CA1175073A - Process for preparing aromatics-rich hydrocarbons from synthesis gas - Google Patents
Process for preparing aromatics-rich hydrocarbons from synthesis gasInfo
- Publication number
- CA1175073A CA1175073A CA000412208A CA412208A CA1175073A CA 1175073 A CA1175073 A CA 1175073A CA 000412208 A CA000412208 A CA 000412208A CA 412208 A CA412208 A CA 412208A CA 1175073 A CA1175073 A CA 1175073A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- palladium
- mixture
- zeolite
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 51
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 51
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 137
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000010457 zeolite Substances 0.000 claims abstract description 36
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 35
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 34
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000006069 physical mixture Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 150000002927 oxygen compounds Chemical class 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910017518 Cu Zn Inorganic materials 0.000 description 5
- 229910017752 Cu-Zn Inorganic materials 0.000 description 5
- 229910017943 Cu—Zn Inorganic materials 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- BEZDDPMMPIDMGJ-UHFFFAOYSA-N pentamethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1C BEZDDPMMPIDMGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/10—Magnesium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
PROCESS FOR PREPARING AROMATICS-RICH
HYDROCARBONS FROM SYNTHESIS GAS
ABSTRACT OF THE DISCLOSURE
A process for preparing a hydrocarbon mixture, rich in aromatic hydrocarbons, is disclosed in which a mixed gas containing carbon monoxide and hydrogen, that is, the so-called "synthesis gas", is subjected to a catalytic reaction with a mixed catalyst comprising a physical mixture of (1) a palladium catalyst comprising palladium supported on a carrier and (2) a zeolite catalyst, thereby to produce an aromatics-rich hydrocarbon mixture.
HYDROCARBONS FROM SYNTHESIS GAS
ABSTRACT OF THE DISCLOSURE
A process for preparing a hydrocarbon mixture, rich in aromatic hydrocarbons, is disclosed in which a mixed gas containing carbon monoxide and hydrogen, that is, the so-called "synthesis gas", is subjected to a catalytic reaction with a mixed catalyst comprising a physical mixture of (1) a palladium catalyst comprising palladium supported on a carrier and (2) a zeolite catalyst, thereby to produce an aromatics-rich hydrocarbon mixture.
Description
5(~73 --1 ~
PROCESS FOR PREPARING ARO~TICS-RICE
HYDROCARBONS FROM SYNTHESIS GAS
This invention relates to an improvement in the known process for converting the so~called "synthesis gas" consisting essentially of carbon monoxide and hydrogen into a hydrocarbon mixture and, more particu-larly~ to a process for preparing a hydrocarbon mixture in which synthesis gas is subjected to a catalytic reaction using a mixed catalyst consisting essentially of a mixture of (1) a supported palladium catalyst comprising palladium supported on a carrier and (2) a zeolite catalyst, whereby to obtain a hydrocarbon mixture which is rich in aromatic substances.
The Fischer-Tropsch synthesis has been used for a long time for the synthesis of syn-thetic liquid fuels from synthesis gas. This method conventionally employs a transition metal, such as Fe, Co or Ni, as the catalyst. The resulting products are mostly straight-chain paraffins and olefins, and only a small amount of aromatic hydrocarbons are produced. Also, the __ carbon atom number distribution of the products spans a wide range. This method is also subject to a certain limitation in the yield when it is used for obtaining a ,. ~
S(~7~
gasoline (C5-C12) fraction, and, further, the obtained gasoline fraction is low in octane number.
There has also been proposed a hydrocarbon prepara-tion process in which, first, methanol is synthesized from a mixed gas of carbon monoxide and hydrogen by using a methanol-synthesizing catalyst, and then the obtained methanol is reacted with a zeolite catalyst, exemplified by zeolite catalyst ZSM-5 (a commercial product available from Mobil Corporation), thereby to obtain a hydrocarbon mixture rich in gasoline fractions of high octane value and mostly composed of isoparaffin and aromatic compounds. However, because this method is a two-stage process comprising (1) the initial prepara-tion of methanol from the synthesis gas ~CO + H2) and
PROCESS FOR PREPARING ARO~TICS-RICE
HYDROCARBONS FROM SYNTHESIS GAS
This invention relates to an improvement in the known process for converting the so~called "synthesis gas" consisting essentially of carbon monoxide and hydrogen into a hydrocarbon mixture and, more particu-larly~ to a process for preparing a hydrocarbon mixture in which synthesis gas is subjected to a catalytic reaction using a mixed catalyst consisting essentially of a mixture of (1) a supported palladium catalyst comprising palladium supported on a carrier and (2) a zeolite catalyst, whereby to obtain a hydrocarbon mixture which is rich in aromatic substances.
The Fischer-Tropsch synthesis has been used for a long time for the synthesis of syn-thetic liquid fuels from synthesis gas. This method conventionally employs a transition metal, such as Fe, Co or Ni, as the catalyst. The resulting products are mostly straight-chain paraffins and olefins, and only a small amount of aromatic hydrocarbons are produced. Also, the __ carbon atom number distribution of the products spans a wide range. This method is also subject to a certain limitation in the yield when it is used for obtaining a ,. ~
S(~7~
gasoline (C5-C12) fraction, and, further, the obtained gasoline fraction is low in octane number.
There has also been proposed a hydrocarbon prepara-tion process in which, first, methanol is synthesized from a mixed gas of carbon monoxide and hydrogen by using a methanol-synthesizing catalyst, and then the obtained methanol is reacted with a zeolite catalyst, exemplified by zeolite catalyst ZSM-5 (a commercial product available from Mobil Corporation), thereby to obtain a hydrocarbon mixture rich in gasoline fractions of high octane value and mostly composed of isoparaffin and aromatic compounds. However, because this method is a two-stage process comprising (1) the initial prepara-tion of methanol from the synthesis gas ~CO + H2) and
(2) the succeeding reaction of the thus-produced methanol to obtain the hydrocarbon mixture, this method is disadvantageous not only in respect of its relatively low energy efficiency or from a thermodynamic viewpoint, but also because it requires a high pressure fo.r the reactions. Further, the yield of the obtained hydrocarbon mixture is low.
Recently, advanced studies have been made on a method for directly obtaining a hydrocarbon mixture, by a single-stage process, employing a combination of (1) a methanol-synthesizing catalyst or a catalyst for the Fischer-Tropsch synthesis and (2) a zeolite-type methanol-conversion catalyst. (See U.S. Patents 4 096 163, 4 180 516, 4 188 336, 4 086 262, 3 894 102, 4 157 338 and 4 093 643).
This method is capable of producing a hydrocarbon ~ mixture in a satisfactorily high yield, under a rela-tively low pressure, because, according to this method, methanol synthesized by using said mixed catalyst is -r~D~m~
S[37~ ' rapidly converted into the hydrocarbons, without incur-ring thermodynamic restrictions.
~ owever, when there is used a mixed catalyst conslsting of (1) the conventional Cu-Zn-Cr system, methanol-synthesizing catalyst or a Fischer-Tropsch catalyst containing Rh, Ru or Os as the active catalyst metal, and using SiO2 or A12O3 as the carrier and (2) a zeolite catalyst used as the catalyst for converting methanol into the hydrocarbons, there occurs an .
excessive reduction of the activity of the mixed catalyst over a period of several hundred hours of the i~
reaction time because the zeolite-type catalyst, exemplified by zeolite catalyst ZSM-5, tends to cause .
. . carbon deposition on the catalyst, and, also, there takes place a change in the product composition with the.
passing of reaction time. Further, when there is used a combination of (1) the aforementioned conventional methanol-synthesizing catalyst and (2) the zeolite catalyst, the hydrogen gas in the synthesis gas causes, rather quickly, a hydrogenation reaction of the intermediate products, so that the resulting final reaction product tends to turn out to be a para~fin-rich product~ Also, hydrogen produced in the reaction can scarcely be used for removing carbon deposits on -the zeolite catalyst. Moreover, the act.ivity of the methanol-synthesizing catalyst is relatively quickly reduced at a temperature around the temperature employed for the methanol-conversion reaction, resulting in an excessive reduction in the performance of the methanol synthesis.
~~ The present inventors have carried out extensive studies concerning the preparation of hydrocarbon mixtures from synthesis gas by a ca~alytic reaction, using a combination of (1) a methanol-synthesizing catalyst and ~2) a methanol-conversion catalyst and, as a result, have obtained the novel findings described below.
All of the methanol-synthesizing catalysts which 3 have hitherto been used in this method show their catalytic activities in a relatively low temperature range, usually in the range of 250 to 300C, and the higher the pressure, the more advantageous is the - -~
process.
Generally, an increase in the methanol synthesis reaction temperature leads to a reduction in the 3 methanol yield and, instead of methanol,.generation of dimethyl ether is encouraged and, also, production of C2 and a limited amount of hydrocarbons is caused. On.
the other hand, a zeolite catalyst, when used for a methanol-conversion reaction, shows its highest activity !
usually in the temperature range of 350 to 400C, and the higher the pressure applied, the more advantageous is the process. Thus, the two different types of catalysts differ in their optimum reaction temperature ranges.
Also, when there is used the combination of (1) a Fischer-Tropsch synthesis catalyst and t2) a zeolite catalyst, because these two catalysts also differ in their optimum reaction temperature ranges, as in the case of the combination of the methanol-synthesizing catalyst and the zeolite catalyst, there occurs a predominant production of gaseous hydrocarbons in the temperature range where the zeolite catalyst acts most effectively.
Thus, in using the known mixed catalysts for the one-step synthesis of hydrocarbons from carbon monoxide ~ ~75073 and hydrogen, problems arise with respect to the reaction rate and the product selectivity because t~e two catalysts used differ in their optimum reaction con-ditions due to their different reaction characteristics>
Also, an increase of the reaction temperature causes a reduction in the activity of the methanol-synthesizing catalyst, resulting in not only a decrease in the reaction rate, but also in a serious adverse effect on the product selectivity.
The hitherto proposed methanol-synthesizing cata-lysts are essentially high-quality hydrogenation cata-lysts by which the olefins, produced as intermediates, are easily hydrogenated, so that the obtained hydro--~ carbons are mostly of the lower saturated aliphatic hydrocarbon type, and there are produced only small amounts of liquid hydrocarbons in the nature of a gasoline fraction and aromatic products. Also, the reaction requires a high hydrogen consumption and hence is uneconomical.
Also, when there is used a Cr-Zn or Cu-Zn type catalyst, which are typical examples of the conventional methanol-synthesizing catalysts, the major products are oxygen-co~taining compounds and, accordingly, the amounts o the olefin and aromatic hydrocarbon products produced are relatively low.
Further, in case there occurs a reduc-tion in the catalyst activity due to the accumulation of carbon deposits on the catalyst, when a mi~ed catalyst including a zeolite catalyst is being used, it is
Recently, advanced studies have been made on a method for directly obtaining a hydrocarbon mixture, by a single-stage process, employing a combination of (1) a methanol-synthesizing catalyst or a catalyst for the Fischer-Tropsch synthesis and (2) a zeolite-type methanol-conversion catalyst. (See U.S. Patents 4 096 163, 4 180 516, 4 188 336, 4 086 262, 3 894 102, 4 157 338 and 4 093 643).
This method is capable of producing a hydrocarbon ~ mixture in a satisfactorily high yield, under a rela-tively low pressure, because, according to this method, methanol synthesized by using said mixed catalyst is -r~D~m~
S[37~ ' rapidly converted into the hydrocarbons, without incur-ring thermodynamic restrictions.
~ owever, when there is used a mixed catalyst conslsting of (1) the conventional Cu-Zn-Cr system, methanol-synthesizing catalyst or a Fischer-Tropsch catalyst containing Rh, Ru or Os as the active catalyst metal, and using SiO2 or A12O3 as the carrier and (2) a zeolite catalyst used as the catalyst for converting methanol into the hydrocarbons, there occurs an .
excessive reduction of the activity of the mixed catalyst over a period of several hundred hours of the i~
reaction time because the zeolite-type catalyst, exemplified by zeolite catalyst ZSM-5, tends to cause .
. . carbon deposition on the catalyst, and, also, there takes place a change in the product composition with the.
passing of reaction time. Further, when there is used a combination of (1) the aforementioned conventional methanol-synthesizing catalyst and (2) the zeolite catalyst, the hydrogen gas in the synthesis gas causes, rather quickly, a hydrogenation reaction of the intermediate products, so that the resulting final reaction product tends to turn out to be a para~fin-rich product~ Also, hydrogen produced in the reaction can scarcely be used for removing carbon deposits on -the zeolite catalyst. Moreover, the act.ivity of the methanol-synthesizing catalyst is relatively quickly reduced at a temperature around the temperature employed for the methanol-conversion reaction, resulting in an excessive reduction in the performance of the methanol synthesis.
~~ The present inventors have carried out extensive studies concerning the preparation of hydrocarbon mixtures from synthesis gas by a ca~alytic reaction, using a combination of (1) a methanol-synthesizing catalyst and ~2) a methanol-conversion catalyst and, as a result, have obtained the novel findings described below.
All of the methanol-synthesizing catalysts which 3 have hitherto been used in this method show their catalytic activities in a relatively low temperature range, usually in the range of 250 to 300C, and the higher the pressure, the more advantageous is the - -~
process.
Generally, an increase in the methanol synthesis reaction temperature leads to a reduction in the 3 methanol yield and, instead of methanol,.generation of dimethyl ether is encouraged and, also, production of C2 and a limited amount of hydrocarbons is caused. On.
the other hand, a zeolite catalyst, when used for a methanol-conversion reaction, shows its highest activity !
usually in the temperature range of 350 to 400C, and the higher the pressure applied, the more advantageous is the process. Thus, the two different types of catalysts differ in their optimum reaction temperature ranges.
Also, when there is used the combination of (1) a Fischer-Tropsch synthesis catalyst and t2) a zeolite catalyst, because these two catalysts also differ in their optimum reaction temperature ranges, as in the case of the combination of the methanol-synthesizing catalyst and the zeolite catalyst, there occurs a predominant production of gaseous hydrocarbons in the temperature range where the zeolite catalyst acts most effectively.
Thus, in using the known mixed catalysts for the one-step synthesis of hydrocarbons from carbon monoxide ~ ~75073 and hydrogen, problems arise with respect to the reaction rate and the product selectivity because t~e two catalysts used differ in their optimum reaction con-ditions due to their different reaction characteristics>
Also, an increase of the reaction temperature causes a reduction in the activity of the methanol-synthesizing catalyst, resulting in not only a decrease in the reaction rate, but also in a serious adverse effect on the product selectivity.
The hitherto proposed methanol-synthesizing cata-lysts are essentially high-quality hydrogenation cata-lysts by which the olefins, produced as intermediates, are easily hydrogenated, so that the obtained hydro--~ carbons are mostly of the lower saturated aliphatic hydrocarbon type, and there are produced only small amounts of liquid hydrocarbons in the nature of a gasoline fraction and aromatic products. Also, the reaction requires a high hydrogen consumption and hence is uneconomical.
Also, when there is used a Cr-Zn or Cu-Zn type catalyst, which are typical examples of the conventional methanol-synthesizing catalysts, the major products are oxygen-co~taining compounds and, accordingly, the amounts o the olefin and aromatic hydrocarbon products produced are relatively low.
Further, in case there occurs a reduc-tion in the catalyst activity due to the accumulation of carbon deposits on the catalyst, when a mi~ed catalyst including a zeolite catalyst is being used, it is
3~ necessary to:perform a reduction treatment under severe --~ high-temperature conditions after carbon removal by oxidation. The hitherto proposed catalysts, particularly Ru- or Os-type catalysts, are apt to be ~175~7;~
converted into volatile oxides during the oxidation treatment and, thus, they leave the catalyst layer.
It was thus found that the method for obtaining aromatic hydrocarbons by a single step process from carbon monoxlde and hydrogen, by using a mixed catalyst conslsting essentially of a conventional methanol-synthesizing catalyst and a methanol-conversion catalyst, has the disadvantagP that, due to the different reaction conditions in the respective reaction stages, the catalysts suffer excessive changes in their activities, resulting in a rapid reduction in their activities with the passing of time and/or a change in the composition of the final products obtained, As a result of various studies conducted by the present inventors for the purpose of eliminating said disadvantage of the conventional one-step process for producing hydrocarbons from synthesis gas by using a mixed catalyst, the present inventors discovered a novel mixed catalyst which exhibits only a small reduction in its activity during long-term use and which also causes substantially no change in the composition of the final product obtained. Further, while the products obtained from the one-step hydrocarbon preparation process, using a mixed catalyst consisti.ng of said conventional methanol-synthesizing catalyst and a methanol-conversion catalyst, are mostly intended to provide a gasoline fraction having a carbon atom number range of from 6 to 8, it was found that the use of the mixed catalyst, according to this invention, makes it possible to selectively obtain a relatively high proportion of _ higher aromatic hydrocarbons having a carbon atom number range of from 10 to 12.
S~ ~3 According to one aspect of the present invention there is provided a catalytic process for preparing a hydrocarbon mixture which comprises:
contacting a synthesis gas consisting essentially of carbon monoxide and hydrogen, with a mixed catalyst comprising a physical admixture of (1) particles of a supported palladium catalyst comprising palladium supported on a solid catalyst carrier and (2) particles of zeolite catalyst effective to convert methanol to a liquid hydrocarbon gasoline-range mixture substantially free of oxygen compounds, thereby to produce an aromatics-rich hydrocarbon mixture.
According to a further aspect of the present invention there is provided a process for preparing a hydrocarbon mixture, which comprises flowing a stream of synthesis gas consisting essentially of carbon monoxide and hydrogen, wherein the molar ratio of hydrogen/carbon monoxide is in the range of from 0.5/1.0 to 2 0/1.0, at a temperature of from 3~0 to 400C, at a pressure of from 10 to 100 kg/cm2G, through a catalyst bed consisting essentially of a physical mixture of (1) particles of supported palladium catalyst consisting essentially of from 1 to 10 wt% of palladium metal supported on a neutral or weakly alkaline catalyst carrier selected from the group consisting of silica, alumina, magnesia, calcium oxide, lanthanum oxide and zirconium oxide, and (2) particles of zeolite catalyst effective to convert methanol to an aromatics-rich, gasoline-range mixture of hydrocarbons substan-tially free of oxygen-containing compounds, said zeolite catalyst being acidic, havinga pore diameter of from 5 to lO Angstroms and having a silica to alumina mole ratio of at least 12, the weight ratio of palladium catalyst/zeolite catalyst in said mixture being from 1.0/0.25 to 1.0/4.0, whereby to produce a hydrocarbon mixture rich in aromatic compounds including methylpolysubstituted benzenes, said hydrocarbon mixture being substantially free of oxygen-contain-ing compounds.
~`~
- 6a _ 5(?73 Thus, the present invention provides a novel hydrocarbon preparation process characterized in that a mixed gas containing carbon monoxide and hydrogen, that is, the so-called synthesis gas, is subjected to a catalytic reaction by contact with a mixed catalyst comprising a physical mixture of (1) a supported palladium catalyst comprising palladium supported on a carrier and (2~ a zeolite catalyst effective to convert methanol primarily to a gasoline fraction (C5-C12), thereby to produce an aromatics-rich hydrocarbon mixture as a final product.
The aromatic hydrocarbons contained in the hydro-carbon mixture, obtained according to the process of this invention, are mostly methyl-polysubstituted benzenes. Heretofore, these products have been obtained by using a so-called BTX fraction, such as benzene or toluene, but if the catalyst of this invention is used, it is possible to synthesize said methyl-polysubs-tituted benzenes, with high selectivity, by a. single~step process from a starting gaseous mixture of carbon monoxide and hydrogen.
An important advantage of the catalyst accordiny to this invention is that it makes it possible to control the product composition selectively within a certain range by adjusting the mixing ratio of the two types of catalysts. In other words, it is possible to obtain desi.red products, with high selectivity, by suitably controlling the methanol-synthesizing reaction and the methanol-conversion reaction.
Another advantage of the catalyst of this invention is that because the palladium ca-tal.yst used as the methanol-synthesizing catalyst is stable in a high temperature range, production of oxygen-containing ~ ~75~ ~3 compounds is markedly suppressed as compared with the case wherein a conventional methanol-synthesizing catalyst is used.
The synthesis yas used in this invention is a gaseous mixture principally composed of hydrogen and carbon monoxide, which can be obtained from a car~onaceous fuel, such as coal, natural gas or petroleum, in a known way. The synthesis gas may contain, besides hydrogen and carbon monoxide, small quantities of carbon dioxide, methane, nitrogen and the like. The molar ratio of hydrogen to carbon monoxide in the synthesis gas is preferably within the range of from 0.5-2.0/1.0 for the purpose of this invention.
Generally, the higher the molar amount of CO, relative to hydrogen, the higher is the yield of the aromatic hydrocarbons obtained.
The mixed catalyst of this invention is essentially composed of the two components, that is, (1) a supported palladium catalyst comprising palladium supported on a carrier and l2) a zeolite catalyst.
~ s the carrier for the palladium catalyst, there can be used silica, alumina, magnesia, calcium oxide, lanthanum oxide and the like. However, proper selection of the palladium-supporting carrier is an important factor in practicing the present inventionr and it is essential that the carrier has suitable pores and that it is not high in acidity. If the carrier has strong acidity, the selectivity of the methanol synthesis is lowered so as to cause an excessive production of methane.
_ For this reason, it is not preferred, for the purposes of this invention, to have the palladium directly carried or supported on the zeolite catalyst.
7S~'3 Preferred examples of the carrier for palladium, used in this invention, are neutral or weakly alkaline oxides, such as silica gel, magnesia, calcium oxide, lanthanum oxide and zirconium oxide.
It is preferred that the supported palladium catalyst contains from 1 to 10 wt.~ of palladium metal and the balance is the carrier.
A catalyst comprising palladium supported on said carrier is low in its capacity for hydrogenating oleEins, so that the production of olefins is restricted, thereby allowing selecti~e and increased production of aromatic hydrocarbon products.
A preferred embodiment of the first catalyst component of the mixed catalyst, using palladium sup-ported on silica gel, will now be described. Silica gel of 20-40 mesh size is fed into an acidic aqueous solution (made acidic with hydrochloric acid) in which palladium chloride has been dissolved to provide a palladium concentration of 1 to 10% by weight. The mixed solution is evaporated to dryness over a hot bath.
After drying in air at 120C, the mixture is reduced in a hydrogen stream at temperatures of 100C, 200C and 400C in succession, for a total period of several hours, thereby to obtain the first catalyst component.
The palladium catalyst thus produced has palladium uniformly dispersed to a favorable degree on the carrier surface and it is suited for use, in admix~ure with the zeolite catalyst, as a mixed catalyst in the process of this invention.
As for the zeolite catalyst used as a methanol---- conversion catalyst, it is desirable that the zeolite catalyst has a pore diàmeter of 5-10 A and a relatively strong acidity. Preferred examples of such zeolite ~.~L75~'3 catalysts are the commercially available zeolites ZSM-5 of Mobil Corporation and~ ordenite (available under the commercial name "Zeolon"). In general, acidic crystalline aluminosilicates (zeolites) in which the silica to alumina ratio i5 at least 12, such as those disclosed in U.S. Patent NoO 4 180 516, are usable in the process of this invention.
Incidentally', the zeolite must be converted into a proton type in the conventional way before it is used.
The mixing weight ratio of the palladium catalyst to the zeolite catalyst can be suitably selected within the range of l:0.1-10, preferably 1:0.25-4.
The mixed catalyst of this invention thus can have a mixing ratio that varies over a very wide range. It shows a high reactivity and is also extremely high in selectivity for producing aromatic hydrocarbons, particularly methyl-polysubstituted benzenes, over a wide range of mixing ratios. Moreover, the catalyst of this invention exhibits long retention of catalytic activity and the catalytic activity remains unchanged for a long time even when the palladium catalyst/zeolite catalyst mixing weight ratio is changed. Hence, tha distribution tselectivi~y) of the products obtained does not change widely over time.
The physically mixed catalyst of this invention can be prepared in various conventional ways.
In the process of this invention, the synthesis gas is contacted with said mixed catalyst at a temperature of 250 to 450C, preferably 300 to 400C, under a pressure of 5-lO0 kg/cm2G, preferably lO-lO~ kg/cm2G.
The catalyst can be used either in the form of a fixed bed or in the form of a fluidized bed. By carrying out the reaction under these conditlons, there can be ~D~
~75~73 obtained hydrocarbons rich in aromatic compounds, particularly methyl-polysubstituted benzenes (tetra-methylbenzene, pentamethylbenzene and hexamethylbenzene), and these hydrocarbons can be separated and recovered in a conventional way~
The present invention is further described herein-below by reference to the following illustrative examples thereof, but the scope of the invention is not limited by these examples.
Example 1 In separate tests, 5g of a mixed catalyst composed of a 1:1 (parts by weight) mixture of (1) a palladium-on-silica catalyst tPd: 4 wt%) and (2) either ZSM-5 or -Zeolon, was fed into a fixed-bed, pressure-resistant, circulation-type reactor. The stainless steel reactor body had an inner diameter of 10 rNm, and the length of the catalyst layer was 10-15 mm.
A gaseous mixture of carbon monoxide and hydrogen (H2/CO molar ratio = 2.0) was fed into said reactor at a flow rate of 225 ml/min (W/F = 8~9y of ca-talyst-hr/mol, W = number of grams of catalyst, F = number oE moles of supplied gas per hour) and was reacted at a temperature of 355C under a pressure of 20 kg/cm G. The reaction products were determined by analyzing the outlet gas by gas chromatography.
The results of the reac-tion showed hydrocarbon yields of 11 wt% and 8. 3 wt% ~C-based wt%). These values are not significantly-higher, as compared with the case of using a catalyst containing a differerlt __ 30 methanol-synthesizing catalyst, but it was noteworthy that the CO2 yield was relatively low, or about 2-5~o ~ ~75~
As for the product hydrocarbon distribution, there was obtained a very high aromatic selectivity of about 35% and 50~, respectively.
The results are shown in the following table. For the purpose of comparison, there are also shown the results obtained by using a zeolite catalyst combined with a conventional methanol-synthesizing catalyst (Cu + Zn~. -._ , ~ ~7S~'73 !
Catalyst Pd/SiO2+ZSM-5Pd/SiO2+ZeolonCu-Zn+ZSr~5 Hydrocarbon yield 11.0 8 3 11.0 (C-base wt%) Oxygen-containing trace 0.1 0. 6 car~?ounds C2 (%) 5.5 2~5 11.0 Hydrocar~on distri-bution (C--wt%) Aliphatic Cl .7.5 9.2 7.7 C2 15 . 1 14. 5 13 . 5 C3 30.8 11.2 26.9 C4 5.9 6.5 12.7 C5 2.4 2.7 9.1 C6 1.5 1.8 10.4 C7 0.3 1.7 7.5 C8 0.9 1.2 8.4 Total 64.4 48.8 96.2 Aromatic C7 8 - 0'4 Cg 0.8 0.6 1~1 Clo 20.4 107 2.0 Cll 12. 5 20.6 0-4 C12 2.0 22.2 0.
13 - 5.6 l~tal 35.7 51.1 3.9 -Examp le 2 Experiments were carried out by using a Pd on SiO2/ZSM-5 mixed catalyst under the same conditions as ~LiL'75~)~3 !
14- ~
described in Example 1 except that the hydrogen to carbon monoxide molar ratio of the synthesis gas was cha~ged. The hydrocarbon product distributions in the respective tests are shown in the following table.
For the purpose of comparison, there are also sho~m the results obtained by using a Cu-Zn/ZSM-5 mixed catalyst.
Catalyst _ Pd/SiO~+Z5~5 ~ Zn+ZSM-5 - - --H2/CO molar ratio 0.5 1.0 2.0 0.5 1.0 2.0 Hydrocarbon yield 4.0 8.0 11~0 4.6 6.4 11.0 (C-base wt%) Breakdown of the obtained hydro-carbons according to carbon number (wt%) 29.840.251.0 60.0 65.1 70.2 C - C 10.28.0 8.2 30.1 30.0 28.3 over C8 65.255.730.4 10.1 5.0 1.9 ArcnEItic hydrocarbon content in obtained 68.160.535.0 5.0 4.2 2.9 hydrocarbons (wt%) Example 3 This experiment was conducted under the same conditions as described in Example l except for changing of the mixing ratio of Pd/SiO2 to ZSM-5. The product yield and aromatic selectivity are shown in the following table.
For reference purposes, there are also shown the results obtained by using a Cu-Zn/ZSM-5 mixed catalyst.
~75~73 Catalyst I Pd/SiO2+ZSM-5 Cu-Zn+ZSM-5 Catalyst mixing 20 25 50 75 2025 50 75 ratio* ~wt%~
Hydrocar~on yield 8.9 9.2 11.0 12.1 20.8 24.9 11.0 6.1 (C-base wt%) O~ygen-containing O.O O.O O~0 0.4 0.2 0.2 0.4 1.0 campounds (wt96) Arcmatic selecti- 62.1 59.2 35.4 20.1 1.2 2.0 5.3 2.9 vity (%) * Wt% of Pd/SiO2 or Cu-Zn in the mixed catalyst.
Example 4 Similar experiments were carried out by using silica gel, magnesium oxide, zirconium oxide and lanthanum oxide as the palladium-supporting carrier (Pd: I
converted into volatile oxides during the oxidation treatment and, thus, they leave the catalyst layer.
It was thus found that the method for obtaining aromatic hydrocarbons by a single step process from carbon monoxlde and hydrogen, by using a mixed catalyst conslsting essentially of a conventional methanol-synthesizing catalyst and a methanol-conversion catalyst, has the disadvantagP that, due to the different reaction conditions in the respective reaction stages, the catalysts suffer excessive changes in their activities, resulting in a rapid reduction in their activities with the passing of time and/or a change in the composition of the final products obtained, As a result of various studies conducted by the present inventors for the purpose of eliminating said disadvantage of the conventional one-step process for producing hydrocarbons from synthesis gas by using a mixed catalyst, the present inventors discovered a novel mixed catalyst which exhibits only a small reduction in its activity during long-term use and which also causes substantially no change in the composition of the final product obtained. Further, while the products obtained from the one-step hydrocarbon preparation process, using a mixed catalyst consisti.ng of said conventional methanol-synthesizing catalyst and a methanol-conversion catalyst, are mostly intended to provide a gasoline fraction having a carbon atom number range of from 6 to 8, it was found that the use of the mixed catalyst, according to this invention, makes it possible to selectively obtain a relatively high proportion of _ higher aromatic hydrocarbons having a carbon atom number range of from 10 to 12.
S~ ~3 According to one aspect of the present invention there is provided a catalytic process for preparing a hydrocarbon mixture which comprises:
contacting a synthesis gas consisting essentially of carbon monoxide and hydrogen, with a mixed catalyst comprising a physical admixture of (1) particles of a supported palladium catalyst comprising palladium supported on a solid catalyst carrier and (2) particles of zeolite catalyst effective to convert methanol to a liquid hydrocarbon gasoline-range mixture substantially free of oxygen compounds, thereby to produce an aromatics-rich hydrocarbon mixture.
According to a further aspect of the present invention there is provided a process for preparing a hydrocarbon mixture, which comprises flowing a stream of synthesis gas consisting essentially of carbon monoxide and hydrogen, wherein the molar ratio of hydrogen/carbon monoxide is in the range of from 0.5/1.0 to 2 0/1.0, at a temperature of from 3~0 to 400C, at a pressure of from 10 to 100 kg/cm2G, through a catalyst bed consisting essentially of a physical mixture of (1) particles of supported palladium catalyst consisting essentially of from 1 to 10 wt% of palladium metal supported on a neutral or weakly alkaline catalyst carrier selected from the group consisting of silica, alumina, magnesia, calcium oxide, lanthanum oxide and zirconium oxide, and (2) particles of zeolite catalyst effective to convert methanol to an aromatics-rich, gasoline-range mixture of hydrocarbons substan-tially free of oxygen-containing compounds, said zeolite catalyst being acidic, havinga pore diameter of from 5 to lO Angstroms and having a silica to alumina mole ratio of at least 12, the weight ratio of palladium catalyst/zeolite catalyst in said mixture being from 1.0/0.25 to 1.0/4.0, whereby to produce a hydrocarbon mixture rich in aromatic compounds including methylpolysubstituted benzenes, said hydrocarbon mixture being substantially free of oxygen-contain-ing compounds.
~`~
- 6a _ 5(?73 Thus, the present invention provides a novel hydrocarbon preparation process characterized in that a mixed gas containing carbon monoxide and hydrogen, that is, the so-called synthesis gas, is subjected to a catalytic reaction by contact with a mixed catalyst comprising a physical mixture of (1) a supported palladium catalyst comprising palladium supported on a carrier and (2~ a zeolite catalyst effective to convert methanol primarily to a gasoline fraction (C5-C12), thereby to produce an aromatics-rich hydrocarbon mixture as a final product.
The aromatic hydrocarbons contained in the hydro-carbon mixture, obtained according to the process of this invention, are mostly methyl-polysubstituted benzenes. Heretofore, these products have been obtained by using a so-called BTX fraction, such as benzene or toluene, but if the catalyst of this invention is used, it is possible to synthesize said methyl-polysubs-tituted benzenes, with high selectivity, by a. single~step process from a starting gaseous mixture of carbon monoxide and hydrogen.
An important advantage of the catalyst accordiny to this invention is that it makes it possible to control the product composition selectively within a certain range by adjusting the mixing ratio of the two types of catalysts. In other words, it is possible to obtain desi.red products, with high selectivity, by suitably controlling the methanol-synthesizing reaction and the methanol-conversion reaction.
Another advantage of the catalyst of this invention is that because the palladium ca-tal.yst used as the methanol-synthesizing catalyst is stable in a high temperature range, production of oxygen-containing ~ ~75~ ~3 compounds is markedly suppressed as compared with the case wherein a conventional methanol-synthesizing catalyst is used.
The synthesis yas used in this invention is a gaseous mixture principally composed of hydrogen and carbon monoxide, which can be obtained from a car~onaceous fuel, such as coal, natural gas or petroleum, in a known way. The synthesis gas may contain, besides hydrogen and carbon monoxide, small quantities of carbon dioxide, methane, nitrogen and the like. The molar ratio of hydrogen to carbon monoxide in the synthesis gas is preferably within the range of from 0.5-2.0/1.0 for the purpose of this invention.
Generally, the higher the molar amount of CO, relative to hydrogen, the higher is the yield of the aromatic hydrocarbons obtained.
The mixed catalyst of this invention is essentially composed of the two components, that is, (1) a supported palladium catalyst comprising palladium supported on a carrier and l2) a zeolite catalyst.
~ s the carrier for the palladium catalyst, there can be used silica, alumina, magnesia, calcium oxide, lanthanum oxide and the like. However, proper selection of the palladium-supporting carrier is an important factor in practicing the present inventionr and it is essential that the carrier has suitable pores and that it is not high in acidity. If the carrier has strong acidity, the selectivity of the methanol synthesis is lowered so as to cause an excessive production of methane.
_ For this reason, it is not preferred, for the purposes of this invention, to have the palladium directly carried or supported on the zeolite catalyst.
7S~'3 Preferred examples of the carrier for palladium, used in this invention, are neutral or weakly alkaline oxides, such as silica gel, magnesia, calcium oxide, lanthanum oxide and zirconium oxide.
It is preferred that the supported palladium catalyst contains from 1 to 10 wt.~ of palladium metal and the balance is the carrier.
A catalyst comprising palladium supported on said carrier is low in its capacity for hydrogenating oleEins, so that the production of olefins is restricted, thereby allowing selecti~e and increased production of aromatic hydrocarbon products.
A preferred embodiment of the first catalyst component of the mixed catalyst, using palladium sup-ported on silica gel, will now be described. Silica gel of 20-40 mesh size is fed into an acidic aqueous solution (made acidic with hydrochloric acid) in which palladium chloride has been dissolved to provide a palladium concentration of 1 to 10% by weight. The mixed solution is evaporated to dryness over a hot bath.
After drying in air at 120C, the mixture is reduced in a hydrogen stream at temperatures of 100C, 200C and 400C in succession, for a total period of several hours, thereby to obtain the first catalyst component.
The palladium catalyst thus produced has palladium uniformly dispersed to a favorable degree on the carrier surface and it is suited for use, in admix~ure with the zeolite catalyst, as a mixed catalyst in the process of this invention.
As for the zeolite catalyst used as a methanol---- conversion catalyst, it is desirable that the zeolite catalyst has a pore diàmeter of 5-10 A and a relatively strong acidity. Preferred examples of such zeolite ~.~L75~'3 catalysts are the commercially available zeolites ZSM-5 of Mobil Corporation and~ ordenite (available under the commercial name "Zeolon"). In general, acidic crystalline aluminosilicates (zeolites) in which the silica to alumina ratio i5 at least 12, such as those disclosed in U.S. Patent NoO 4 180 516, are usable in the process of this invention.
Incidentally', the zeolite must be converted into a proton type in the conventional way before it is used.
The mixing weight ratio of the palladium catalyst to the zeolite catalyst can be suitably selected within the range of l:0.1-10, preferably 1:0.25-4.
The mixed catalyst of this invention thus can have a mixing ratio that varies over a very wide range. It shows a high reactivity and is also extremely high in selectivity for producing aromatic hydrocarbons, particularly methyl-polysubstituted benzenes, over a wide range of mixing ratios. Moreover, the catalyst of this invention exhibits long retention of catalytic activity and the catalytic activity remains unchanged for a long time even when the palladium catalyst/zeolite catalyst mixing weight ratio is changed. Hence, tha distribution tselectivi~y) of the products obtained does not change widely over time.
The physically mixed catalyst of this invention can be prepared in various conventional ways.
In the process of this invention, the synthesis gas is contacted with said mixed catalyst at a temperature of 250 to 450C, preferably 300 to 400C, under a pressure of 5-lO0 kg/cm2G, preferably lO-lO~ kg/cm2G.
The catalyst can be used either in the form of a fixed bed or in the form of a fluidized bed. By carrying out the reaction under these conditlons, there can be ~D~
~75~73 obtained hydrocarbons rich in aromatic compounds, particularly methyl-polysubstituted benzenes (tetra-methylbenzene, pentamethylbenzene and hexamethylbenzene), and these hydrocarbons can be separated and recovered in a conventional way~
The present invention is further described herein-below by reference to the following illustrative examples thereof, but the scope of the invention is not limited by these examples.
Example 1 In separate tests, 5g of a mixed catalyst composed of a 1:1 (parts by weight) mixture of (1) a palladium-on-silica catalyst tPd: 4 wt%) and (2) either ZSM-5 or -Zeolon, was fed into a fixed-bed, pressure-resistant, circulation-type reactor. The stainless steel reactor body had an inner diameter of 10 rNm, and the length of the catalyst layer was 10-15 mm.
A gaseous mixture of carbon monoxide and hydrogen (H2/CO molar ratio = 2.0) was fed into said reactor at a flow rate of 225 ml/min (W/F = 8~9y of ca-talyst-hr/mol, W = number of grams of catalyst, F = number oE moles of supplied gas per hour) and was reacted at a temperature of 355C under a pressure of 20 kg/cm G. The reaction products were determined by analyzing the outlet gas by gas chromatography.
The results of the reac-tion showed hydrocarbon yields of 11 wt% and 8. 3 wt% ~C-based wt%). These values are not significantly-higher, as compared with the case of using a catalyst containing a differerlt __ 30 methanol-synthesizing catalyst, but it was noteworthy that the CO2 yield was relatively low, or about 2-5~o ~ ~75~
As for the product hydrocarbon distribution, there was obtained a very high aromatic selectivity of about 35% and 50~, respectively.
The results are shown in the following table. For the purpose of comparison, there are also shown the results obtained by using a zeolite catalyst combined with a conventional methanol-synthesizing catalyst (Cu + Zn~. -._ , ~ ~7S~'73 !
Catalyst Pd/SiO2+ZSM-5Pd/SiO2+ZeolonCu-Zn+ZSr~5 Hydrocarbon yield 11.0 8 3 11.0 (C-base wt%) Oxygen-containing trace 0.1 0. 6 car~?ounds C2 (%) 5.5 2~5 11.0 Hydrocar~on distri-bution (C--wt%) Aliphatic Cl .7.5 9.2 7.7 C2 15 . 1 14. 5 13 . 5 C3 30.8 11.2 26.9 C4 5.9 6.5 12.7 C5 2.4 2.7 9.1 C6 1.5 1.8 10.4 C7 0.3 1.7 7.5 C8 0.9 1.2 8.4 Total 64.4 48.8 96.2 Aromatic C7 8 - 0'4 Cg 0.8 0.6 1~1 Clo 20.4 107 2.0 Cll 12. 5 20.6 0-4 C12 2.0 22.2 0.
13 - 5.6 l~tal 35.7 51.1 3.9 -Examp le 2 Experiments were carried out by using a Pd on SiO2/ZSM-5 mixed catalyst under the same conditions as ~LiL'75~)~3 !
14- ~
described in Example 1 except that the hydrogen to carbon monoxide molar ratio of the synthesis gas was cha~ged. The hydrocarbon product distributions in the respective tests are shown in the following table.
For the purpose of comparison, there are also sho~m the results obtained by using a Cu-Zn/ZSM-5 mixed catalyst.
Catalyst _ Pd/SiO~+Z5~5 ~ Zn+ZSM-5 - - --H2/CO molar ratio 0.5 1.0 2.0 0.5 1.0 2.0 Hydrocarbon yield 4.0 8.0 11~0 4.6 6.4 11.0 (C-base wt%) Breakdown of the obtained hydro-carbons according to carbon number (wt%) 29.840.251.0 60.0 65.1 70.2 C - C 10.28.0 8.2 30.1 30.0 28.3 over C8 65.255.730.4 10.1 5.0 1.9 ArcnEItic hydrocarbon content in obtained 68.160.535.0 5.0 4.2 2.9 hydrocarbons (wt%) Example 3 This experiment was conducted under the same conditions as described in Example l except for changing of the mixing ratio of Pd/SiO2 to ZSM-5. The product yield and aromatic selectivity are shown in the following table.
For reference purposes, there are also shown the results obtained by using a Cu-Zn/ZSM-5 mixed catalyst.
~75~73 Catalyst I Pd/SiO2+ZSM-5 Cu-Zn+ZSM-5 Catalyst mixing 20 25 50 75 2025 50 75 ratio* ~wt%~
Hydrocar~on yield 8.9 9.2 11.0 12.1 20.8 24.9 11.0 6.1 (C-base wt%) O~ygen-containing O.O O.O O~0 0.4 0.2 0.2 0.4 1.0 campounds (wt96) Arcmatic selecti- 62.1 59.2 35.4 20.1 1.2 2.0 5.3 2.9 vity (%) * Wt% of Pd/SiO2 or Cu-Zn in the mixed catalyst.
Example 4 Similar experiments were carried out by using silica gel, magnesium oxide, zirconium oxide and lanthanum oxide as the palladium-supporting carrier (Pd: I
4 wt%~. The results obtained are shown in the :Eollowing table.
The reaction conditions were as follows:
H~/CO : 1.0 Reaction pressure: 20 kgtcm G
W/F : 9.0g of catalyst-hr/mol Temperature : 360C
The other conditions were the same as in Example 1.
_ .
~.~'75~73 Carrier Pd/SiO Pd/MgO Pd/ZrO2Pd/Ln 03 +ZSM-52 +ZSM-5 ~ZSM-5 +Z5M-~
Hydrocarbon yield 9.2 6.6 10.0 15.3 (C-base wt~) Hydroc~rbon distribution (C~%) Cl - C4 38.5 38.8 41.3 43.3 C5 - C8 7.8 9.1 10.0 8.8 over C8 53.7 52.1 48.7 47.9 Aromatic hydro-carbon content 59.5 57.2 55.3 45.1 ~C-wt%) _
The reaction conditions were as follows:
H~/CO : 1.0 Reaction pressure: 20 kgtcm G
W/F : 9.0g of catalyst-hr/mol Temperature : 360C
The other conditions were the same as in Example 1.
_ .
~.~'75~73 Carrier Pd/SiO Pd/MgO Pd/ZrO2Pd/Ln 03 +ZSM-52 +ZSM-5 ~ZSM-5 +Z5M-~
Hydrocarbon yield 9.2 6.6 10.0 15.3 (C-base wt~) Hydroc~rbon distribution (C~%) Cl - C4 38.5 38.8 41.3 43.3 C5 - C8 7.8 9.1 10.0 8.8 over C8 53.7 52.1 48.7 47.9 Aromatic hydro-carbon content 59.5 57.2 55.3 45.1 ~C-wt%) _
Claims (8)
1. A catalytic process for preparing a hydrocarbon mixture which comprises: contacting a synthesis gas consisting essentially of carbon monoxide and hydrogen, with a mixed catalyst comprising a physical admixture of (1) particles of a supported palladium catalyst comprising palladium supported on a solid catalyst carrier and (2) particles of zeolite catalyst effective to convert methanol to a liquid hydrocarbon gasoline-range mixture substantially free of oxygen compounds, thereby to produce an aromatics-rich hydrocarbon mixture.
2. The process according to Claim 1, wherein said carrier is silica.
3. The process according to Claim 1 or 2, wherein said zeolite catalyst has a pore diameter of 5 to 10 .ANG..
4. The process according to Claim 1, wherein the catalytic reaction is performed at a temperature of 250°
to 450°C under a pressure of 5 to 100 kg/cm2G.
to 450°C under a pressure of 5 to 100 kg/cm2G.
5. The process according to Claim 1, wherein the hydrogen/carbon monoxide molar ratio of said synthesis gas is from 0.5/1.0 to 2.0/1Ø
6. The process according to Claim 1, wherein said supported palladium catalyst contains 1 to 10% by weight of palladium metal.
7. The process according to Claim 1, wherein the mixing ratio of said palladium catalyst/said zeolite is from 0.1/1.0 to 10/1.0 parts by weight.
8. A process for preparing a hydrocarbon mixture, which comprises flowing a stream of synthesis gas consisting essentially of carbon monoxide and hydrogen, wherein the molar ratio of hydrogen/carbon monoxide is in the range of from 0.5/1.0 to 2.0/1.0, at a temperature of from 300 to 400°C, at a pressure of from 10 to 100 kg/cm2G, through a catalyst bed consisting essentially of a physical mixture of (1) particles of supported palladium catalyst consisting essentially of from 1 to 10 wt% of palladium metal supported on a neutral or weakly alkaline catalyst carrier selected from the group consisting of silica, alumina, magnesia, calcium oxide, lanthanum oxide and zirconium oxide, and (2) particles of zeolite catalyst effective to convert methanol to an aromatics-rich, gasoline-range mixture of hydrocarbons substantially free of oxygen-containing compounds, said zeolite catalyst being acidic, having a pore diameter of from 5 to 10 Angstroms and having a silica to alumina mole ratio of at least 12, the weight ratio of palladium catalyst/zeolite catalyst in said mixture being from 1.0/0.25 to 1.0/4.0, whereby to produce a hydrocarbon mixture rich in aromatic compounds including methyl-polysubstituted benzenes, said hydrocarbon mixture being substantially free of oxygen-containing compounds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15427881A JPS5857494A (en) | 1981-09-29 | 1981-09-29 | Preparation of aromatic-rich hydrocarbon from synthetic gas |
| JP154278/81 | 1981-09-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1175073A true CA1175073A (en) | 1984-09-25 |
Family
ID=15580657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000412208A Expired CA1175073A (en) | 1981-09-29 | 1982-09-27 | Process for preparing aromatics-rich hydrocarbons from synthesis gas |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5857494A (en) |
| AU (1) | AU8867482A (en) |
| CA (1) | CA1175073A (en) |
| DE (1) | DE3236093A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2556237B1 (en) * | 1983-12-07 | 1986-09-19 | Raffinage Cie Francaise | NOVEL CATALYTIC COMPOSITION AND APPLICATION TO THE CONVERSION OF SYNTHESIS GAS TO A MIXTURE OF HIGH AROMATIC HYDROCARBONS |
| JPS61191517A (en) * | 1985-02-20 | 1986-08-26 | Toyo Eng Corp | Production of hydrocarbon rich in isoparaffin |
| JP5517681B2 (en) * | 2010-03-09 | 2014-06-11 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing aromatic compound |
-
1981
- 1981-09-29 JP JP15427881A patent/JPS5857494A/en active Pending
-
1982
- 1982-09-24 AU AU88674/82A patent/AU8867482A/en not_active Abandoned
- 1982-09-27 CA CA000412208A patent/CA1175073A/en not_active Expired
- 1982-09-29 DE DE19823236093 patent/DE3236093A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5857494A (en) | 1983-04-05 |
| DE3236093A1 (en) | 1983-04-07 |
| AU8867482A (en) | 1983-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1196617A (en) | Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas | |
| EP0188530B1 (en) | Enhanced conversion of syngas to liquid motor fuels | |
| US4587008A (en) | Process comprising reforming, synthesis, and hydrocracking | |
| US3770619A (en) | Process for hydrocarbon purification by selective hydrogenation | |
| JP5639595B2 (en) | Catalytic cracking of hydrocarbon streams to maximize light olefins | |
| NZ210202A (en) | Production of c 5 + hydrocarbons | |
| US7459485B2 (en) | Hydrocarbon synthesis process using a hydrocarbon synthesis catalyst and an acidic catalyst | |
| US4443561A (en) | Process for the preparation of organic compounds | |
| JPH0581635B2 (en) | ||
| EP0159759B1 (en) | Process for the preparation of hydrocarbons | |
| JPS59227976A (en) | Conversion of methanol, dimethyl ether or both to olefins | |
| US5126377A (en) | Catalyst for conversion of synthesis gas into hydrocarbons | |
| US4131568A (en) | Catalytic synthesis of low molecular weight hydrocarbons | |
| US4659743A (en) | Process and catalyst for converting synthesis gas to liquid hydrocarbon mixture | |
| US4652538A (en) | Catalysts for conversion of syngas to liquid motor fuels | |
| EP0167353A1 (en) | Process for the catalytic conversion of methanol to hydrocarbons | |
| US4617320A (en) | Enhanced conversion of syngas to liquid motor fuels | |
| CA1175073A (en) | Process for preparing aromatics-rich hydrocarbons from synthesis gas | |
| CA1122620A (en) | Process for the preparation of an aromatic hydrocarbon mixture | |
| EP0140365A1 (en) | Conversion of syngas to liquid motor fuels | |
| JPS61191517A (en) | Production of hydrocarbon rich in isoparaffin | |
| US4950821A (en) | Process for the converson of natural gas into middle distillates | |
| CA1177464A (en) | Process and catalyst for converting synthesis gas to liquid hydrocarbon mixture | |
| JP2841500B2 (en) | Method for producing propane by hydrogenation of carbon dioxide | |
| Inui et al. | Contrast between H-ZSM-5 and HFe-silicates of the pentasil pore structure in propylene conversion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |