs 2 hours further in room temperature at 50 DEG C.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to CeAlO 3(IV) every 1.0g contains the Pd/CeAlO of the Pd of 330 μm of ol 3.
Use mortar, directly P/ZSM5 (2.5g) and Pd/CeAlO30.24g is fully carried out ground physical mixed with the state of powder, modulation Pd/CeAlO3+P/ZSM5.
[catalyzer modulation example 5] containing metal zeolite catalyst (Pd/LaMnO 3+ P/ZSM5) modulation
25 quality % ammoniacal liquor (with light pure pharmaceutical worker's industry Inc.) 460ml is mixed with distilled water 140ml, modulates 19 quality % ammoniacal liquor 600ml.While stir the ammoniacal liquor modulated, while dripped the distilled water lanthanum nitrate hexahydrate (with light pure pharmaceutical worker's industry Inc.) of 8.7g and the manganous nitrate hexahydrate (Northeast chemical company system) of 5.7g being dissolved in 200ml through 1 hour and the solution obtained, stir further on one side in room temperature, while leave standstill 1 hour, then stop being stirred in room temperature and leave standstill 0.5 hour, carry out slaking.Filter the mixture that obtains, after dried screening, pulverize with mortar, in atmosphere, burn till 5 hours, modulation LaMnO at the temperature of 750 DEG C 3.
By LaMnO 310g impregnated in the distilled water of 100ml, under reduced pressure, carries out degassed in room temperature.To this LaMnO 3the mixed solution of/water, adds the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g being dissolved in 100ml and the solution obtained gradually in room temperature, after stirring 2 hours, stirs 2 hours further in room temperature at 50 DEG C.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to LaMnO 3every 1.0g contains the Pd/LaMnO of the Pd of 330 μm of ol 3.
Use mortar, with the state of powder directly by P/ZSM5 (2.5g) and Pd/LaMnO 30.24g fully carries out ground physical mixed, modulation Pd/LaMnO 3+ P/ZSM5.
[embodiment 1] activity rating: synthetic naphtha decomposition reaction
Reagent mix become Skellysolve A 29 quality %, normal hexane 14 quality %, 2-methylpentane 14 quality %, octane 29 quality %, methylcyclohexane 7 quality %, hexanaphthene 7 quality % and fully stir, using obtained liquid as synthetic naphtha.
To the Ru/CeO of modulation in catalyzer modulation example 1 2+ P/ZSM5 catalyzer carries out pressurizeing, compressing, and makes aggegation block, and pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out synthetic naphtha decomposition reaction, thus carries out activity rating.The Ru/CeO of 0.86g is filled in reaction tubes 2+ P/ZSM5, as catalyzer, under atmospheric pressure, makes nitrogen be circulated in reactor with the flow of 50Ncc/min, while be warming up to 600 DEG C.At the temperature of 600 DEG C, with the flow of 50Ncc/min, hydrogen is circulated in reactor, while carry out the reduction treatment of 1 hour.After reduction treatment, at the temperature of 600 DEG C, circulated gases is switched to nitrogen from hydrogen, make it be circulated in reactor with the flow of 50Ncc/min, while carry out the pre-treatment of 1.5 hours, be warming up to 650 DEG C as temperature of reaction.At the temperature of 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the synthetic naphtha of raw material to be supplied to the flow of 0.75g/h with the flow of 7.5g/h and water vapour and to carry out reaction tubes, and pressurization is to make total head become 0.15MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, at the reaction temperatures as raw material synthetic naphtha gas with as the volume ratio V of the water vapour of oxidizing gas s/ V obe 0.48, the dividing potential drop of synthetic naphtha gas is 0.10MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 1.
[embodiment 2]
About the Pd/CeO of modulation in catalyzer modulation example 2 2+ P/ZSM5 catalyzer, except filling the Pd/CeO of 0.86g 2+ P/ZSM5, as beyond catalyzer, operates similarly to Example 1, carries out activity rating by synthetic naphtha decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 1.
[embodiment 3]
About the Pd/CeO of modulation in catalyzer modulation example 2 2+ P/ZSM5 catalyzer, except water vapour feed rate is set to 3.8g/h, total head is set to except 0.35MPa, and operating similarly to Example 1, is 10h at the WHSV relative to mesopore zeolite quality -1, V s/ V obe under the condition of 2.4, carry out activity rating by synthetic naphtha decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 1.
[embodiment 4]
About the Ni/CeO of modulation in catalyzer modulation example 3 2+ P/ZSM5 catalyzer, except filling the Ni/CeO of 0.86g 2+ P/ZSM5, as beyond catalyzer, operates similarly to Example 1, carries out activity rating by synthetic naphtha decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 1.
[embodiment 5]
About the Pd/CeAlO of modulation in catalyzer modulation example 4 3+ P/ZSM5 catalyzer, except filling the Pd/CeAlO of 0.86g 3+ P/ZSM5, as beyond catalyzer, operates similarly to Example 1, carries out activity rating by synthetic naphtha decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 1.
[embodiment 6]
About the Pd/LaMnO of modulation in catalyzer modulation example 5 3+ P/ZSM5 catalyzer, except filling the Pd/LaMnO of 0.86g 3+ P/ZSM5, as beyond catalyzer, operates similarly to Example 1, carries out activity rating by synthetic naphtha decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 1.
[comparative example 1]
In atmosphere, at the temperature of 500 DEG C, using the SiO as mesopore zeolite 2/ Al 2o 3mol ratio is the NH of 500 4 +type MFI zeolite (Sued-ChemieCatalysts Inc.) burns till 4 hours, modulates SiO thus 2/ Al 2o 3mol ratio is the H of 500 +type MFI zeolite catalyst (H-ZSM5).
To SiO 2/ Al 2o 3mol ratio be 500 H-ZSM5 catalyzer carry out pressurizeing, compressing, make aggegation block, pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out synthetic naphtha decomposition reaction, thus carry out activity rating.The SiO of 0.75g is filled in reaction tubes 2/ Al 2o 3mol ratio be the H-ZSM5 of 500 as catalyzer, under atmospheric pressure, with the flow of 50Ncc/min, nitrogen is circulated in reactor, while be warming up to 650 DEG C of temperature of reaction.At the temperature of 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the synthetic naphtha of raw material is supplied to reaction tubes with the flow of 7.5g/h, and carry out pressurizeing to make total head become 0.10MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, the synthetic naphtha gas as raw material at the reaction temperatures and the volume ratio V as the water vapour of oxidizing gas s/ V obe 0, the dividing potential drop of synthetic naphtha gas is 0.11MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in table 1.
[comparative example 2]
About the P/ZSM5 catalyzer of modulation in catalyzer modulation example 1, except filling the P/ZSM5 of 0.79g as except catalyzer, operating in the same manner as comparative example 1, carrying out activity rating by synthetic naphtha decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 1.
[comparative example 3]
To the Ru/CeO of modulation in catalyzer modulation example 1 2+ P/ZSM5 catalyzer carries out pressurizeing, compressing, and makes aggegation block, and pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carries out activity rating.The Ru/CeO of 0.86g is filled in reaction tubes 2+ P/ZSM5, as catalyzer, under atmospheric pressure, with the flow of 50Ncc/min makes nitrogen be circulated in reactor, while be warming up to 600 DEG C.At the temperature of 600 DEG C, with the flow of 50Ncc/min, hydrogen is circulated in reactor, while carry out the reduction treatment of 1 hour.After reduction treatment, at 600 DEG C, circulated gases is switched to nitrogen from hydrogen, make it be circulated in reactor with the flow of 50Ncc/min, carry out the pre-treatment of 1.5 hours, while be warming up to 650 DEG C of temperature of reaction.At the temperature of 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the synthetic naphtha of raw material is supplied to reaction tubes with the flow of 7.5g/h, and carry out pressurizeing to make total head become 0.10MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, the synthetic naphtha gas as raw material at the reaction temperatures and the volume ratio V as the water vapour of oxidizing gas s/ V obe 0, the dividing potential drop of synthetic naphtha gas is 0.11MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 1.
[table 1]
Use and under water vapour adding conditional, implement the result of the embodiment 1 ~ 6 of synthetic naphtha decomposition reaction containing Pd or Ru as the P/ZSM5 catalyzer of integrant, with implement under the non-adding conditional of water vapour synthetic naphtha decomposition reaction comparative example 1 ~ 3 result compared with, after synthetic naphtha decomposition reaction starts, the ethene+propene yield of 13 hours and 21 hours is all high.In addition, at V s/ V obe the result of embodiment 1,2 and 4 ~ 6 implementing under the condition of less than 2.0 to react, and at V s/ V obe that the result of embodiment 3 implementing under the condition of more than 2.0 to react is compared, after synthetic naphtha decomposition reaction starts, the ethene+propene yield of 13 hours and 21 hours is all high.And then, use the result of embodiment 1,2,4,5 of the catalyzer containing Ce, with use containing belong to periodictable the 3rd race's element La but not containing the Pd/LaMnO of Ce 3the result of the embodiment 6 of+P/ZSM5 catalyzer is compared, and after synthetic naphtha decomposition reaction starts, the ethene+propene yield of 13 hours and 21 hours is all high.That is, specify that the containing metal zeolite catalyst containing Pd or Ru, when water vapour adds reaction conditions use, in catalyst performance and catalyst life these two aspects excellence, wherein, at V s/ V obe more excellent when using under the condition of less than 2.0, excellent further when particularly containing zeolite containing Ce as the metal of integrant.
[catalyzer modulation example 6] containing metal zeolite catalyst (Pd/CeO 2+ Al-P/ZSM5) modulation
Boehmite (with light pure pharmaceutical worker industry Inc.) 0.67g and Secondary ammonium phosphate (with light pure pharmaceutical worker's industry Inc.) 1.7g is added in the distilled water of 100ml, in stirring at room temperature, in the mixed solution obtained thus, be added on the SiO of modulation in catalyzer modulation example 1 2/ Al 2o 3mol ratio is the H-ZSM5 (10g) of 30, further in stirring at room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, 5 hours are burnt till at the temperature of 600 DEG C, and then, while make the mixed gas flow of nitrogen and water vapour pass to the flow becoming nitrogen 160Ncc/min and water vapour 40Ncc/min, while carry out the steam treatment of 24 hours at 700 DEG C, modulation Al-P/ZSM5.
Use mortar, with the state of powder directly by Al-P/ZSM5 (2.7g) and the Pd/CeO modulating the 0.23g modulated in example 2 at catalyzer 2carry out physical mixed fully, modulation Pd/CeO 2+ Al-P/ZSM5.
[catalyzer modulation example 7] containing metal zeolite catalyst (Ru/CeO 2+ Al-P/ZSM5) modulation
Except being used in the Ru/CeO of modulation in catalyzer modulation example 1 20.23g replaces Pd/CeO 2beyond 0.23g, modulate in the same manner as example 6 with catalyzer and operate, modulation Ru/CeO 2+ Al-P/ZSM5.
[catalyzer modulation example 8] containing metal zeolite catalyst (Pd-Pt/CeO 2+ Al-P/ZSM5) modulation
Cerium oxide (IV) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this cerium oxide (IV)/water, the distilled water and the solution obtained that platinum chloride (IV) the sour hexahydrate (with light pure pharmaceutical worker's industry Inc.) of four ammonia palladium (II) the muriate monohydrates of 0.44g and 0.85g are dissolved in 100ml is added gradually in room temperature, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate the Pd-Pt/CeO that every 1.0g contains the Pt of Pd and the 165 μm ol of 165 μm of ol 2.
Use mortar, with the state of powder directly by the Al-P/ZSM5 (2.7g) of modulation in catalyzer modulation example 6 and Pd-Pt/CeO 20.23g carries out physical mixed fully, modulation Pd-Pt/CeO 2+ Al-P/ZSM5.
[embodiment 7] activity rating: normal hexane decomposition reaction
To the Pd/CeO of modulation in catalyzer modulation example 6 2+ Al-P/ZSM5 catalyzer carries out pressurizeing, compressing, and makes aggegation block, and pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carries out activity rating.Pd/CeO is filled in reaction tubes 2+ Al-P/ZSM5 (0.94g), as catalyzer, under atmospheric pressure, makes nitrogen be circulated in reactor with the flow of 50Ncc/min, while be warming up to 400 DEG C.At the temperature of 400 DEG C, make hydrogen be circulated in reactor with the flow of 50Ncc/min, carry out the reduction treatment of 1 hour.After reduction treatment, at 400 DEG C, circulated gases is switched to nitrogen from hydrogen, make it be circulated in reactor with the flow of 50Ncc/min, while carry out the pre-treatment of 1.5 hours, be warming up to 650 DEG C of temperature of reaction.At the temperature of 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and water vapour with the flow of 0.75g/h, and make total head become 0.10MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the water vapour of oxidizing gas s/ V obe 0.48, the dividing potential drop of normal hexane gas is 0.068MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 2.
[embodiment 8]
About the Ru/CeO of modulation in catalyzer modulation example 7 2+ Al-P/ZSM5 catalyzer, except filling the Ru/CeO of 0.94g 2+ Al-P/ZSM5, as beyond catalyzer, operates similarly to Example 7, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 2.
[embodiment 9]
About the Pd-Pt/CeO of modulation in catalyzer modulation example 8 2+ Al-P/ZSM5 catalyzer, except filling the Pd-Pt/CeO of 0.94g 2+ Al-P/ZSM5, as beyond catalyzer, operates similarly to Example 7, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 2.
[comparative example 4]
The Al-P/ZSM5 catalyzer of modulation in catalyzer modulation example 6 is pressurizeed, compressed, make aggegation block, pulverized by this aggegation block, whole grain becomes 0.25mm ~ 0.50mm particle diameter, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carry out activity rating.In reaction tubes, fill the Al-P/ZSM5 of 0.87g as catalyzer, under atmospheric pressure, with the flow of 50Ncc/min, nitrogen is circulated in reactor, while be warming up to 650 DEG C of temperature of reaction.At the temperature of 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, get and the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and water vapour with the flow of 0.75g/h by generation, and make total head become 0.10MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the water vapour of oxidizing gas s/ V obe 0.48, the dividing potential drop of normal hexane gas is 0.068MPa.After reaction starts, after a predetermined time, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 2.
[table 2]
About water vapour adding conditional (V s/ V o=0.48) the normal hexane decomposition reaction under, Pd, Ru or Pd-Pt mixture is supported at cerium oxide (IV) and goes up and the result of carrying out the embodiment 7 ~ 9 of the containing metal zeolite catalyst of physical mixed with Al-P/ZSM5 by use, with use not containing metal (X) as the comparative example 4 of the Al-P/ZSM5 catalyzer of integrant result compared with, all high at the ethene+propene yield of reaction beginning 1 hour, 19 hours and 29 hours.That is, specify that under water vapour adding conditional, containing the containing metal zeolite catalyst of Pd, Ru or Pd-Pt mixture as metal (X), compared with the zeolite catalyst of not containing metal (X), catalyst performance and catalyst life these two aspects excellent.
[catalyzer modulation example 9] containing metal zeolite catalyst (Pd-Ru/CeO 2+ Al-P/ZSM5) modulation
Cerium oxide (IV) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this cerium oxide (IV)/water, the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g and chlorination six ammino ruthenium (III) of 1.0g being dissolved in 100ml is added gradually and the solution obtained at normal temperature, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate the Pd-Ru/CeO containing the Ru of Pd and the 330 μm ol of 330 μm of ol relative to the every 1.0g of cerium oxide (IV) 2.
Except using Pd-Ru/CeO 20.23g replaces Pd/CeO 2beyond 0.23g, modulate in the same manner as example 6 with catalyzer and operate, modulation Pd-Ru/CeO 2+ Al-P/ZSM5.
[embodiment 10] activity rating: normal hexane decomposition reaction
About the Pd-Ru/CeO of modulation in catalyzer modulation example 9 2+ Al-P/ZSM5 catalyzer, except filling the Pd-Ru/CeO of 0.94g 2+ Al-P/ZSM5, as beyond catalyzer, operates similarly to Example 7, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 3.
[embodiment 11]
Respectively to the Pd-Ru/CeO of modulation in the Al-P/ZSM5 modulated in catalyzer modulation example 6 and catalyzer modulation example 9 2carry out pressurizeing, compressing, make aggegation block, pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm.First the Al-P/ZSM5 (0.87g) through whole grain is filled in reaction tubes, then starts the Pd-Ru/CeO of the whole grain of wadding warp 20.075g, thus make Pd-Ru/CeO 2layer and Al-P/ZSM5 catalyst layer separately conduct other layer individual coexist, with raw material successively with Pd-Ru/CeO 2the mode of layer, Al-P/ZSM5 layer contact configures.Use the reactor of such catalyst filling, operate similarly to Example 7, carry out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 3.
[table 3]
About using containing Pd and Ru as metal (X) as the Pd-Ru/CeO of integrant 2+ Al-P/ZSM5 physical mixed catalyzer at water vapour adding conditional (V s/ V o=0.48) the normal hexane decomposition reaction carried out under, uses Pd-Ru/CeO with the state of powder 2carry out the result of the embodiment 10 of the catalyzer of physical mixed with Al-P/ZSM5 each other, and make Pd-Ru/CeO 2the result of the embodiment 11 that layer and Al-P/ZSM5 layer coexist as other layer individual separately, compared with the result of the comparative example 4 of table 2, it is all high to react the ethene+propene yield starting latter 1 hour, 19 hours and 29 hours.That is, specify that under water vapour adding conditional, when composition containing metal (X) and the composition containing mesopore zeolite are carried out the catalyzer of physical mixed by use, make the physical mixed catalyzer that each composition coexists as other layer individual, compared with the zeolite catalyst of not containing metal (X), catalyst performance and catalyst life these two aspects excellence, with the physical mixed catalyzer that each composition is mixed with each other by the state of powder, catalyst performance and catalyst life these two aspects more excellent.
The modulation of [catalyzer modulation example 10] containing metal zeolite catalyst (Pt-Ce/Al-P/ZSM5)
To the Al-P/ZSM5 (2.0g) of modulation in catalyzer modulation example 6, in the mode that Pt atom becomes 0.50 quality %, the loading amount of Ce to become 0.30 quality % with Ce atom, platinum chloride (IV) sour hexahydrate and cerous nitrate (III) hexahydrate (with light pure pharmaceutical worker industry Inc.) are dissolved in appropriate distilled water in the loading amount of Pt, use this solution to be held by first wet impregnation (incipientwetness) method.The powder that drying is obtained, drip the hydrazine aqueous solution by the 0.13mol/L that hydrazine monohydrate (with light pure pharmaceutical worker's industry Inc.) is dissolved in distilled water to modulate, after Pt liquid-phase reduction, filter cleaning with distilled water, 100 DEG C of dryings 24 hours, modulation Pt-Ce/Al-P/ZSM5.
[embodiment 12] activity rating: normal hexane decomposition reaction
The Pt-Ce/Al-P/ZSM5 of modulation in catalyzer modulation example 10 is pressurizeed, compressed, make aggegation block, pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carry out activity rating.In reaction tubes, fill the Pt-Ce/Al-P/ZSM5 of 0.91g as catalyzer, under atmospheric pressure, nitrogen is circulated in reactor, while be warming up to 650 DEG C of temperature of reaction.At 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and water vapour with the flow of 2.3g/h, and make total head become 0.10MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the water vapour of oxidizing gas s/ V obe 1.4, the dividing potential drop of normal hexane gas is 0.041MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 4.
[comparative example 5]
About the Al-P/ZSM5 catalyzer modulated in catalyzer modulation example 6, except filling the Al-P/ZSM5 of 0.87g as except catalyzer, operating similarly to Example 12, being evaluated by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 4.
[embodiment 13] activity rating: normal hexane decomposition reaction
To the Pd/CeO of modulation in catalyzer modulation example 6 2+ Al-P/ZSM5 catalyzer carries out pressurizeing, compressing, and makes aggegation block, and pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carries out activity rating.Pd/CeO is filled in reaction tubes 2+ Al-P/ZSM5 (2.4g), as catalyzer, under atmospheric pressure, makes nitrogen be circulated in reactor with the flow of 50Ncc/min, while be warming up to 400 DEG C.At 400 DEG C, make hydrogen be circulated in reactor with the flow of 50Ncc/min, carry out the reduction treatment of 1 hour.After reduction treatment, at 400 DEG C, circulated gases is switched to nitrogen from hydrogen, make it be circulated in reactor with the flow of 50Ncc/min, while carry out the pre-treatment of 1.5 hours, be warming up to 635 DEG C of temperature of reaction.At the temperature of 635 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and by water vapour with the flow of 3.0g/h, and make total head become 0.10MPa, make reaction start under the following conditions, described condition is: be 4.0h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the water vapour of oxidizing gas s/ V obe 1.9, the dividing potential drop of normal hexane gas is 0.034MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 4.
[comparative example 6]
The Al-P/ZSM5 catalyzer of modulation in catalyzer modulation example 6 is pressurizeed, compressed, make aggegation block, this aggegation block is pulverized, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carries out activity rating.In reaction tubes, fill the Al-P/ZSM5 of 2.2g as catalyzer, under atmospheric pressure, with the flow of 50Ncc/min, nitrogen is circulated in reactor, while be warming up to 635 DEG C of temperature of reaction.At the temperature of 635 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and by water vapour with the flow of 3.0g/h, and make total head become 0.10MPa, make reaction start under the following conditions, described condition is: be 4.0h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the water vapour of oxidizing gas s/ V obe 1.9, the dividing potential drop of normal hexane gas is 0.034MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 4.
[table 4]
About adding water vapour to V s/ V othe normal hexane decomposition reaction carried out under the condition of=1.4, use containing the result of Pt as the embodiment 12 of the Pt-Ce/Al-P/ZSM5 catalyzer of metal (X), with use not containing metal (X) Al-P/ZSM5 catalyzer comparative example 5 result compared with, ethene+propene yield that reaction starts latter 9 hours and 17 hours is all high.In addition, about adding water vapour to V s/ V othe normal hexane decomposition reaction carried out under the condition of=1.9, uses containing the Pd/CeO of Pd as metal (X) 2the result of the embodiment 13 of+Al-P/ZSM5 catalyzer, with use not containing metal (X) Al-P/ZSM5 catalyzer comparative example 6 result compared with, ethene+propene yield that reaction starts latter 1 hour, 11 hours and 27 hours is also all high.
The modulation of [catalyzer modulation example 11] containing metal zeolite catalyst (P/Pt-Zn/ZSM5)
By using the SiO as mesopore zeolite 2/ Al 2o 3mol ratio is the NH of 61 4 +type MFI zeolite in atmosphere, burn till 4 hours, modulation SiO at the temperature of 500 DEG C 2/ Al 2o 3mol ratio is the H of 50 +type MFI zeolite catalyst (H-ZSM5).To SiO 2/ Al 2o 3mol ratio is the H-ZSM5 (2.0g) of 50, in the mode that Pt atom becomes 0.50 quality %, the loading amount of Zn to become 0.30 quality % with Zn atom, platinum chloride (IV) sour hexahydrate and zinc chloride (with light pure pharmaceutical worker industry Inc.) are dissolved in appropriate distilled water in the loading amount of Pt, use this solution, held by incipient wetness (incipientwetness) method.The powder that drying is obtained, drip the hydrazine aqueous solution by the 0.13mol/L that hydrazine monohydrate (with light pure pharmaceutical worker's industry Inc.) is dissolved in distilled water to modulate, after Pt liquid-phase reduction, filter cleaning with distilled water, 100 DEG C of dryings 24 hours, modulation Pt-Zn/ZSM5.To impregnation 85% phosphate aqueous solution in obtained Pt-Zn/ZSM5 (with light pure pharmaceutical worker's industry Inc.) 0.087g, after carrying out drying, in atmosphere, burn till 10 hours, modulation P/Pt-Zn/ZSM5 at the temperature of 650 DEG C.
[embodiment 14] activity rating: normal hexane decomposition reaction
The P/Pt-Zn/ZSM5 catalyzer of modulation in catalyzer modulation example 11 is pressurizeed, compressed, make aggegation block, pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carry out activity rating.In reaction tubes, fill P/Pt-Zn/ZSM5 (1.1g) as catalyzer, under atmospheric pressure, nitrogen is circulated in reactor, while be warming up to 650 DEG C of temperature of reaction.At 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and water vapour with the flow of 0.75g/h, and make total head become 0.10MPa, make reaction start under the following conditions, described condition is: be 6.8h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the water vapour of oxidizing gas s/ V obe 0.48, the dividing potential drop of normal hexane gas is 0.068MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 5.
[comparative example 7]
To the SiO of modulation in catalyzer modulation example 11 2/ Al 2o 3mol ratio is the H-ZSM5 (2.0g) of 61, impregnation 85% phosphate aqueous solution (with light pure pharmaceutical worker's industry Inc.) 0.087g, after drying, in atmosphere, burns till 10 hours, modulation P/ZSM5 at the temperature of 650 DEG C.Pressurize to obtained powder, compress, make aggegation block, pulverized by this aggegation block, whole grain uses after becoming the particle diameter of 0.25mm ~ 0.50mm in the reaction.
About modulated SiO 2/ Al 2o 3mol ratio is the P/ZSM5 of 61, except filling P/ZSM5 (1.1g) as except catalyzer, operating similarly to Example 14, being evaluated by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 5.
[table 5]
About water vapour adding conditional (V s/ V o=0.48) the normal hexane decomposition reaction under, use containing the result of Pt as the embodiment 14 of the P/Pt-Zn/ZSM5 catalyzer of metal (X), with use not containing metal (X) P/ZSM5 catalyzer comparative example 7 result compared with, it is high that reaction starts the ethene+propene yield of latter 41 hours.
The modulation of [catalyzer modulation example 12] containing metal zeolite catalyst (Ru/ZSM5)
By the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio be 500 H-ZSM5 (5.0g) impregnated in 20ml distilled water, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this zeolite/water, at room temperature drip distilled water monobutyltin trichloride six ammino ruthenium (III) of 0.051g being dissolved in 80ml and the solution obtained, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate the Ru/ZSM5 that every 1.0g contains the Ru of 330 μm of ol.
[catalyzer modulation example 13] containing metal zeolite catalyst (Pd/Al 2o 3+ H-ZSM5) modulation
Gama-alumina (sumitomo chemical company system) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this gama-alumina/water, at room temperature add the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g being dissolved in 100ml and the solution obtained gradually, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with to 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to every Al 2o 31.0g contains the Pd/Al of the Pd of 330 μm of ol 2o 3.
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio is H-ZSM5 (2.5g) and the Pd/Al of 500 2o 30.25g carries out physical mixed fully, modulation Pd/Al 2o 3+ H-ZSM5.
[catalyzer modulation example 14] containing metal zeolite catalyst (Pd/SiO 2+ H-ZSM5) modulation
Aerosil (Sigma-Aldrich's system) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this aerosil/water, at room temperature add the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g being dissolved in 100ml and the solution obtained gradually, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to SiO 2every 1.0g contains the Pd/SiO of the Pd of 330 μm of ol 2.
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio is H-ZSM5 (2.5g) and the Pd/SiO of 500 20.25g carries out physical mixed fully, modulation Pd/SiO 2+ H-ZSM5.
[catalyzer modulation example 15] containing metal zeolite catalyst (Pd/La 2o 3+ H-ZSM5) modulation
Lanthanum trioxide (III) (with light pure pharmaceutical worker's industry Inc.) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this lanthanum trioxide (III)/water, the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g being dissolved in 100ml is added gradually and the solution obtained in room temperature, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to La 2o 3every 1.0g contains the Pd/La of the Pd of 330 μm of ol 2o 3.
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio is H-ZSM5 (2.5g) and the Pd/La of 500 2o 30.25g carries out physical mixed fully, modulation Pd/La 2o 3+ H-ZSM5.
[catalyzer modulation example 16] containing metal zeolite catalyst (Pd/ZrO 2+ H-ZSM5) modulation
Zirconium white (IV) (with light pure pharmaceutical worker's industry Inc.) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this zirconium white (IV)/water, the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g being dissolved in 100ml is added gradually and the solution obtained in room temperature, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to ZrO 2every 1.0g contains the Pd/ZrO of the Pd of 330 μm of ol 2.
Use mortar, with the SiO of the state of powder by modulation in comparative example 1 2/ Al 2o 3the H-ZSM5 (2.5g) of mol ratio 500 and Pd/ZrO 20.25g carries out physical mixed fully, modulation Pd/ZrO 2+ H-ZSM5.
[catalyzer modulation example 17] containing metal zeolite catalyst (Pd/SrTiO 3+ H-ZSM5) modulation
Use mortar, with the state of powder directly by Strontium carbonate powder (with light pure pharmaceutical worker's industry Inc.) 10g and titanium oxide (IV) (Tian Chuan Physicochemical Inc.) 5.4g trifle physical mixed fully, in atmosphere, 10 hours are burnt till, modulation SrTiO at the temperature of 1150 DEG C 3.
By modulated SrTiO 310g impregnated in the distilled water of 100ml, under reduced pressure, carries out degassed in room temperature.To this SrTiO 3the mixed solution of/water, at room temperature adds the distilled water four ammonia palladium (II) the muriate monohydrates of 0.87g being dissolved in 100ml and the solution obtained gradually, after stirring 2 hours, stirs 2 hours further in room temperature at 50 DEG C.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to SrTiO 3every 1.0g contains the Pd/SrTiO of the Pd of 330 μm of ol 3.
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio is H-ZSM5 (2.5g) and the Pd/SrTiO of 500 30.25g carries out physical mixed fully, modulation Pd/SrTiO 3+ H-ZSM5.
[embodiment 15] activity rating: normal hexane decomposition reaction
The Ru/ZSM5 catalyzer of modulation in catalyzer modulation example 12 is pressurizeed, compressed, make aggegation block, pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carry out activity rating.In reaction tubes, fill the Ru/ZSM5 of 0.75g as catalyzer, under atmospheric pressure, nitrogen is circulated in reactor, while be warming up to 650 DEG C.At 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and carbonic anhydride with the flow of 1.9g/h, and make total head become 0.17MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the carbonic anhydride of oxidizing gas s/ V obe 0.50, the dividing potential drop of normal hexane gas is 0.11MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[embodiment 16]
About the Pd/Al of modulation in catalyzer modulation example 13 2o 3+ H-ZSM5 catalyzer, except filling the Pd/Al of 0.83g 2o 3+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[embodiment 17]
About the Pd/SiO of modulation in catalyzer modulation example 14 2+ H-ZSM5 catalyzer, except filling the Pd/SiO of 0.83g 2+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[embodiment 18]
About the Pd/La modulated in catalyzer modulation example 15 2o 3+ H-ZSM5 catalyzer, except filling the Pd/La of 0.83g 2o 3+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component.
[embodiment 19]
About the Pd/ZrO of modulation in catalyzer modulation example 16 2+ H-ZSM5 catalyzer, except filling the Pd/ZrO of 0.83g 2+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[embodiment 20]
About the Pd/SrTiO of modulation in catalyzer modulation example 17 3+ H-ZSM5 catalyzer, except filling the Pd/SrTiO of 0.83g 3+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[comparative example 8]
To the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio be 500 H-ZSM5 catalyzer carry out pressurizeing, compressing, make aggegation block, pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carries out activity rating.In reaction tubes, fill the H-ZSM5 of 0.75g as catalyzer, under atmospheric pressure, nitrogen is circulated in reactor, while be warming up to 650 DEG C of temperature of reaction.At 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and makes total head become 0.11MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the carbonic anhydride of oxidizing gas s/ V obe 0, the dividing potential drop of normal hexane gas is 0.11MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[comparative example 9]
About the Ru/ZSM5 catalyzer of modulation in catalyzer modulation example 12, except fill the Ru/ZSM5 of 0.75g as catalyzer, do not supply carbonic anhydride, total head be set to except 0.11MPa, operating similarly to Example 15, is 10h at the WHSV relative to mesopore zeolite quality -1, V s/ V obe under the condition of 0, carry out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[comparative example 10]
To the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio be 500 H-ZSM5 catalyzer carry out pressurizeing, compressing, make aggegation block, pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carries out activity rating.In reaction tubes, fill the H-ZSM5 of 0.75g as catalyzer, under atmospheric pressure, nitrogen is circulated in reactor, while be warming up to 650 DEG C of temperature of reaction.At 650 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and carbonic anhydride with the flow of 1.9g/h and pressurizes, and make total head become 0.17MPa, make reaction start under the following conditions, described condition is: be 10h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material early under temperature of reaction and the volume ratio V as the carbonic anhydride of oxidizing gas s/ V obe 0.50, the dividing potential drop of normal hexane gas is 0.11MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly imported gas chromatograph (detector: FID), analyze the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[comparative example 11]
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio be 500 H-ZSM5 (2.5g) and cerium oxide (IV) 0.25g carry out physical mixed fully, modulation CeO 2+ H-ZSM5.
About modulated CeO 2+ H-ZSM5 catalyzer, except filling the CeO of 0.83g 2+ H-ZSM5, as beyond catalyzer, operates in the same manner as comparative example 10, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 6.
[table 6]
Use and under carbonic anhydride adding conditional, implement the result of the embodiment 15 ~ 20 of normal hexane decomposition reaction containing Pd or Ru as the containing metal zeolite catalyst of integrant, with under the non-adding conditional of carbonic anhydride, implement the comparative example 8 of normal hexane decomposition reaction compare with the result of 9, ethene+propene yield that normal hexane decomposition reaction starts latter 1 hour, 22 hours and 37 hours is all high.In addition, the result of embodiment 15 ~ 20, with use not containing metal (X) as the catalyzer of integrant and implement under carbonic anhydride adding conditional the comparative example 10 of normal hexane decomposition reaction result and use containing Ce but not containing metal (X) as integrant catalyzer and implement compared with the arbitrary result in the result of the comparative example 11 of normal hexane decomposition reaction under carbonic anhydride adding conditional, all high at the ethene+propene yield of 1 hour, 22 hours and 37 hours.That is, specify that containing the containing metal zeolite catalyst of Pd or Ru as metal (X), when carbonic anhydride adds reaction conditions use, catalyst performance and catalyst life these two aspects excellence.
[catalyzer modulation example 18] containing metal zeolite catalyst (Pd/CeO 2+ H-ZSM5) modulation
Cerium oxide (IV) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this cerium oxide (IV)/water, the distilled water four ammonia palladium (II) the muriate monohydrates of 0.17g being dissolved in 100ml is added gradually and the solution obtained in room temperature, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.While use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to CeO 2every 1.0g contains the Pd/CeO of the Pd of 66 μm of ol 2.
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3the H-ZSM5 (2.5g) that mol ratio the is 500 and Pd/CeO modulated 20.25g carries out physical mixed fully, modulates the Pd/CeO containing the Pd of 6.6 μm of ol relative to the every 1.0g of zeolite 2+ H-ZSM5.
[catalyzer modulation example 19] containing metal zeolite catalyst (Pd/CeO 2+ H-ZSM5) modulation
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio is the H-ZSM5 (2.5g) of the 500 and Pd/CeO of modulation in catalyzer modulation example 2 20.25g carries out physical mixed fully, modulates the Pd/CeO containing the Pd of 33 μm of ol relative to the every 1.0g of zeolite 2+ H-ZSM5.
[catalyzer modulation example 20] containing metal zeolite catalyst (Pd/CeO 2+ H-ZSM5) modulation
Cerium oxide (IV) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this cerium oxide (IV)/water, the distilled water four ammonia palladium (II) the muriate monohydrates of 1.7g being dissolved in 100ml is added gradually and the solution obtained in room temperature, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained mixed solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to CeO 2every 1.0g contains the Pd/CeO of the Pd of 660 μm of ol 2.
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3the H-ZSM5 (2.5g) that mol ratio the is 500 and Pd/CeO modulated 20.25g carries out physical mixed fully, modulates the Pd/CeO containing the Pd of 66 μm of ol relative to the every 1.0g of zeolite 2+ H-ZSM5.
[catalyzer modulation example 21] containing metal zeolite catalyst (Ru/CeO 2+ H-ZSM5) modulation
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio is the H-ZSM5 (2.5g) of the 500 and Ru/CeO of modulation in catalyzer modulation example 1 20.25g carries out physical mixed fully, modulates the Ru/CeO containing the Ru of 33 μm of ol relative to the every 1.0g of zeolite 2+ H-ZSM5.
[catalyzer modulation example 22] containing metal zeolite catalyst (Rh/CeO 2+ H-ZSM5) modulation
Cerium oxide (IV) 10g be impregnated in the distilled water of 100ml, under reduced pressure, carry out degassed in room temperature.To the mixed solution of this cerium oxide (IV)/water, the rhodium nitrate (III) (Northeast chemical company system) adding 0.96g gradually in room temperature is dissolved in the distilled water of 100ml and the solution obtained, after stirring 2 hours at 50 DEG C, stir 2 hours further in room temperature.Use vaporizer, with 50 DEG C of water-baths, obtained solution is heated, under reduced pressure carry out evaporation drying on one side.After the residue drying after evaporation drying, in atmosphere, burn till 4 hours at the temperature of 500 DEG C, modulate relative to CeO 2every 1.0g contains the Rh/CeO of the Rh of 330 μm of ol 2.
Use mortar, with the state of powder directly by the SiO of modulation in comparative example 1 2/ Al 2o 3the H-ZSM5 (2.5g) that mol ratio the is 500 and Rh/CeO modulated 20.25g carries out physical mixed fully, modulates the Rh/CeO containing the Rh of 33 μm of ol relative to the every 1.0g of zeolite 2+ H-ZSM5.
[catalyzer modulation example 23] containing metal zeolite catalyst (Pd/CeO 2+ Ru/ZSM5) modulation
Use mortar, with the state of powder directly by the Ru/ZSM5 (2.5g) of modulation in catalyzer modulation the example 12 and Pd/CeO modulating modulation in example 2 at catalyzer 20.25g carries out physical mixed fully, modulates the Pd/CeO of the Ru containing Pd and the 33 μm ol of 33 μm of ol relative to the every 1.0g of zeolite 2+ Ru/ZSM5.
[embodiment 21]
About the Pd/CeO containing the Pd of 6.6 μm of ol relative to the every 1.0g of zeolite of modulation in catalyzer modulation example 18 2+ H-ZSM5 catalyzer, except filling the Pd/CeO of 0.83g 2+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 7.
[embodiment 22]
About the Pd/CeO containing the Pd of 33 μm of ol relative to the every 1.0g of zeolite of modulation in catalyzer modulation example 19 2+ H-ZSM5 catalyzer, except filling the Pd/CeO of 0.83g 2+ H-ZSM, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 7.
[embodiment 23]
About the Pd/CeO containing the Pd of 66 μm of ol relative to the every 1.0g of zeolite of modulation in catalyzer modulation example 20 2+ H-ZSM5 catalyzer, except filling the Pd/CeO of 0.83g 2+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 7.
[embodiment 24]
About the Ru/CeO of modulation in catalyzer modulation example 21 2+ H-ZSM5 catalyzer, except filling the Ru/CeO of 0.83g 2+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 7.
[embodiment 25]
About the Rh/CeO of modulation in catalyzer modulation example 22 2+ H-ZSM5 catalyzer, except filling the Rh/CeO of 0.83g 2+ H-ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 7.
[embodiment 26]
About the Pd/CeO of modulation in catalyzer modulation example 23 2+ Ru/ZSM5 catalyzer, except filling the Pd/CeO of 0.83g 2+ Ru/ZSM5, as beyond catalyzer, operates similarly to Example 15, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 7.
[comparative example 12]
About the Pd/CeO containing the Pd of 33 μm of ol relative to the every 1.0g of zeolite of modulation in catalyzer modulation example 19 2+ H-ZSM5 catalyzer, except filling the Pd/CeO of 0.83g 2+ H-ZSM5, as beyond catalyzer, operates in the same manner as comparative example 9, carries out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 7.
[table 7]
Use and under carbonic anhydride adding conditional, implement the result of the embodiment 21 ~ 26 of normal hexane decomposition reaction containing Pd, Ru or Rh as the containing metal zeolite catalyst of integrant, with use containing Pd as the containing metal zeolite catalyst of integrant and compared with the result implementing the comparative example 12 of normal hexane decomposition reaction under the non-adding conditional of carbonic anhydride, ethene+propene yield that synthetic naphtha decomposition reaction starts latter 1 hour, 22 hours and 37 hours is all high.In addition, to the normal hexane decomposition reaction carried out under carbonic anhydride adding conditional, use containing metal (X) and the Ce result as the embodiment 21 ~ 26 of the catalyzer of integrant, even if with use containing Ce as integrant but not the comparative example 11 of the table 6 of the catalyzer of containing metal (X) result and uses containing metal (X) as integrant but not containing the embodiment 15 ~ 20 of the table 6 of the catalyzer of Ce result compared with, the also equal height of the ethene+propene yield 1 hour, 22 hours and 37 hours.That is, specify that containing Pd, Ru or Rh containing metal zeolite catalyst as metal (X), when using under carbonic anhydride interpolation reaction conditions, excellent in catalyst performance and catalyst life these two aspects, further containing Ce as more excellent time groups of elements (Y).
[catalyzer modulation example 24] containing metal zeolite catalyst (Pd/CeO 2+ P/Pt-Ce/ZSM5) modulation
To the SiO of modulation in catalyzer modulation example 11 2/ Al 2o 3mol ratio is the H-ZSM5 (2.0g) of 50, in the loading amount of Pt in the mode that Pt atom becomes 0.50 quality %, the loading amount of Ce to become 0.30 quality % with Ce atom, platinum chloride (IV) sour hexahydrate and cerous nitrate (III) hexahydrate (with light pure pharmaceutical worker industry Inc.) is made to be dissolved in appropriate distilled water, use this solution, held by incipient wetness (incipientwetness) method.The powder that drying is obtained, drip the hydrazine aqueous solution by the 0.13mol/L that hydrazine monohydrate (with light pure pharmaceutical worker's industry Inc.) is dissolved in distilled water to modulate, after Pt liquid-phase reduction, filter cleaning with distilled water, 100 DEG C of dryings 24 hours, modulation Pt-Ce/ZSM5.To impregnation 85% phosphate aqueous solution in obtained Pt-Ce/ZSM5 (with light pure pharmaceutical worker's industry Inc.) 0.087g, after carrying out drying, in atmosphere, burn till 10 hours, modulation P/Pt-Ce/ZSM5 at the temperature of 650 DEG C.
Use mortar, directly the Pd/CeO20.19g of P/Pt-Ce/ZSM5 (2.0g) and modulation in catalyzer modulation example 2 is carried out physical mixed, modulation Pd/CeO fully with the state of powder 2+ P/Pt-Ce/ZSM5.
[embodiment 27] activity rating: normal hexane decomposition reaction
To the Pd/CeO of modulation in catalyzer modulation example 24 2+ P/Pt-Ce/ZSM5 catalyzer carries out pressurizeing, compressing, and makes aggegation block, and pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carries out activity rating.The Pd/CeO of 1.8g is filled in reaction tubes 2+ P/Pt-Ce/ZSM5, as catalyzer, under atmospheric pressure, makes nitrogen be circulated in reactor with the flow of 50Ncc/min, while be warming up to 600 DEG C.At the temperature of 600 DEG C, with the flow of 50Ncc/min, hydrogen is circulated in reactor, while carry out the reduction treatment of 1 hour.After reduction treatment, at 600 DEG C, circulated gases is switched to nitrogen from hydrogen, make it be circulated in reactor with the flow of 50Ncc/min, while carry out the pre-treatment of 1.5 hours, be warming up to 630 DEG C of temperature of reaction.At 630 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and by carbonic anhydride with the flow of 7.7g/h, and make total head become 0.11MPa, make reaction start under the following conditions, described condition is: be 5.0h relative to the WHSV of mesopore zeolite quality -1, the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the carbonic anhydride of oxidizing gas s/ V obe 2.0, the dividing potential drop of normal hexane gas is 0.037MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 8.
[embodiment 28]
About the Pd/CeO of modulation in catalyzer modulation example 24 2+ P/Pt-Ce/ZSM5 catalyzer, except carbonic anhydride feed rate is set to 11g/h, total head is set to except 0.11MPa, and operating similarly to Example 27, is 10h at the WHSV relative to mesopore zeolite quality -1, V s/ V obe 3.0, the dividing potential drop of normal hexane gas is under the condition of 0.028MPa, carry out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 8.
[comparative example 13]
To the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio be 500 H-ZSM5 catalyzer carry out pressurizeing, compressing, make aggegation block, pulverized by this aggegation block, whole grain becomes the particle diameter of 0.25mm ~ 0.50mm, by using fixed bed flow type reaction unit to carry out normal hexane decomposition reaction, thus carries out activity rating.In reaction tubes, fill the H-ZSM5 of 1.5g as catalyzer, under atmospheric pressure, make in nitrogen flow-through reactor with the flow of 50Ncc/min, while be warming up to 630 DEG C of temperature of reaction.At 630 DEG C, the circulation of the nitrogen in reaction tubes is stopped, replace, the normal hexane of raw material is supplied to reaction tubes with the flow of 7.5g/h and by carbonic anhydride with the flow of 7.7g/h, and make total head become 0.11MPa, make reaction start under the following conditions, described condition is: be 5.0h relative to the WHSV of mesopore zeolite quality -1the normal hexane gas as raw material at the reaction temperatures and the volume ratio V as the carbonic anhydride of oxidizing gas s/ V obe 2.0, the dividing potential drop of normal hexane gas is 0.037MPa.After reaction starts, after a predetermined time elapses, resultant of reaction is directly directed into gas chromatograph (detector: FID), analyzes the composition of resultant.The yield of each resultant calculated based on the quality of carbon component is shown in Table 8.
[comparative example 14]
About the SiO of modulation in comparative example 1 2/ Al 2o 3mol ratio is the H-ZSM5 catalyzer of 500, and except carbonic anhydride feed rate is set to 11g/h, total head is set to except 0.11MPa, and operating in the same manner as comparative example 13, is 5h at the WHSV relative to mesopore zeolite quality -1, V s/ V obe under the condition of 3.0, carry out activity rating by normal hexane decomposition reaction.The yield of each resultant calculated based on the quality of carbon component is shown in Table 8.
[table 8]
In the normal hexane decomposition reaction carried out under carbonic anhydride adding conditional, use containing the embodiment 27 (V of Pd and Pt as the containing metal zeolite catalyst of integrant s/ V o=2.0) and embodiment 28 (V s/ V o=3.0) result, with not containing metal (X) as the comparative example 13 (V of integrant s/ V o=2.0) and comparative example 14 (V s/ V o=3.0) result is compared, all high at 1 hour, the 22 hours お I び ethene+propene yield of 37 hours.That is, specify that containing the containing metal zeolite catalyst of Pd and Pt as metal (X), when using under carbonic anhydride interpolation reaction conditions, even if carbonic anhydride is being increased to V relative to the volume ratio of raw material normal hexane gas s/ V owhen=3.0, also in catalyst performance and catalyst life these two aspects excellence.
About following item, also can containing within the scope of the invention.
The manufacture method of (2-1) a kind of light alkene class, the manufacture method of the light alkene class of 2 ~ 4 that to be the carbonatoms being principal constituent with ethene, propylene be, it is characterized in that, the raw material (O) that to make with the saturated hydrocarbons that is 35 ~ 180 DEG C of scopes of the boiling point under 1 air pressure be principal constituent contacts with containing metal zeolite catalyst with oxidizing gas (S), and described containing metal zeolite catalyst contains periodictable 8th ~ 10 race metal (X) and has by ten tetrahedral TO 4the mesopore zeolite (Z1) of the ten-ring structure that (T represents Si atom or Al atom, and O represents Sauerstoffatom) unit is formed is as integrant.
The manufacture method of (2-2) light alkene class as described in (2-1), described oxidizing gas (S) is for being selected from more than a kind in water vapour and carbonic anhydride.
The manufacture method of (2-3) light alkene class as described in (2-1) or (2-2), under catalyst temperature when making described raw material (O) contact with described containing metal zeolite catalyst with described oxidizing gas (S), namely under the temperature of reaction in the contact decomposition reaction of described raw material (O), in other words, at the temperature of the catalyst layer in contact decomposition reaction, the volume (V shared by gas of described oxidizing gas (S) s) relative to the volume (V shared by described raw material (O) gas o) ratio (V s/ V o) be 0.01 ~ 2 scope.
The manufacture method of (2-4) light alkene class according to any one of (2-1) ~ (2-3), the temperature of reaction in the contact decomposition reaction of described raw material (O) is the scope of 500 ~ 750 DEG C.
The manufacture method of (2-5) light alkene class according to any one of (2-1) ~ (2-4), mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 ').
The manufacture method of (2-6) light alkene class according to any one of (2-1) ~ (2-5), described containing metal zeolite catalyst further containing more than one the element be selected from the group that is made up of periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) as integrant, described element (Y2) is for being selected from more than one the element in P, As, Sb and Bi.
The manufacture method of (2-7) light alkene class as described in (2-6), described containing metal zeolite catalyst contains described element (Y2), and described periodictable the 15th race's element (Y2) is P.
The manufacture method of (2-8) light alkene class as described in (2-6) or (2-7), described containing metal zeolite catalyst contains described element (Y1), and described periodictable the 3rd race's element (Y1) is Ce.
The manufacture method of (2-9) light alkene class according to any one of (2-5) ~ (2-8), described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), and described mesopore zeolite (Z1 ') holds described metal (X).
The manufacture method of (2-10) light alkene class as described in (2-9), described mesopore zeolite (Z1 ') holds more than one element in the group being selected from and being made up of periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) further, and described element (Y2) is for being selected from more than one the element of P, As, Sb and Bi.
The manufacture method of (2-11) light alkene class as described in (2-6), containing metal zeolite catalyst contains described element (Y1), described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), and containing metal zeolite catalyst is the described metal (X) that holds on the oxide compound (Z2) of described element (Y1) and the physical mixed body of described mesopore zeolite (Z1 ').
The manufacture method of (2-11 ') light alkene class as described in (2-11), described element (Y1) is Ce.
The manufacture method of (2-12) light alkene class as described in (2-6), containing metal zeolite catalyst contains described element (Y1) and described element (Y2), described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), and containing metal zeolite catalyst is the described metal (X) that holds on the oxide compound (Z2) of described element (Y1) and the physical mixed body being carried with the described mesopore zeolite of described element (Y2) (Z1 ').
The manufacture method of (2-12 ') light alkene class as described in (2-12), described element (Y1) is Ce.
The manufacture method of (2-12 ") light alkene class as described in (2-12), described element (Y2) is P.
The manufacture method of (2-13) light alkene class as described in (2-12), described mesopore zeolite (Z1 ') holds Al further.
The manufacture method of (2-14) light alkene class as described in (2-13), containing metal zeolite catalyst contains P as described element (Y2) as must element, and the Al be supported on described mesopore zeolite (Z1 ') derives from and is selected from boehmite, at least one aluminum contained compound (A) intended in boehmite, aluminum oxide, aluminium salt and amorphous silica-aluminum oxide.
The manufacture method of (2-15) light alkene class as described in (2-14), described aluminum contained compound (A) is any one in boehmite or plan boehmite.
The manufacture method of (2-16) light alkene class according to any one of (2-13) ~ (2-15), the composition of Si and Al contained by described mesopore zeolite (Z1 '), by the mol ratio (SiO being converted into silicon-dioxide and aluminum oxide 2/ Al 2o 3) count 30 ~ 100 scope, and the total of the Al composition contained by described containing metal zeolite catalyst counts the scope of 1 ~ 10 quality % with Al atom.
The manufacture method of (2-17) light alkene class according to any one of (2-14) ~ (2-16), the composition of P and Al contained by described containing metal zeolite catalyst, counts the scope of 0.1 ~ 1.0 with atomic molar ratio (P/Al).
The manufacture method of (2-18) light alkene class according to any one of (2-11) ~ (2-17), described oxide compound (Z2) is cerium oxide.
The manufacture method of (2-19) light alkene class according to any one of (2-11) ~ (2-18), described inorganic solid compounds (Z3) is perovskite compound.
The manufacture method of (2-20) light alkene class as described in (2-6), containing metal zeolite catalyst contains described element (Y1), described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), the physical mixed body of the containing metal zeolite catalyst described metal (X) that to be the described metal (X) that holds of the oxide compound (Z2) of described element (Y1) hold with described mesopore zeolite (Z1 ').
The manufacture method of (2-20 ') light alkene class as described in (2-20), described element (Y1) is Ce.
The manufacture method of (2-21) light alkene class as described in (2-20), described mesopore zeolite (Z1 ') is carried with more than one the element be selected from described element (Y1) and described element (Y2) further.
The manufacture method of (2-22) light alkene class as described in (2-10), described mesopore zeolite (Z1 ') is carried with Al further.
The manufacture method of (2-23) light alkene class according to any one of (2-1) ~ (2-22), described metal (X) is for being selected from the metal in Ru, Rh, Ir, Ni, Pd and Pt.
The manufacture method of (2-24) light alkene class as described in (2-5), containing metal zeolite catalyst is described metal (X) and the physical mixed body of the described metal (X) held on described mesopore zeolite (Z1 '), and described metal (X) is supported in the inorganic solid compounds (Z3) all different from the oxide compound (Z2) of described mesopore zeolite (Z1 ') and periodictable the 3rd race's element (Y1).
The manufacture method of (2-25) light alkene class as described in (2-5), containing metal zeolite catalyst is described metal (X) and the physical mixed body being carried with the described mesopore zeolite of periodictable the 15th race's element (Y2) (Z1 '), and described metal (X) is supported in the inorganic solid compounds (Z3) all different from the oxide compound (Z2) of described mesopore zeolite (Z1 ') and periodictable the 3rd race's element (Y1).
The manufacture method of (2-26) light alkene class as described in (2-5), containing metal zeolite catalyst is described metal (X) and the physical mixed body of described mesopore zeolite (Z1 '), and described metal (X) is supported in the inorganic solid compounds (Z3) all different from the oxide compound (Z2) of described mesopore zeolite (Z1 ') and periodictable the 3rd race's element (Y1).
[utilizability in industry]
The present invention can be used in the manufacture method of the unsaturated hydro carbons using containing metal zeolite catalyst.

Claims (23)

1. the carbonatoms that is principal constituent with ethene, propylene is the manufacture method of the light alkene class of 2 ~ 4, it is characterized in that, the raw material (O) that to make with the saturated hydrocarbons that is 35 ~ 180 DEG C of scopes of the boiling point under 1 air pressure be principal constituent contacts with containing metal zeolite catalyst with oxidizing gas (S), and described containing metal zeolite catalyst contains periodictable 8th ~ 10 race metal (X) and has by ten tetrahedral TO 4the mesopore zeolite (Z1) of the ten-ring structure that unit is formed is as integrant, and wherein T represents Si atom or Al atom, and O represents Sauerstoffatom.
2. the manufacture method of light alkene class as claimed in claim 1, described oxidizing gas (S) is for being selected from more than a kind in water vapour and carbonic anhydride.
3. the manufacture method of light alkene class as claimed in claim 1 or 2, under the temperature of reaction in the contact decomposition reaction of described raw material (O), the volume (V shared by gas of described oxidizing gas (S) s) relative to the volume (V shared by described raw material (O) gas o) ratio (V s/ V o) be 0.01 ~ 2 scope.
4. the manufacture method of the light alkene class according to any one of claims 1 to 3, the temperature of reaction in the contact decomposition reaction of described raw material (O) is the scope of 500 ~ 750 DEG C.
5. the manufacture method of the light alkene class according to any one of Claims 1 to 4, mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 ').
6. the manufacture method of the light alkene class according to any one of Claims 1 to 5,
Described containing metal zeolite catalyst further containing more than one the element be selected from the group that is made up of periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) as integrant,
Described element (Y2) is for being selected from more than one the element in P, As, Sb and Bi.
7. the manufacture method of light alkene class as claimed in claim 6,
Described containing metal zeolite catalyst contains described element (Y2),
Described element (Y2) is P.
8. the manufacture method of light alkene class as claimed in claims 6 or 7,
Described containing metal zeolite catalyst contains described element (Y1),
Described element (Y1) is Ce.
9. the manufacture method of the light alkene class according to any one of claim 5 ~ 8,
Described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '), in described mesopore zeolite (Z1 '), be carried with described metal (X).
10. the manufacture method of light alkene class as claimed in claim 9,
More than one the element in the group being selected from and being made up of periodictable the 3rd race's element (Y1) and periodictable the 15th race's element (Y2) is also held in described mesopore zeolite (Z1 '),
Described element (Y2) is for being selected from more than one the element in P, As, Sb and Bi.
The manufacture method of 11. light alkene classes according to any one of claim 6 ~ 8,
Described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '),
Containing metal zeolite catalyst is for being supported at the described metal (X) of the oxide compound (Z2) of described element (Y1) or being supported at the described metal (X) of the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described mesopore zeolite (Z1 '), the physical mixed body with described mesopore zeolite (Z1 ').
The manufacture method of 12. light alkene classes according to any one of claim 6 ~ 8,
Described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '),
Containing metal zeolite catalyst for be supported at the oxide compound (Z2) of described element (Y1) described metal (X) or be supported at the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described mesopore zeolite (Z1 ') described metal (X), with the physical mixed body of described mesopore zeolite (Z1 ') being carried with described element (Y2).
The manufacture method of 13. light alkene classes as claimed in claim 12, is also carried with Al in described mesopore zeolite (Z1 ').
The manufacture method of 14. light alkene classes as claimed in claim 13, containing metal zeolite catalyst contains P as described element (Y2) as must element, and the Al being supported at described mesopore zeolite (Z1 ') derives from and is selected from boehmite, at least one aluminum contained compound (A) intended in boehmite, aluminum oxide, aluminium salt and amorphous silica-aluminum oxide.
The manufacture method of 15. light alkene classes as claimed in claim 14, described aluminum contained compound (A) is for boehmite or intend any one of boehmite.
The manufacture method of 16. light alkene classes according to any one of claim 13 ~ 15,
The composition of Si and Al contained by described mesopore zeolite (Z1 '), by the mol ratio (SiO being converted into silicon-dioxide and aluminum oxide 2/ Al 2o 3) count 30 ~ 100 scope, and the total of the Al composition contained by described containing metal zeolite catalyst counts the scope of 1 ~ 10 quality % with Al atom.
The manufacture method of 17. light alkene classes according to any one of claim 14 ~ 16,
The composition of P and Al contained by described containing metal zeolite catalyst, counts the scope of 0.1 ~ 1.0 with atomic molar ratio (P/Al).
The manufacture method of 18. light alkene classes according to any one of claim 11 ~ 17, described oxide compound (Z2) is cerium oxide.
The manufacture method of 19. light alkene classes according to any one of claim 11 ~ 18, described inorganic solid compounds (Z3) is perovskite compound.
The manufacture method of 20. light alkene classes according to any one of claim 6 ~ 8,
Described mesopore zeolite (Z1) is MFI type, the mesopore zeolite of MWW type or FER type (Z1 '),
Containing metal zeolite catalyst for be supported at the oxide compound (Z2) of described element (Y1) described metal (X) or be supported at the inorganic solid compounds (Z3) all different with described oxide compound (Z2) from described mesopore zeolite (Z1 ') described metal (X), with the physical mixed body of described metal (X) being supported at described mesopore zeolite (Z1 ').
The manufacture method of 21. light alkene classes as claimed in claim 20, is also carried with more than one the element be selected from described element (Y1) and described element (Y2) in described mesopore zeolite (Z1 ').
The manufacture method of 22. light alkene classes as claimed in claim 10, is also carried with Al in described mesopore zeolite (Z1 ').
The manufacture method of 23. light alkene classes according to any one of claim 1 ~ 22, described metal (X) is for being selected from the metal in Ru, Rh, Ir, Ni, Pd and Pt.
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