CN109174170A - A kind of preparation method of active metal high dispersive hydroisomerization catalyst - Google Patents
A kind of preparation method of active metal high dispersive hydroisomerization catalyst Download PDFInfo
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- CN109174170A CN109174170A CN201811193963.2A CN201811193963A CN109174170A CN 109174170 A CN109174170 A CN 109174170A CN 201811193963 A CN201811193963 A CN 201811193963A CN 109174170 A CN109174170 A CN 109174170A
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- active metal
- hydroisomerization catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 claims description 5
- -1 cetyl pyridinium quaternary ammonium salt Chemical class 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- QCQNTHIIWHZNNX-UHFFFAOYSA-M azanium benzyl-dimethyl-octadecylazanium dichloride Chemical compound [Cl-].C(CCCCCCCCCCCCCCCCC)[N+](CC1=CC=CC=C1)(C)C.[Cl-].[NH4+] QCQNTHIIWHZNNX-UHFFFAOYSA-M 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims 1
- 239000012190 activator Substances 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 229960004830 cetylpyridinium Drugs 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 21
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J29/70—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
- B01J29/74—Noble metals
-
- 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
- B01J29/70—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
- B01J29/74—Noble metals
- B01J29/7461—MRE-type, e.g. ZSM-48
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to function catalyst preparation technical field more particularly to a kind of preparation methods of active metal high dispersive hydroisomerization catalyst.First in the Pt aqueous metal salt containing cationic surfactant, using the Pt nanoparticle of hydrazine hydrate reduction method preparation uniform particle diameter；Molecular sieve is impregnated in again after sufficiently being adsorbed in the aqueous solution of the prepared nanoparticle containing Pt, is washed, dry, roasting obtains hydroisomerisation catalysts.This method is simple, easy to operate, and active metal has high dispersion degree in prepared catalyst and metal partial size can be controlled in 2.0-4.0 nm, and the hydroisomerization catalyst activity being prepared is high, excellent for the selectivity and yield of long-chain isoparaffin.
Description
Technical field
The invention belongs to function catalyst preparation technical fields more particularly to a kind of active metal high dispersive hydroisomerizing to urge
The preparation method of agent.
Background technique
Metal dispersity in the prior art in bifunctional catalyst is often poor, will seriously affect the conversion ratio of catalyst
And isomerisation selectivity.The catalyst for possessing high dispersive high activity metal particle is obtained using reasonable preparation method, is long-chain
Research emphasis in the exploitation of alkane hydroisomerisation catalysts.
Long chain alkane hygrogenating isomerization reaction uses bifunctional catalyst, which has metal active constituent and acidity
Carrier, active metal play the role of dehydrogenation/plus hydrogen, and acid carrier provides suitable acidic site for isomerization, specific surface with
And suitable cellular structure.In the case where facing hydrogen atmosphere, long chain alkane is isomerized to isoparaffin mechanism on bifunctional catalyst
Be commonly considered as: 1) n-alkane is first in the absorption of active metal position and dehydrogenation generation alkene；2) alkene is shifted from metal center
To acid centre and obtain proton and generate carbonium ion, then carry out skeletal isomerization at alkene or cracking be one it is new just
Carbon ion and a small-numerator olefin；3) alkene moves to metal center and adds hydrogen and be desorbed.The gold that bifunctional catalyst is included
The performance of the shape-selective three factors meeting combined influence catalyst of category-acidity-.
Hygrogenating isomerization reaction mechanism shows that metal active has important role for catalyst activity and selectivity of product,
That is the metal of high activity increases the concentration of the resulting alkene of dehydrating alkanes, while the alkene that isomery obtains can add rapidly hydrogen saturation
At alkane, secondary cracking reaction is reduced.So that alkane molecule hydroisomerization plays a leading role, product will be to divide with raw material
Based on the identical isoparaffin of sub- carbon number.
CN 105688979B reports that a kind of utilization reduction of ethylene glycol prepares Pt nanoparticle, then uses collosol and gel again
The method that method prepares hydroisomerisation catalysts, the favorable dispersibility of metal active constituent in gained catalyst, and had
Conversion ratio and isomerisation selectivity.But catalyst preparation process step is more, and it is cumbersome, it is difficult to control catalyst reproducibility.
US 4859311 reports a kind of method for preparing the hydroisomerisation catalysts that active metal Pt rationally disperses.?
Active metal salt Pt (NH is added when Zeolite synthesis3)4(NO3)2, pure molecular sieve carried active metal catalyst is first prepared, later
Add binder extruded moulding.Isomerized products yield can be improved in the reaction of hydroisomerizing pour point depression in gained catalyst.But it is catalyzed
Agent activity is not high.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of high dispersion metal load hydrogenation heterogeneous catalyst, especially
The dispersion degree for emphasizing active metal in improvement catalyst, to improve the activity and isomerized products yield of hydroisomerization catalyst.
The present invention is hydrazine hydrate reduction preparation small particle and uniform active metal particles under aqueous ammonia conditions, is then carried on molecular sieve
Prepare hydroisomerization catalyst.This method is simple, easy to operate, and active metal has high dispersion degree and gold in prepared catalyst
Belong to size tunable system in 2.0-4.0nm.Reported hydroisomerization catalyst activity is high in the present invention, for long-chain isoparaffin
Selectivity and yield are excellent.
To achieve the above object, the present invention adopts the following technical scheme:
To achieve the goal one, technical scheme is as follows:
A kind of preparation method of high dispersion metal load hydrogenation heterogeneous catalyst, steps are as follows:
(1) preparation of Pt nanoparticle: the water by carried metal presoma (Pt presoma), with cationic surfactant
Ultrasonic disperse is carried out after solution mixing, then stirs to transparent, obtains Pt- aqueous surfactant solutions；Pt- activating agent is adjusted with ammonium hydroxide
The pH to 11~13 of aqueous solution is stirred 30 minutes, and hydrazine hydrate solution is added under room temperature and restores rapidly, obtains Pt nanoparticle
Son；
(2) preparation of hydroisomerisation catalysts: the activating agent that molecular sieve is added to the particle containing Pt of above-mentioned preparation is molten
In liquid, stir 4 hours, filtration washing, it is dry, after roasting in air, obtain the hydroisomerisation catalysts.
In above-mentioned technical proposal, related carried metal presoma is four ammino platinum of acetic acid, four ammino platinum of nitric acid, nitrous
Sour four ammino platinum, one or more of four ammino platinum of sulfuric acid or four ammino platinum chlorides；
In above-mentioned technical proposal, cationic surfactant is cetyl trimethylammonium bromide (CTAB), cetyl
Trimethyl ammonium chloride (CTAC), Dodecyl Dimethyl Amine acetate, octadecyl dimethyl benzyl ammonium ammonium chloride, hexadecane
Yl pyridines quaternary ammonium salt, one or more of dioctadecyldimethylammonium bromide cationic surfactant；
In above-mentioned technical proposal, related carried metal content is 0.01~2wt% of catalyst gross mass；
In above-mentioned technical proposal, the concentration of involved cationic surfactant is 0.01~0.1mol/L；
In above-mentioned technical proposal, the molar ratio of involved hydrazine hydrate and Pt metal is in 2~10:1；
In above-mentioned technical proposal, the time of ultrasonic disperse is 10~60min in steps involved (1)；
In above-mentioned technical proposal, in steps involved (1) with ammonium hydroxide adjust Pt- aqueous surfactant solutions pH to 11.5~
12.5；
The recovery time is 0.5~2 hour after hydrazine hydrate solution is added in above-mentioned technical proposal, in steps involved (1)；
In above-mentioned technical proposal, the molecular sieve for accounting for catalyst quality 98%-99.99% of addition in steps involved (2)
It is SAPO-11, ZSM-22, ZSM-23, SAPO-31, SAPO-41 for one-dimensional ten yuan of duct molecular sieves of moderate strength acidity,
One of ZSM-48, SSZ-32, SSZ-32x or a variety of；
In above-mentioned technical proposal, the drying temperature in steps involved (2) is 100~150 DEG C, and drying time is 12~24
Hour；
In above-mentioned technical proposal, maturing temperature in steps involved (2) is 400~600 DEG C, calcining time is 3.0~
6.0 hour.
Remarkable advantage of the invention is:
(1) present invention preparation hydroisomerisation catalysts have excellent long-chain because metal partial size is smaller and dispersion is uniform
Alkane conversion and isoparaffin selectivity.
(2) the method for the present invention is simple, easy to operate, and active metal has high dispersion degree and clipped wire in prepared catalyst
Diameter can be controlled in 2.0-4.0nm.Reported hydroisomerization catalyst activity is high in the present invention, the selection for long-chain isoparaffin
Property and yield are excellent.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Comparative example 1
Catalyst preparation:
Tetra- ammino platinum chloride aqueous solution (9.4g/ml) of 5.0ml is taken, 10.0ml water is added and stirs evenly, then adds thereto
Enter 10.0g SAPO-11 molecular sieve, stirs 8.0 hours, static 4.0 hours at room temperature.Sample stirs under the conditions of 80 DEG C after dipping
Mix and be evaporated, 120 DEG C oven drying 12.0 hours, roasted 4.0 hours at 500 DEG C after grinding.
By it is above-mentioned prepare catalyst tabletting and be crushed to 20~40 mesh be used for catalytic performance test.
Evaluating catalyst method and condition:
Catalyst catalytic performance evaluation is carried out using high pressure fixed bed reactors in this example, and reaction raw materials are positive 16
Alkane.Catalyst packing quality is 2.0ml.Before reaction, catalyst needs 400 DEG C of reductase 12 hours under normal pressure, is down to reaction to temperature
Temperature is passed through raw hydrogen and is reacted with hexadecane.Reaction condition are as follows: reaction temperature is 340 DEG C, and reaction pressure is
3.5MPa, the volume space velocity of raw material are 1.0h-1, the molar ratio of hydrogen and hexadecane is 40:1.Reaction result is shown in Table 1.
Wherein, the calculation formula of hexadecane conversion ratio, isomerized products selectivity is as follows:
Isomerized products yield=hexadecane conversion ratio × isomerized products selectivity × 100%
Embodiment 1
Catalyst preparation:
(1) preparation of Pt nanoparticle:
Claim tetra- ammino platinum chloride aqueous solution (0.93wt%) of 5.0ml to configure 20ml aqueous solution, 0.8g cetyl three is added
Methyl bromide ammonium (CTAB) ultrasonic disperse 30 minutes, until the transparent non-foam of solution, obtains Pt (NH3)4 2+- CTAB aqueous solution uses
Concentration is that 0.5M ammonia spirit adjusts pH 11, stirs 30 minutes, the hydrazine hydrate solution of the amount of 2 times of Pt substances is added at room temperature,
Reduction obtains Pt nanoparticle rapidly.
(2) preparation of hydroisomerisation catalysts:
10.0g molecular sieve is added in the CTAB solution of the particle containing Pt of above-mentioned preparation, is stirred 4 hours, filtration washing,
120 DEG C of dryings obtain the hydroisomerisation catalysts in air after 500 DEG C of roastings.
By it is above-mentioned prepare catalyst tabletting and be crushed to 20~40 mesh be used for catalytic performance test.
Evaluating catalyst method and condition:
As described in comparative example 1, reaction result is shown in Table 1 for evaluation and analysis method.
Embodiment 2
Catalyst preparation:
(1) preparation of Pt nanoparticle:
Claim tetra- ammino platinum chloride aqueous solution (0.93wt%) of 5.0ml to configure 20ml aqueous solution, 0.8g cetyl three is added
Methyl bromide ammonium (CTAB) ultrasonic disperse 30 minutes, until the transparent non-foam of solution, obtains Pt (NH3)4 2+- CTAB aqueous solution uses
Concentration is that 0.5M ammonia spirit adjusts pH 11, stirs 30 minutes, the hydrazine hydrate solution of the amount of 4 times of Pt substances is added at room temperature,
Reduction obtains Pt nanoparticle rapidly.
(2) preparation of hydroisomerisation catalysts:
10.0g molecular sieve is added in the CTAB solution of the particle containing Pt of above-mentioned preparation, is stirred 4 hours, filtration washing,
120 DEG C of dryings obtain the hydroisomerisation catalysts in air after 500 DEG C of roastings.
By it is above-mentioned prepare catalyst tabletting and be crushed to 20~40 mesh be used for catalytic performance test.
Evaluating catalyst method and condition:
As described in comparative example 1, reaction result is shown in Table 1 for evaluation and analysis method.
Embodiment 3
Catalyst preparation:
(1) preparation of Pt nanoparticle:
Claim tetra- ammino platinum chloride aqueous solution (0.93wt%) of 5.0ml to configure 20ml aqueous solution, 0.8g cetyl three is added
Methyl bromide ammonium (CTAB) ultrasonic disperse 30 minutes, until the transparent non-foam of solution, obtains Pt (NH3)4 2+- CTAB aqueous solution uses
Concentration is that 0.5M ammonia spirit adjusts pH 11, stirs 30 minutes, the hydrazine hydrate solution of the amount of 6 times of Pt substances is added at room temperature,
Reduction obtains Pt nanoparticle rapidly.
(2) preparation of hydroisomerisation catalysts:
10.0g molecular sieve is added in the CTAB solution of the particle containing Pt of above-mentioned preparation, is stirred 4 hours, filtration washing,
120 DEG C of dryings obtain the hydroisomerisation catalysts in air after 500 DEG C of roastings.
By it is above-mentioned prepare catalyst tabletting and be crushed to 20~40 mesh be used for catalytic performance test.
Evaluating catalyst method and condition:
As described in comparative example 1, reaction result is shown in Table 1 for evaluation and analysis method.
Embodiment 4
Catalyst preparation:
(1) preparation of Pt nanoparticle:
Claim tetra- ammino platinum chloride aqueous solution (0.93wt%) of 5.0ml to configure 20ml aqueous solution, 0.8g cetyl three is added
Methyl bromide ammonium (CTAB) ultrasonic disperse 30 minutes, until the transparent non-foam of solution, obtains Pt (NH3)4 2+- CTAB aqueous solution uses
Concentration is that 0.5M ammonia spirit adjusts pH 11, stirs 30 minutes, the hydrazine hydrate solution of the amount of 8 times of Pt substances is added at room temperature,
Reduction obtains Pt nanoparticle rapidly.
(2) preparation of hydroisomerisation catalysts:
10.0g molecular sieve is added in the CTAB solution of the particle containing Pt of above-mentioned preparation, is stirred 4 hours, filtration washing,
120 DEG C of dryings obtain the hydroisomerisation catalysts in air after 500 DEG C of roastings.
By it is above-mentioned prepare catalyst tabletting and be crushed to 20~40 mesh be used for catalytic performance test.
Evaluating catalyst method and condition:
As described in comparative example 1, reaction result is shown in Table 1 for evaluation and analysis method.
Table 1
Comparative example 2
Catalyst preparation:
Tetra- ammino platinum nitrate aqueous solution (0.93wt%) of 5.0ml is taken, 10.0ml water is added and stirs evenly, then adds thereto
Enter 10.0g ZSM-22 molecular sieve, stirs 8.0 hours, static 4.0 hours at room temperature.Sample stirs under the conditions of 80 DEG C after dipping
Be evaporated, 120 DEG C oven drying 12.0 hours, roasted 4.0 hours at 500 DEG C after grinding.
By it is above-mentioned prepare catalyst tabletting and be crushed to 20~40 mesh be used for catalytic performance test.
Evaluating catalyst method and condition:
As described in comparative example 1, reaction result is shown in Table 2 for evaluation and analysis method.
Embodiment 5
Catalyst preparation:
(1) preparation of Pt nanoparticle:
Claim tetra- ammino platinum nitrate aqueous solution (0.93wt%) of 5.0ml to configure 20ml aqueous solution, 0.8g cetyl three is added
Ammonio methacrylate (CTAC) ultrasonic disperse 30 minutes, until the transparent non-foam of solution, obtains Pt (NH3)4 2+- CTAC aqueous solution uses
Concentration is that 0.5M ammonia spirit adjusts pH 11, stirs 30 minutes, the hydrazine hydrate solution of the amount of 8 times of Pt substances is added at room temperature,
Reduction obtains Pt nanoparticle rapidly.
(2) preparation of hydroisomerisation catalysts:
10.0g molecular sieve is added in the CTAC solution of the particle containing Pt of above-mentioned preparation, is stirred 4 hours, filtration washing,
120 DEG C of dryings obtain the hydroisomerisation catalysts in air after 500 DEG C of roastings.
By it is above-mentioned prepare catalyst tabletting and be crushed to 20~40 mesh be used for catalytic performance test.
Evaluating catalyst method and condition:
As described in comparative example 1, reaction result is shown in Table 2 for evaluation and analysis method.
Table 2
| Comparative example 2 | Embodiment 5 | |
| Pt presoma | Four ammino platinum nitrates | Four ammino platinum nitrates |
| Pt load capacity/% | 0.5 | 0.5 |
| CTAC/g | - | 0.8 |
| pH | - | 11 |
| Pt: hydrazine hydrate (molar) | - | 1:6 |
| Pt average grain diameter/nm | 5.5 | 2.7 |
| Dispersion degree/% | 20.6 | 41.9 |
| Hexadecane alkane conversion ratio/% | 60.2 | 86.3 |
| Isoparaffin selectivity/% | 78.9 | 82.6 |
| Isoparaffin yield/% | 47.5 | 71.3 |
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (10)
1. a kind of preparation method of active metal high dispersive hydroisomerization catalyst, it is characterised in that: containing cation first
In the Pt aqueous metal salt of surfactant, using the Pt nanoparticle of hydrazine hydrate reduction method preparation uniform particle diameter；It will divide again
It after son sieve is impregnated in the aqueous solution of the prepared nanoparticle containing Pt sufficiently absorption, washs, dry, roasting obtains hydroisomerization
Catalyst.
2. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 1, feature exist
In: specific steps include:
(1) ultrasound point the preparation of Pt nanoparticle: is carried out after Pt presoma is mixed with the aqueous solution of cationic surfactant
It dissipates, then stirs to transparent, obtain Pt- aqueous surfactant solutions；The pH to 11 ~ 13 that Pt- aqueous surfactant solutions are adjusted with ammonium hydroxide, is stirred
It mixes 30 minutes, hydrazine hydrate solution is added under room temperature and restores rapidly, obtains Pt nanoparticle；
(2) preparation of hydroisomerisation catalysts: molecular sieve is added in the activator solution of the particle containing Pt of above-mentioned preparation,
Stirring 4 hours, filtration washing is dry, after roasting in air, obtains the hydroisomerisation catalysts.
3. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 2, feature exist
In: the Pt presoma is four ammino platinum of acetic acid, four ammino platinum of nitric acid, four ammino platinum of nitrous acid, four ammino platinum of sulfuric acid or four ammonia
Close one or more of platinum chloride；The Pt content is 0.01 ~ 2 wt% of catalyst quality.
4. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 2, feature exist
In: cationic surfactant is cetyl trimethylammonium bromide CTAB, hexadecyltrimethylammonium chloride CTAC, dodecane
Base dimethyl tertiary amine acetate, octadecyl dimethyl benzyl ammonium ammonium chloride, cetyl pyridinium quaternary ammonium salt, double octadecyls two
One or more of methyl bromide ammonium cationic surfactant；The concentration of the cationic surfactant be 0.01 ~
0.1 mol/L。
5. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 2, feature exist
In: the molar ratio of the hydrazine hydrate and Pt metal is in 2 ~ 10:1.
6. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 2, feature exist
In: the time of ultrasonic disperse is 10 ~ 60 min in step (1)；Pt- aqueous surfactant solutions are adjusted with ammonium hydroxide in step (1)
PH to 11.5 ~ 12.5.
7. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 2, feature exist
In: the recovery time is 0.5 ~ 2 hour after hydrazine hydrate solution is added in step (1).
8. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 2, feature exist
In: the molecular sieve for the catalyst quality 98%-99.99% being added in step (2) is one-dimensional ten yuan of ducts point of moderate strength acidity
Son sieve, be SAPO-11, ZSM-22, ZSM-23, SAPO-31, SAPO-41, ZSM-48, SSZ-32, one of SSZ-32x or
It is a variety of.
9. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 2, feature exist
In: the drying temperature in step (2) is 100 ~ 150 DEG C, and drying time is 12 ~ 24 hours.
10. a kind of preparation method of active metal high dispersive hydroisomerization catalyst according to claim 2, feature
Be: the maturing temperature in step (2) is 400 ~ 600 DEG C, and calcining time is 3.0 ~ 6.0 hours.
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