CA1111074A - Process for preparing aromatic hydrocarbons - Google Patents
Process for preparing aromatic hydrocarbonsInfo
- Publication number
- CA1111074A CA1111074A CA310,511A CA310511A CA1111074A CA 1111074 A CA1111074 A CA 1111074A CA 310511 A CA310511 A CA 310511A CA 1111074 A CA1111074 A CA 1111074A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- mixture
- hydrocarbons
- catalysts
- process according
- 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 133
- 239000000203 mixture Substances 0.000 claims abstract description 94
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 36
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 35
- 229910001868 water Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 36
- 230000003197 catalytic effect Effects 0.000 claims description 29
- 239000000306 component Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910017052 cobalt Chemical group 0.000 claims description 9
- 239000010941 cobalt Chemical group 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 abstract description 12
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 30
- 229940105305 carbon monoxide Drugs 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000004760 silicates Chemical class 0.000 description 12
- 230000006870 function Effects 0.000 description 10
- 239000003502 gasoline Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- -1 acyclic hydrocarbons Chemical class 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000002309 gasification Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JCVAWLVWQDNEGS-UHFFFAOYSA-N 1-(2-hydroxypropylamino)propan-2-ol;thiolane 1,1-dioxide;hydrate Chemical compound O.O=S1(=O)CCCC1.CC(O)CNCC(C)O JCVAWLVWQDNEGS-UHFFFAOYSA-N 0.000 description 1
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 description 1
- 102100031830 Afadin- and alpha-actinin-binding protein Human genes 0.000 description 1
- 101710182459 Afadin- and alpha-actinin-binding protein Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QEFDIAQGSDRHQW-UHFFFAOYSA-N [O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[Cr+3].[Fe+2] QEFDIAQGSDRHQW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- XUZDJUDKWXESQE-UHFFFAOYSA-N chromium copper zinc Chemical compound [Cr].[Zn].[Cu] XUZDJUDKWXESQE-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- 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
-
- 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
- B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
-
- 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
- B01J29/88—Ferrosilicates; Ferroaluminosilicates
-
- 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
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
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- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/88—Ferrosilicates; Ferroaluminosilicates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A B S T R A C T
Process for preparing aromatic hydrocarbons. A gas with a H2/CO molar ratio less than 1.0, is contacted with a trifunctional catalyst containing one or more metals catalyzing the conversion of a H2/CO mixture into hydro-carbons and/or oxygen-containing hydrocarbons, one or more metals catalyzing the water gas shift reaction and a crystalline iron silicate.
Process for preparing aromatic hydrocarbons. A gas with a H2/CO molar ratio less than 1.0, is contacted with a trifunctional catalyst containing one or more metals catalyzing the conversion of a H2/CO mixture into hydro-carbons and/or oxygen-containing hydrocarbons, one or more metals catalyzing the water gas shift reaction and a crystalline iron silicate.
Description
PROCESS FOR PREPARINC ARO~IATIC IIYDROCARBONS
The invention relates to a process for preparing aromatic hydro-carbons by catalytic reaction of carbon monoxide with hydrogen.
Hydrocarbon mixtures boiling in the gasoline range can be obtained, for instance, by straight-run distillation of crude mineral oil, by conver-sion of heavier mineral oil fractions, for instance, by catalytic cracking, thermal cracking and hydrocracking and by conversion of lighter mineral oil fractions, for instance, by alkylation. To improve the octane number of the hydrocarbon mixtures thus obtained, they are often subjected to catalytic reforming, as a result of which the aromatics content increases.
; In view of the increasing need of gasoline and the decreasing re-serves of mineral oil there is a great interest in processes permitting the conversion in an economically justified way of carbon-containing materials not based on mineral oil, such as coal, into hydrocarbon mixtures boiling in `the gasoline range. It is desirable that these hydrocarbon mixtures should have a sufficiently high octane number, as a result of which they are suit-able for use as gasoline without any further refining.
It is known that carbon-containing materials, such as coal, can be converted in a relatively simple way into mixtures of carbon ~onoxide and hydrogen by steam gasification. It is further known that mixtures of carbon monoxide and hydrogen IYhose H2/CO molar ratio is more than 1.0 can be con-verted in good yield into mixtures of hydrocarbons by contacting the gas mixtures with suitable catalysts. Attempts to achieve a commercially attrac-tive process for the preparation of gasoline from carbon-containing mate-rials, such as coal, by combining the two processes have met with serious objections. These objections are in the first place connected with the com-position of the mixture of carbon monoxide and hydrogen that is obtained in the steam gasificat:ion and further with the composition of the mixture of ... . . .
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hydrocarbons formed in the conversion of the mixture of carbon monoxide and hydrogen.
It has been found that in the steam gasification for obtaining a high yield of a mixture of carbon monoxide and hydrogen and for suppressing the formation of methane, tarry products and phenols, tempera-tures higher than 1000C should be used. It has further been found that the H2/C0 molar ratio in the product obtained in the steam gasification is highly dependent - on the temperature used and that at temperatures higher than 1000C gas mix-`~ tures are obtained in which the H2/C0 molar ratio is smaller than 1Ø Such10 gas mixtures are less suitable for conversion in the second stage of the above-mentioned combination process in which gas mixtures with a H2/C0 molar ratio above 1.0 are desired. An intermediate increase of the H2/C0 molar ratio to above 1.0 by applying the water gas shift reaction to these gas mixtures with low H2/C0 ratio is not suitable for commercial use, because this step implies that the gas with increased H2/C0 molar ratio thus ob-tained should then be subjected to an expensive gas separation treatment to remove carbon dioxide, before the gas can be converted in the second stage .~ of the combination process.
As regards the composition of the mixture of hydrocarbons formed 20 in the conversion of the mixture of carbon monoxide and hydrogen it is noted , that this mixture has a very wide molecular weight distribution and that it contains hardly any aromatics. This means that only part of this mixture consists of hydrocarbons boiling in the gasoline range and that, moreover, before this part can be used as gasoline it first has to be subjected to a catalytic reforming treatment to increase the aromatics content.
: The Applicant has carried out an extensive investigation to ex-amine to what extent it is possible to prepare from mixtures of carbon mon-oxide and hydrogen such as they are obtained in the high-temperature steam
The invention relates to a process for preparing aromatic hydro-carbons by catalytic reaction of carbon monoxide with hydrogen.
Hydrocarbon mixtures boiling in the gasoline range can be obtained, for instance, by straight-run distillation of crude mineral oil, by conver-sion of heavier mineral oil fractions, for instance, by catalytic cracking, thermal cracking and hydrocracking and by conversion of lighter mineral oil fractions, for instance, by alkylation. To improve the octane number of the hydrocarbon mixtures thus obtained, they are often subjected to catalytic reforming, as a result of which the aromatics content increases.
; In view of the increasing need of gasoline and the decreasing re-serves of mineral oil there is a great interest in processes permitting the conversion in an economically justified way of carbon-containing materials not based on mineral oil, such as coal, into hydrocarbon mixtures boiling in `the gasoline range. It is desirable that these hydrocarbon mixtures should have a sufficiently high octane number, as a result of which they are suit-able for use as gasoline without any further refining.
It is known that carbon-containing materials, such as coal, can be converted in a relatively simple way into mixtures of carbon ~onoxide and hydrogen by steam gasification. It is further known that mixtures of carbon monoxide and hydrogen IYhose H2/CO molar ratio is more than 1.0 can be con-verted in good yield into mixtures of hydrocarbons by contacting the gas mixtures with suitable catalysts. Attempts to achieve a commercially attrac-tive process for the preparation of gasoline from carbon-containing mate-rials, such as coal, by combining the two processes have met with serious objections. These objections are in the first place connected with the com-position of the mixture of carbon monoxide and hydrogen that is obtained in the steam gasificat:ion and further with the composition of the mixture of ... . . .
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hydrocarbons formed in the conversion of the mixture of carbon monoxide and hydrogen.
It has been found that in the steam gasification for obtaining a high yield of a mixture of carbon monoxide and hydrogen and for suppressing the formation of methane, tarry products and phenols, tempera-tures higher than 1000C should be used. It has further been found that the H2/C0 molar ratio in the product obtained in the steam gasification is highly dependent - on the temperature used and that at temperatures higher than 1000C gas mix-`~ tures are obtained in which the H2/C0 molar ratio is smaller than 1Ø Such10 gas mixtures are less suitable for conversion in the second stage of the above-mentioned combination process in which gas mixtures with a H2/C0 molar ratio above 1.0 are desired. An intermediate increase of the H2/C0 molar ratio to above 1.0 by applying the water gas shift reaction to these gas mixtures with low H2/C0 ratio is not suitable for commercial use, because this step implies that the gas with increased H2/C0 molar ratio thus ob-tained should then be subjected to an expensive gas separation treatment to remove carbon dioxide, before the gas can be converted in the second stage .~ of the combination process.
As regards the composition of the mixture of hydrocarbons formed 20 in the conversion of the mixture of carbon monoxide and hydrogen it is noted , that this mixture has a very wide molecular weight distribution and that it contains hardly any aromatics. This means that only part of this mixture consists of hydrocarbons boiling in the gasoline range and that, moreover, before this part can be used as gasoline it first has to be subjected to a catalytic reforming treatment to increase the aromatics content.
: The Applicant has carried out an extensive investigation to ex-amine to what extent it is possible to prepare from mixtures of carbon mon-oxide and hydrogen such as they are obtained in the high-temperature steam
- 2 -gasification of carbon-containing materials such as coal, aromatic hydro-carbon mixtures with a high octane number that are suitable for use as gas-oline without any further refining. In the investigation emphasis has been placed on the implementation of this conversion in one stage.
It has been found that the above-mentioned requirements can indeed be met by contacting the gas mixture with a catalyst which combines three functions. In the first place the catalyst should comprise one or more metal components having catalytic activity for the conversion of a H2/C0 mixture into hydrocarbons and/or oxygen-containing hydrocarbons. ~he cat-. 10 alyst should further contain a crystalline silicate which a) is thermally stable to temperatures higher than 600C, b) is capable of absorbing, after dehydration at 400C in vacuum, more than
It has been found that the above-mentioned requirements can indeed be met by contacting the gas mixture with a catalyst which combines three functions. In the first place the catalyst should comprise one or more metal components having catalytic activity for the conversion of a H2/C0 mixture into hydrocarbons and/or oxygen-containing hydrocarbons. ~he cat-. 10 alyst should further contain a crystalline silicate which a) is thermally stable to temperatures higher than 600C, b) is capable of absorbing, after dehydration at 400C in vacuum, more than
3 %w water at 25C and saturated water vapour pressure, and c) has, in dehydrated form, the following overall composition, expressed in moles of the oxides.
)( )2/n l a Fe203. b A1303. c Ga203 ~ .y~d SiO2- e GeO2), where R = one or more mono- or bivalent cations, a > 0.1, b > 0.
c > O.
a + b + c = 1.
y > 10.
d > 0.1, e > 0.
d + e = 1, and n = the valency of R.
Finally, the catalyst should contain one or more metal components having X
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catalytic ac-tivity for the water gas shift reaction.
The present patent application therefore relates to a process for preparing aromatic hydrocarbons by catalytic reaction of carbon monoxide with hydrogen> in which process a mixture of carbon monoxide and hydrogen, whose ~2/C0 molar ratio is less than 1.() is convertecl in one step into an aromatic hydrocarbon mixture by contacting the gas mixture with a trifunc-tional catalyst containing one or more metal components having catalytic activity for the conversion of a H2/C0 mixture into hydrocarbons and/or oxygen-containing hydrocarbons, one or more metal components having cata-lytic activity for the water gas shift reaction and a crystalline silicate as defined hereinbefore.
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` The process according to the invention starts from a mixture of carbon monoxide and hydrogen whose H2/CO molar ratio is less than 1Ø As ~:~ was mentioned earlier, such a mixture can be readily prepared by steam gas-"
ification of a carbon-containing material at a high temperature. Examples of such materials are brown coal, anthracite, coke, crude mineral oil and fractions thereof, as well as oils extracted from tar sand and bituminous shale. During the steam gasification the feed, in finely divided form, is converted with steam and oxygen or air, if desired enriched with oxygen, into a gas mixture containing, inter alia, hydrogen, carbon monoxide, carbon dioxide, nitrogen and water. The steam gasification is preferably carried out at a temperature between 1000 and 2000 C and a pressure between 10 and 50 bar. In order to be able to remove contaminants such as ash, carbon-con-taining material and hydrogen sulphide from the gas obtained in the steam gasification, which has a temperature higher than 1000C. this gas should first be cooled down to a temperature between 100 and 200C. This cooling can very suitably be effected in a boiler in which steam is generated with the aid of the waste heat. The cooled gas can be freed from nearly all , _ ~ _ .;
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solid components by washing it with water. After this washing treatment, during which the temperature of the gas has fallen to 20-80C, the gas is further purified by removal of hydrogen sulphide and carbon dioxide. This may very suitably be effected with the aid of the ADIP process or the SUL-FINOL process.
~ he trifunctional catalysts which are used in the process accord-ing to the invention contain, in addition to the metal components, a crys-talline silicate of a special class. These silicates effect a high conver-sion of aliphatic hydrocarbons into aromatic hydrocarbons in commerciallydesirable yields and they are in general very active in conversion reactions in which aromatic hydrocarbons are involved.
In the process according to the invention preference is given to the use of silicates in which no gallium or germanium are present, in other words: silicates of which, in the above-mentioned overall composition, c and e are 0. Such silicates are the subject of Netherlands patent applica-tion No. 7,613,957. Further, in the process according to the invention preference is given to the use of silicates of which, in the above-mentioned overall composition, a is greater than 0.3 and in particular of which a is greater than 0.5. Particular preference is given to silicates in which no aluminium is present, in other words: silicates of which in the above-men-tioned overall composition b is 0. It should be noted that in the silicates which are used in the process according to the invention, y is preferably less than 600 and in particular less than 300. Finally, in the process according to the invention preference is given to silicates whose X-ray powder diffraction pattern has, inter alia, the reflections given in Table A
of Netherlands Patent Application 7,613,957, published June 20, 1978.
The trifunctional catalysts which are used in the process accord-ing to the invention contain one or more metal components having catalytic ' , ' ~ ~' ', , - ' : : ' 7~6 activity for the conversion of a H2/CO mixture into hydrocarbons and/or oxygen-containing hydrocarbons, one or more metal components having cata-: lytic activity for the water gas shift reaction and a crystalline silicate such as defined hereinbefore having catalytic activity for the conversion of acyclic hydrocarbons ancl/or oxygen-containing acyclic hydrocarbons into an aromatic hydrocarbon mixture boiling in the gasoline range. The ratio in which the three catalytic functions are present in the catalyst may vary within wide limits and is substantially determined by the activity of each of the catalytic functions. For, in the process according to the invention ; 10 the object is that of the acyclic hydrocarbons and/or oxygen-containing acyclic hydrocarbons formed under the influence of the first catalytic func-tion, as much as possible is converted under the~influence of a second cata-lytic function into an aromatic hydrocarbon mixture boiling in the gasoline .- range, and that of the water liberated in the conversion of the mixture of carbon monoxide and hydrogen into hydrocarbons and/or in the conversion of oxygen-containing hydrocarbons into an aromatic hydrocarbon mixture, as much as possible reacts under the influence of a third catalytic function with the carbon monoxide present in an excess amount in the mixture of carbon monoxide and hydrogen with formation of a mixture of hydrogen and carbon di-oxide. In the composition of an optimum trifunctional catalyst to be used in the process according to the invention, which catalyst contains a given quantity of a first catalytic function having a given activity, it is there-fore possible to do with less of the other catalytic functions according as these are more active.
Although the catalysts according to the invention are described in this patent application as catalysts containing one or more metal components having catalytic activity for the conversion of a 112/C0 mixture into hydro-carbons and/or oxygen-containing hydrocarbons and one or more metal compon-' " ' ' ` ~ ` ~
3i74 ents having catalytic activity for the water gas shiEt reaction, this means in no way that metal components each having in themselves one of the two catalytic functions should always separately be present in the catalysts according to the invention. For~ it has been found that metal components and combinations of metal components having catalytic activity for the con-version of a ~12/C0 mixture into substantially oxygen-containing hydrocarbons as a rule also have sufficient catalytic activity for the water gas shift reaction, so that in such a case incorporation of one metal component or one combination of metal componen~s into the catalysts according to the inven-tion will suffice. Examples of such metal components are the metals chosenfrom the group formed by the metals zinc, copper and chromium. When use is made of trifunctional catalysts according to the invention containing these metals, preference is given to catalysts containing combinations of at least two of these metals, for instance the combination zinc-copper, zinc-chromium or zinc-copper-chromium. Particular preference is given to a trifunctional catalyst containing, in addition to the crystalline silicate the metal com-bination zinc-chromium. Metal components and combinations of metal compon-ents having catalytic activity for the conversion of a H2/C0 mixture into substantially hydrocarbons have as a rule no or insufficient activity for the water gas shift reaction. When use is made of such metal components or combinations of metal components in the catalysts according to the inven-tion, one or more separate metal components having catalytic activity for the water gas shift reaction should therefore be incorporated therein.
The trifunctional catalysts which are used according to the inven-tion are preferably composed of two or three separate catalysts, which will for convenience be designated catalysts X, Y and Z. Catalyst X is the cata-lyst containing the metal components having catalytic activity for the con-version of a H2/C0 mixture into hydrocarbons and/or oxygen-containing hydro-,' ' ', ' , '. ~ .
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carbons. Catalyst Y is the crystalline silicate. Catalyst Z is the cata-lyst containing the metal component having catalytic activity for the water - gas shift reaction. As has been explained hereinbefore the use o:E a Z-cata-lyst may be omitted in some cases.
If as the X-catalyst a catalyst is used whicll is capable of con-verting a H2/CO mixture into substantially oxygen-containing hydrocarbons, preference is given to a catalyst which is capable of converting the H2/CO
mixture into substantially methanol and/or dimethyl ether. For the conver-sion of a H2/CO mixture into substantially methanol, catalysts containing . 10 the metal combinations mentioned hereinbefore are very suitable. If de-,. sired, the said metal combinations may be emplaced on a carrier material.
'- By introducing an acid function into these catalysts, for instance by em-placing the metal combination on an acid carrier, it may be effected that . apart from the conversion of the H2/CO mixture into methanol a considerable part of the mixture will be converted into dimethyl ether.
X-catalysts which are capable of converting a H2/CQ mixture into substantially hydrocarbons are referred to in the literature as Fischer-Tropsch catalysts. Such catalysts often contain one or more metals of the iron group or ruthenium together with one or more promoters to increase the ; activity and/or selectivity and sometimes a carrier material such as kieselguhr. They can be prepared by precipitation, melting and by impreg-~ nation. The preparation of the catalysts containing one or more metals of ; the iron group, by impregnation, takes place by impregnating a porous car-rier with one or more aqueous solutions of salts of metals of the iron group and, optionally, of promoters, followed by drying and calcining the composi-tion. If in the process according to the invention use is made of a cata-lyst combination in which catalyst X is a Fischer-Tropsch catalyst, it is preferred to choose for this purpose an iron or cobalt catalyst, in partic-: - 8 -'' X ' .'~
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ular such a catalyst which has been prepared by impregnation. Very suitable Fischer-Tropsch catalysts for use in the catalyst combinations according to the invention are the catalysts preparecl by impregnation according to the Netherlands Patent Application 7,612,~l60, published May 12, 1978. The cata-lysts concerned contain per 100 pbw carrier 10-75 pbw of one or more metals of the iron group, together with one or more promoters in a quantity of 1-- 50% of the quantity of metals of the iron group present on the catalyst, which catalysts have such a specific average pore diameter (p) of at most 10,000 nm and such a specific average particle diameter (d) of at most 5 mm, the quotient p/d is more than 2 (p in nm and d in nm).
If in the process according to the invention the object is to use a catalyst combination of which X is a Fischer-Tropsch iron catalyst, it is preferred to choose an iron catalyst containing a promoter combination con-sisting of an alkali metal, a metal that is easy to reduce, such as copper or silver and, optionally, a metal that is hard to reduce, such as aluminium or zinc. A very suitable iron catalyst for the present purpose is a cata-lyst prepared by impregnation containing iron, potassium and copper on sil-ica as the carrier. If in the process according to the invention the object is to use a catalyst combination of which X is a Fischer-Tropsch cobalt catalyst, it is preferred to choose a cobalt catalyst containing a promoter combination consisting of an alkaline-earth metal and thorium, uranium or cerium. A very suitable Fischer-Tropsch cobalt catalyst for the present purpose is a catalyst prepared by impregnation containing cobalt, magnesium and thorium on silica as the carrier. Other very suitable Fischer-Tropsch cobalt catalysts prepared by impregnation are catalysts containing, in addi-tion to cobalt, one of the elements chromium, titanium, zirconium and zinc on silica as the carrier. If desired, it is also possible to use in the process according to the invention catalyst combinations containing an X-_ g _ X
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catalyst, which is capable of converting a H2CO mixture into a mixture con-taining both hydrocarbons and oxygen-containing hydrocarbons in comparable quantities. As a rule, such a catalyst has sufficient catalytic activity for the water gas shift reaction, so that -the use of a Z-catalyst in the combination can be omitted. An example of an X-catalyst of thi-s type is an iron-chromium oxide catalyst. If desired, it is also possible to use in the process according to the invention catalyst combinations containing two or more X-catalysts, for instance in addition to a catalyst of the X-type which is capable of converting a H2/CO mixture into substantially hydrocarbons, a second catalyst of the X-type which is capable of converting a H2CO mixture into substantially oxygen-containing hydrocarbons.
Z-catalysts which are capable of converting a H2O/CO mixture into a H2/CO2 mixture are referred to in the literature as CO-shift catalysts.
Such catalysts often contain one or more metals of the group formed by iron, chromium, copper, zinc, cobalt, nickel and molybdenum as the catalytically active component, either as such, or in the form of their oxides or sul-phides. Examples of suitable CO-shift catalysts are the mixed sulphidic cat-alysts according to the Netherlands Patent Application 7,305,340 published October 21, 1974, Netherlands Patent Application 7,304,793, published October 9, 1974 and Canadian Patent Application No. 287,679. If in the pro-cess according to the invention use is made of a catalyst combination in which a Z-catalyst is present, it is preferred to choose a catalyst which contains both copper and zinc, in particular a catalyst in which the Cu/Zn atomic ratio lies between 0.25 and 4Ø
In the trifunctional catalysts the catalysts X, Y and, optionally, Z may be present as a mixture, in which, in principle, each particle of cata-lyst X is surrounded by a number of particles of catalyst Y and, optionally, catalyst Z and conversely. If the process is carried out with the use of a X
fixed catalyst bed, this bed may be built up of alternate layers of parti-` cles of catalysts X, Y and, optionally, Z. If the two or three catalysts are used as a mixture, this mixture may be a macromixture or a micromixture.
~` In the first case the trifunctional catalyst consists of two or three kinds of macroparticles of which one kind is completely made up of catalyst X, the ;.
second kind completely of catalyst Y and, optionally, a third kind complete-ly of catalyst Z. In the second case the trifunctional catalyst consists of one kind of macroparticles, each macroparticle being made up of a large num-ber of microparticles of each of the catalysts X, Y and, optionally, Z.
Trifunctional catalysts according to the invention in the form of micromix-tures may be prepared, for instance, by thoroughly mixing a fine powder of catalyst X with a fine powder of catalyst Y and, optionally, with a fine pow-der of catalyst Z and shaping the mixture to larger particles, for instance, by extruding or pelleti~ing. In the process according to the invention it is preferred to use trifunctional catalysts in the form of micromixtures.
The trifunctional catalysts which are used according to the inven-tion may also have been prepared by incorporating the metal components hav-ing catalytic activity for converting a H2JCO mixture into hydrocarbons and/
or oxygen-containing hydrocarbons and, optionally, the metal components hav-ing catalytic activity for the water gas shift reaction into the crystalline silicate, for instance by impregnation or by ion exchange.
The crystalline silicates which are used in the trifunctional cat-alysts according to the invention are usually prepared from an aqueous mix-ture as the starting material which contains the following compounds in a given ratio; one or more compounds of an alkali or alkaline-earth metal, one or more compounds containing a mono- or bivalent organic cation or from which such a cation is formed during the preparation of the silicate, one or more silicon compounds, one or more iron compounds, and, optionally, one or ,.. .
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more aluminium, gallium and/or germanium compounds. The preparation is ef-fected by maintaining the mixture at elevated temperature until the silicate has been formed and then separating the crystals of the silicate from the ~;
mother liquor. The silicates thus prepared contain alkali and/or alkaline-earth metal ions and mono- and/or bivalent organic cations. Before being .:~` used in the trifunctional catalysts according to the invention at least part of the mono- and/or bivalent organic cations introduced during the preparation are preferably converted into hydrogen ions, for instance by calcining and at least part of the exchangeable mono- and/or bivalent . 10 cations introduced during the preparation are preferably replaced by other ions, in particular hydrogen ions, ammonium ions and/or ions of the rare-earth metals. The crystalline silicates used in the trifunctional catalysts . according to the invention preferably have an alkali metal content of less than 1 %w and in particulàr of less than 0.05 %w. If desired, a binder ma-terial such as bentonite or kaolin may be incorporated in the trifunctional catalysts.
The process according to the invention preferably starts from a mixture of carbon monoxide and hydrogen whose H2/C0 molar ratio is more than 0.4.
The process according to the invention is preferably carried out at a temperature of from 200 to 500C and in particular of from 300 to 450C, a pressure of from 1 to 150 bar and in particular of from 5 to 100 bar and a space velocity of from 50 to 5000 and in particular of from 300 to 3000 Nl gas/l catalyst/hour.
~: The process according to the invention can very suitably be car-ried out by passing the feed in upward or in downward direction through a vertically disposed reactor in which a fixed or a moving bed of the trifunc-tional catalyst concerned is present. The process may, for instance, be . ~r . .
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carried out in the so-called fixed-bed operation, in bunker-flow operation or in ebulated-bed operation. It is preferred to use catalyst particles then with a diameter between 1 and 5 mm. If desired, the process may also be carried out in fluidized-bed operation or with the use of a suspension of the catalyst in a hydrocarbon oil~ It is preferred to use catalyst par-ticles then with a diameter between 10 and 150 ~m.
The invention will now be explained with reference to the follow-ing examples~
Example I
A crystalline iron silicate ~silicate A) was prepared as follows.
A mixture of Fe(N03)3~ SiO2~ NaN03 and [(C3117)4N]OH in water with the molar omposition Na 0- 1-5[(C3H7)4N]20- 0-~25 Pe23 2 2 heated for 48 hours in an autoclave at 150C under autogenous pressure.
After the reaction mixture had cooled down, the silicate formed was filtered - off, washed with water until the pH of the wash water was about 8 and dried for two hours at 120C. Silicate A thus prepared had the following chemical composition 0.8[(C3H7)4N/2o. 0.3 Na20. Fe203 2 2 The silicate had an X-ray powder diffraction pattern substantially as given in Table B of Netherlands patent application No. 7,613,957. The silicate was thermally stable to temperatures higher than 900C and was cap-able, after dehydration at 400C, to absorb in vacuum 7 ~w water at 25C and saturated water vapour pressure. With silicate A as the starting material silicate B was prepared by, successively, calcining silicate A at 500 C, boiling with 1.0 molar NH~1N03 solution, washing with water, boiling again with 1.0 molar NH4N03 solution and washing, drying for two hours at 120C
and calcining for four hours at 500C.
Example II
A crystalline silicate (silicate C) was prepared in substantially ~Y~
the same way as silicate A, the difference being that in the present case the starting material was an aqueous mixture which contained, in addition to Fe(NO3)3, Al~NO3)3 and which had tlle following molar composition:
Na2 4-5[(C3ll7)4N]2o 0.35 A1203 0.15 Fe2O3. 29.1 SiO2. 468 H20.
Silicate C thus prepared had the following chemical composition:
0.35[(C3~17)4N]20. 0-2 Na20. 0.15 Fe203. 0.35 A1203. 31 SiO2. 9 H20.
The silicate had an X-ray powder diffraction pattern substantially as given in Table B of Netherlands Patent Applica~ion 7~613,957, published June 20, 1978. The silicate was thermally stable to temperatures higher than 1000C and was capable, after a dehydration at 400C in vacuum, of ab-sorbing 8 %w water at 25C and saturated water vapour pressure. With sili-cate C as the starting material silicate D was prepared in the same way as described for the preparation of silicate B from silicate A.
Example III
A catalyst was prepared by mixing a ZnO-Cr203 composition with the crystalline iron silicate B in a weight ratio of 3:1. Both materials were present in the catalyst in the form of particles with a diameter of 0.15-0.3 mm. The ZnO-Cr203 composition used catalyses both the reduction of C0 to methanol and the water gas shift reaction. The catalyst obtained by mixing was tested for the one-stage preparation of an aromatic hydrocarbon mixture starting from a mixture of carbon monoxide and hydrogen. The testing was carried out in a 50-ml reactor, in which a fixed catalyst bed having a vol-ume of 7.5 ml was present. A mixture of carbon monoxide and hydrogen with a H2/C0 molar ratio of 0.5 was passed across the catalyst at a temperature of 37iC, a pressure of 60 bar and a space velocity of 1000 Nl gas/l cata-lyst/h. The results of this experiment are given below C0 conversion, % 50 ll2 conversion, % 53 ~,~
Product composition, %w on Cl+ product `. Cl S
: C
C~, 10 C5 product composition, %w on C5 product paraffins + olefins 20 naphthenes 27 aromatics 53 Example IV
- A catalyst was prepared by mixing the ~nO-Cr203 composition of ex-ample III with the crystalline iron-aluminium silicate D in a weight ratio of 5:1. Both materials were present in the catalyst in the form of par-ticles with a diameter of 0.15-0.3 mm. This catalyst was tested for the one-stage preparation of an aromatic hydrocarbon mixture starting from a mixture of carbon monoxide and hydrogen with a H2/C0 molar ratio of 0.5.
The testing was carried out in substantially the same way as described in example III, the differences being that in the present case a temperature of 350C and a pressure of 80 bar were used. The results of this experiment are given below C0 conversion, % 54 H2 conversion, % 59 Product composition, %w on C product ' 1 ' C 2 ; C2 2 c3 15 10 . .
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. C5 product composition, %1~ on C5 product paraffins + olefins lX
naphthenes 20 aromatics 62 .: ' -::
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)( )2/n l a Fe203. b A1303. c Ga203 ~ .y~d SiO2- e GeO2), where R = one or more mono- or bivalent cations, a > 0.1, b > 0.
c > O.
a + b + c = 1.
y > 10.
d > 0.1, e > 0.
d + e = 1, and n = the valency of R.
Finally, the catalyst should contain one or more metal components having X
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catalytic ac-tivity for the water gas shift reaction.
The present patent application therefore relates to a process for preparing aromatic hydrocarbons by catalytic reaction of carbon monoxide with hydrogen> in which process a mixture of carbon monoxide and hydrogen, whose ~2/C0 molar ratio is less than 1.() is convertecl in one step into an aromatic hydrocarbon mixture by contacting the gas mixture with a trifunc-tional catalyst containing one or more metal components having catalytic activity for the conversion of a H2/C0 mixture into hydrocarbons and/or oxygen-containing hydrocarbons, one or more metal components having cata-lytic activity for the water gas shift reaction and a crystalline silicate as defined hereinbefore.
~ .
` The process according to the invention starts from a mixture of carbon monoxide and hydrogen whose H2/CO molar ratio is less than 1Ø As ~:~ was mentioned earlier, such a mixture can be readily prepared by steam gas-"
ification of a carbon-containing material at a high temperature. Examples of such materials are brown coal, anthracite, coke, crude mineral oil and fractions thereof, as well as oils extracted from tar sand and bituminous shale. During the steam gasification the feed, in finely divided form, is converted with steam and oxygen or air, if desired enriched with oxygen, into a gas mixture containing, inter alia, hydrogen, carbon monoxide, carbon dioxide, nitrogen and water. The steam gasification is preferably carried out at a temperature between 1000 and 2000 C and a pressure between 10 and 50 bar. In order to be able to remove contaminants such as ash, carbon-con-taining material and hydrogen sulphide from the gas obtained in the steam gasification, which has a temperature higher than 1000C. this gas should first be cooled down to a temperature between 100 and 200C. This cooling can very suitably be effected in a boiler in which steam is generated with the aid of the waste heat. The cooled gas can be freed from nearly all , _ ~ _ .;
' ' 7~
solid components by washing it with water. After this washing treatment, during which the temperature of the gas has fallen to 20-80C, the gas is further purified by removal of hydrogen sulphide and carbon dioxide. This may very suitably be effected with the aid of the ADIP process or the SUL-FINOL process.
~ he trifunctional catalysts which are used in the process accord-ing to the invention contain, in addition to the metal components, a crys-talline silicate of a special class. These silicates effect a high conver-sion of aliphatic hydrocarbons into aromatic hydrocarbons in commerciallydesirable yields and they are in general very active in conversion reactions in which aromatic hydrocarbons are involved.
In the process according to the invention preference is given to the use of silicates in which no gallium or germanium are present, in other words: silicates of which, in the above-mentioned overall composition, c and e are 0. Such silicates are the subject of Netherlands patent applica-tion No. 7,613,957. Further, in the process according to the invention preference is given to the use of silicates of which, in the above-mentioned overall composition, a is greater than 0.3 and in particular of which a is greater than 0.5. Particular preference is given to silicates in which no aluminium is present, in other words: silicates of which in the above-men-tioned overall composition b is 0. It should be noted that in the silicates which are used in the process according to the invention, y is preferably less than 600 and in particular less than 300. Finally, in the process according to the invention preference is given to silicates whose X-ray powder diffraction pattern has, inter alia, the reflections given in Table A
of Netherlands Patent Application 7,613,957, published June 20, 1978.
The trifunctional catalysts which are used in the process accord-ing to the invention contain one or more metal components having catalytic ' , ' ~ ~' ', , - ' : : ' 7~6 activity for the conversion of a H2/CO mixture into hydrocarbons and/or oxygen-containing hydrocarbons, one or more metal components having cata-: lytic activity for the water gas shift reaction and a crystalline silicate such as defined hereinbefore having catalytic activity for the conversion of acyclic hydrocarbons ancl/or oxygen-containing acyclic hydrocarbons into an aromatic hydrocarbon mixture boiling in the gasoline range. The ratio in which the three catalytic functions are present in the catalyst may vary within wide limits and is substantially determined by the activity of each of the catalytic functions. For, in the process according to the invention ; 10 the object is that of the acyclic hydrocarbons and/or oxygen-containing acyclic hydrocarbons formed under the influence of the first catalytic func-tion, as much as possible is converted under the~influence of a second cata-lytic function into an aromatic hydrocarbon mixture boiling in the gasoline .- range, and that of the water liberated in the conversion of the mixture of carbon monoxide and hydrogen into hydrocarbons and/or in the conversion of oxygen-containing hydrocarbons into an aromatic hydrocarbon mixture, as much as possible reacts under the influence of a third catalytic function with the carbon monoxide present in an excess amount in the mixture of carbon monoxide and hydrogen with formation of a mixture of hydrogen and carbon di-oxide. In the composition of an optimum trifunctional catalyst to be used in the process according to the invention, which catalyst contains a given quantity of a first catalytic function having a given activity, it is there-fore possible to do with less of the other catalytic functions according as these are more active.
Although the catalysts according to the invention are described in this patent application as catalysts containing one or more metal components having catalytic activity for the conversion of a 112/C0 mixture into hydro-carbons and/or oxygen-containing hydrocarbons and one or more metal compon-' " ' ' ` ~ ` ~
3i74 ents having catalytic activity for the water gas shiEt reaction, this means in no way that metal components each having in themselves one of the two catalytic functions should always separately be present in the catalysts according to the invention. For~ it has been found that metal components and combinations of metal components having catalytic activity for the con-version of a ~12/C0 mixture into substantially oxygen-containing hydrocarbons as a rule also have sufficient catalytic activity for the water gas shift reaction, so that in such a case incorporation of one metal component or one combination of metal componen~s into the catalysts according to the inven-tion will suffice. Examples of such metal components are the metals chosenfrom the group formed by the metals zinc, copper and chromium. When use is made of trifunctional catalysts according to the invention containing these metals, preference is given to catalysts containing combinations of at least two of these metals, for instance the combination zinc-copper, zinc-chromium or zinc-copper-chromium. Particular preference is given to a trifunctional catalyst containing, in addition to the crystalline silicate the metal com-bination zinc-chromium. Metal components and combinations of metal compon-ents having catalytic activity for the conversion of a H2/C0 mixture into substantially hydrocarbons have as a rule no or insufficient activity for the water gas shift reaction. When use is made of such metal components or combinations of metal components in the catalysts according to the inven-tion, one or more separate metal components having catalytic activity for the water gas shift reaction should therefore be incorporated therein.
The trifunctional catalysts which are used according to the inven-tion are preferably composed of two or three separate catalysts, which will for convenience be designated catalysts X, Y and Z. Catalyst X is the cata-lyst containing the metal components having catalytic activity for the con-version of a H2/C0 mixture into hydrocarbons and/or oxygen-containing hydro-,' ' ', ' , '. ~ .
7~
carbons. Catalyst Y is the crystalline silicate. Catalyst Z is the cata-lyst containing the metal component having catalytic activity for the water - gas shift reaction. As has been explained hereinbefore the use o:E a Z-cata-lyst may be omitted in some cases.
If as the X-catalyst a catalyst is used whicll is capable of con-verting a H2/CO mixture into substantially oxygen-containing hydrocarbons, preference is given to a catalyst which is capable of converting the H2/CO
mixture into substantially methanol and/or dimethyl ether. For the conver-sion of a H2/CO mixture into substantially methanol, catalysts containing . 10 the metal combinations mentioned hereinbefore are very suitable. If de-,. sired, the said metal combinations may be emplaced on a carrier material.
'- By introducing an acid function into these catalysts, for instance by em-placing the metal combination on an acid carrier, it may be effected that . apart from the conversion of the H2/CO mixture into methanol a considerable part of the mixture will be converted into dimethyl ether.
X-catalysts which are capable of converting a H2/CQ mixture into substantially hydrocarbons are referred to in the literature as Fischer-Tropsch catalysts. Such catalysts often contain one or more metals of the iron group or ruthenium together with one or more promoters to increase the ; activity and/or selectivity and sometimes a carrier material such as kieselguhr. They can be prepared by precipitation, melting and by impreg-~ nation. The preparation of the catalysts containing one or more metals of ; the iron group, by impregnation, takes place by impregnating a porous car-rier with one or more aqueous solutions of salts of metals of the iron group and, optionally, of promoters, followed by drying and calcining the composi-tion. If in the process according to the invention use is made of a cata-lyst combination in which catalyst X is a Fischer-Tropsch catalyst, it is preferred to choose for this purpose an iron or cobalt catalyst, in partic-: - 8 -'' X ' .'~
;P7~
ular such a catalyst which has been prepared by impregnation. Very suitable Fischer-Tropsch catalysts for use in the catalyst combinations according to the invention are the catalysts preparecl by impregnation according to the Netherlands Patent Application 7,612,~l60, published May 12, 1978. The cata-lysts concerned contain per 100 pbw carrier 10-75 pbw of one or more metals of the iron group, together with one or more promoters in a quantity of 1-- 50% of the quantity of metals of the iron group present on the catalyst, which catalysts have such a specific average pore diameter (p) of at most 10,000 nm and such a specific average particle diameter (d) of at most 5 mm, the quotient p/d is more than 2 (p in nm and d in nm).
If in the process according to the invention the object is to use a catalyst combination of which X is a Fischer-Tropsch iron catalyst, it is preferred to choose an iron catalyst containing a promoter combination con-sisting of an alkali metal, a metal that is easy to reduce, such as copper or silver and, optionally, a metal that is hard to reduce, such as aluminium or zinc. A very suitable iron catalyst for the present purpose is a cata-lyst prepared by impregnation containing iron, potassium and copper on sil-ica as the carrier. If in the process according to the invention the object is to use a catalyst combination of which X is a Fischer-Tropsch cobalt catalyst, it is preferred to choose a cobalt catalyst containing a promoter combination consisting of an alkaline-earth metal and thorium, uranium or cerium. A very suitable Fischer-Tropsch cobalt catalyst for the present purpose is a catalyst prepared by impregnation containing cobalt, magnesium and thorium on silica as the carrier. Other very suitable Fischer-Tropsch cobalt catalysts prepared by impregnation are catalysts containing, in addi-tion to cobalt, one of the elements chromium, titanium, zirconium and zinc on silica as the carrier. If desired, it is also possible to use in the process according to the invention catalyst combinations containing an X-_ g _ X
' ' ' ' , ::
.:
.. , . ' , . . .
.
' ~ ' ' ' , ~
.
.
7~L
. .
catalyst, which is capable of converting a H2CO mixture into a mixture con-taining both hydrocarbons and oxygen-containing hydrocarbons in comparable quantities. As a rule, such a catalyst has sufficient catalytic activity for the water gas shift reaction, so that -the use of a Z-catalyst in the combination can be omitted. An example of an X-catalyst of thi-s type is an iron-chromium oxide catalyst. If desired, it is also possible to use in the process according to the invention catalyst combinations containing two or more X-catalysts, for instance in addition to a catalyst of the X-type which is capable of converting a H2/CO mixture into substantially hydrocarbons, a second catalyst of the X-type which is capable of converting a H2CO mixture into substantially oxygen-containing hydrocarbons.
Z-catalysts which are capable of converting a H2O/CO mixture into a H2/CO2 mixture are referred to in the literature as CO-shift catalysts.
Such catalysts often contain one or more metals of the group formed by iron, chromium, copper, zinc, cobalt, nickel and molybdenum as the catalytically active component, either as such, or in the form of their oxides or sul-phides. Examples of suitable CO-shift catalysts are the mixed sulphidic cat-alysts according to the Netherlands Patent Application 7,305,340 published October 21, 1974, Netherlands Patent Application 7,304,793, published October 9, 1974 and Canadian Patent Application No. 287,679. If in the pro-cess according to the invention use is made of a catalyst combination in which a Z-catalyst is present, it is preferred to choose a catalyst which contains both copper and zinc, in particular a catalyst in which the Cu/Zn atomic ratio lies between 0.25 and 4Ø
In the trifunctional catalysts the catalysts X, Y and, optionally, Z may be present as a mixture, in which, in principle, each particle of cata-lyst X is surrounded by a number of particles of catalyst Y and, optionally, catalyst Z and conversely. If the process is carried out with the use of a X
fixed catalyst bed, this bed may be built up of alternate layers of parti-` cles of catalysts X, Y and, optionally, Z. If the two or three catalysts are used as a mixture, this mixture may be a macromixture or a micromixture.
~` In the first case the trifunctional catalyst consists of two or three kinds of macroparticles of which one kind is completely made up of catalyst X, the ;.
second kind completely of catalyst Y and, optionally, a third kind complete-ly of catalyst Z. In the second case the trifunctional catalyst consists of one kind of macroparticles, each macroparticle being made up of a large num-ber of microparticles of each of the catalysts X, Y and, optionally, Z.
Trifunctional catalysts according to the invention in the form of micromix-tures may be prepared, for instance, by thoroughly mixing a fine powder of catalyst X with a fine powder of catalyst Y and, optionally, with a fine pow-der of catalyst Z and shaping the mixture to larger particles, for instance, by extruding or pelleti~ing. In the process according to the invention it is preferred to use trifunctional catalysts in the form of micromixtures.
The trifunctional catalysts which are used according to the inven-tion may also have been prepared by incorporating the metal components hav-ing catalytic activity for converting a H2JCO mixture into hydrocarbons and/
or oxygen-containing hydrocarbons and, optionally, the metal components hav-ing catalytic activity for the water gas shift reaction into the crystalline silicate, for instance by impregnation or by ion exchange.
The crystalline silicates which are used in the trifunctional cat-alysts according to the invention are usually prepared from an aqueous mix-ture as the starting material which contains the following compounds in a given ratio; one or more compounds of an alkali or alkaline-earth metal, one or more compounds containing a mono- or bivalent organic cation or from which such a cation is formed during the preparation of the silicate, one or more silicon compounds, one or more iron compounds, and, optionally, one or ,.. .
,. ~
, , ' :: . ' ' ` . ` "' ' ,' : ' ' ' :
7~L
more aluminium, gallium and/or germanium compounds. The preparation is ef-fected by maintaining the mixture at elevated temperature until the silicate has been formed and then separating the crystals of the silicate from the ~;
mother liquor. The silicates thus prepared contain alkali and/or alkaline-earth metal ions and mono- and/or bivalent organic cations. Before being .:~` used in the trifunctional catalysts according to the invention at least part of the mono- and/or bivalent organic cations introduced during the preparation are preferably converted into hydrogen ions, for instance by calcining and at least part of the exchangeable mono- and/or bivalent . 10 cations introduced during the preparation are preferably replaced by other ions, in particular hydrogen ions, ammonium ions and/or ions of the rare-earth metals. The crystalline silicates used in the trifunctional catalysts . according to the invention preferably have an alkali metal content of less than 1 %w and in particulàr of less than 0.05 %w. If desired, a binder ma-terial such as bentonite or kaolin may be incorporated in the trifunctional catalysts.
The process according to the invention preferably starts from a mixture of carbon monoxide and hydrogen whose H2/C0 molar ratio is more than 0.4.
The process according to the invention is preferably carried out at a temperature of from 200 to 500C and in particular of from 300 to 450C, a pressure of from 1 to 150 bar and in particular of from 5 to 100 bar and a space velocity of from 50 to 5000 and in particular of from 300 to 3000 Nl gas/l catalyst/hour.
~: The process according to the invention can very suitably be car-ried out by passing the feed in upward or in downward direction through a vertically disposed reactor in which a fixed or a moving bed of the trifunc-tional catalyst concerned is present. The process may, for instance, be . ~r . .
' `
carried out in the so-called fixed-bed operation, in bunker-flow operation or in ebulated-bed operation. It is preferred to use catalyst particles then with a diameter between 1 and 5 mm. If desired, the process may also be carried out in fluidized-bed operation or with the use of a suspension of the catalyst in a hydrocarbon oil~ It is preferred to use catalyst par-ticles then with a diameter between 10 and 150 ~m.
The invention will now be explained with reference to the follow-ing examples~
Example I
A crystalline iron silicate ~silicate A) was prepared as follows.
A mixture of Fe(N03)3~ SiO2~ NaN03 and [(C3117)4N]OH in water with the molar omposition Na 0- 1-5[(C3H7)4N]20- 0-~25 Pe23 2 2 heated for 48 hours in an autoclave at 150C under autogenous pressure.
After the reaction mixture had cooled down, the silicate formed was filtered - off, washed with water until the pH of the wash water was about 8 and dried for two hours at 120C. Silicate A thus prepared had the following chemical composition 0.8[(C3H7)4N/2o. 0.3 Na20. Fe203 2 2 The silicate had an X-ray powder diffraction pattern substantially as given in Table B of Netherlands patent application No. 7,613,957. The silicate was thermally stable to temperatures higher than 900C and was cap-able, after dehydration at 400C, to absorb in vacuum 7 ~w water at 25C and saturated water vapour pressure. With silicate A as the starting material silicate B was prepared by, successively, calcining silicate A at 500 C, boiling with 1.0 molar NH~1N03 solution, washing with water, boiling again with 1.0 molar NH4N03 solution and washing, drying for two hours at 120C
and calcining for four hours at 500C.
Example II
A crystalline silicate (silicate C) was prepared in substantially ~Y~
the same way as silicate A, the difference being that in the present case the starting material was an aqueous mixture which contained, in addition to Fe(NO3)3, Al~NO3)3 and which had tlle following molar composition:
Na2 4-5[(C3ll7)4N]2o 0.35 A1203 0.15 Fe2O3. 29.1 SiO2. 468 H20.
Silicate C thus prepared had the following chemical composition:
0.35[(C3~17)4N]20. 0-2 Na20. 0.15 Fe203. 0.35 A1203. 31 SiO2. 9 H20.
The silicate had an X-ray powder diffraction pattern substantially as given in Table B of Netherlands Patent Applica~ion 7~613,957, published June 20, 1978. The silicate was thermally stable to temperatures higher than 1000C and was capable, after a dehydration at 400C in vacuum, of ab-sorbing 8 %w water at 25C and saturated water vapour pressure. With sili-cate C as the starting material silicate D was prepared in the same way as described for the preparation of silicate B from silicate A.
Example III
A catalyst was prepared by mixing a ZnO-Cr203 composition with the crystalline iron silicate B in a weight ratio of 3:1. Both materials were present in the catalyst in the form of particles with a diameter of 0.15-0.3 mm. The ZnO-Cr203 composition used catalyses both the reduction of C0 to methanol and the water gas shift reaction. The catalyst obtained by mixing was tested for the one-stage preparation of an aromatic hydrocarbon mixture starting from a mixture of carbon monoxide and hydrogen. The testing was carried out in a 50-ml reactor, in which a fixed catalyst bed having a vol-ume of 7.5 ml was present. A mixture of carbon monoxide and hydrogen with a H2/C0 molar ratio of 0.5 was passed across the catalyst at a temperature of 37iC, a pressure of 60 bar and a space velocity of 1000 Nl gas/l cata-lyst/h. The results of this experiment are given below C0 conversion, % 50 ll2 conversion, % 53 ~,~
Product composition, %w on Cl+ product `. Cl S
: C
C~, 10 C5 product composition, %w on C5 product paraffins + olefins 20 naphthenes 27 aromatics 53 Example IV
- A catalyst was prepared by mixing the ~nO-Cr203 composition of ex-ample III with the crystalline iron-aluminium silicate D in a weight ratio of 5:1. Both materials were present in the catalyst in the form of par-ticles with a diameter of 0.15-0.3 mm. This catalyst was tested for the one-stage preparation of an aromatic hydrocarbon mixture starting from a mixture of carbon monoxide and hydrogen with a H2/C0 molar ratio of 0.5.
The testing was carried out in substantially the same way as described in example III, the differences being that in the present case a temperature of 350C and a pressure of 80 bar were used. The results of this experiment are given below C0 conversion, % 54 H2 conversion, % 59 Product composition, %w on C product ' 1 ' C 2 ; C2 2 c3 15 10 . .
.
.: . '' : :
.: :
- : . , .: . ~': .' , '. .:
' " ' ~ ' . :.
- C -C
. C5 product composition, %1~ on C5 product paraffins + olefins lX
naphthenes 20 aromatics 62 .: ' -::
. .
. .
,...
.
.
., ~.
.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing aromatic hydrocarbons by catalytic reaction of carbon monoxide with hydrogen characterized in that a mixture of carbon monoxide and hydrogen whose H2/CO molar ratio is less than 1.0 is converted in one step into an aromatic hydrocarbon mixture by contacting the gas mixture with a trifunctional catalyst containing one or more metal components having catalytic activity for the conversion of a H2/CO mixture into hydrocarbons and/or oxygen-containing hydrocarbons one or more metal components having catalytic activity for the water gas shift reaction and a crystalline silicate which a) is thermally stable to temperatures higher than 600°C
b) is capable of absorbing after dehydration at 400°C in vacuum more than 3%w water at 25°C and saturated water vapour pressure and c) has, in dehydrated form, the following overall composi-tion, expressed in moles of the oxides.
(1.0 + 0.3)(R)2/nO./a Fe2O3. b A12O3. c Ga2O3 /.
y (d SiO2. e GeO2), where R=one or more mono or bivalent cations, a ? 0.1.
b ? 0.
c ? 0.
a + b + c = 1.
y ? 10.
d ? 0.1.
e ? 0.
d + e = 1, and n = the valency of R
b) is capable of absorbing after dehydration at 400°C in vacuum more than 3%w water at 25°C and saturated water vapour pressure and c) has, in dehydrated form, the following overall composi-tion, expressed in moles of the oxides.
(1.0 + 0.3)(R)2/nO./a Fe2O3. b A12O3. c Ga2O3 /.
y (d SiO2. e GeO2), where R=one or more mono or bivalent cations, a ? 0.1.
b ? 0.
c ? 0.
a + b + c = 1.
y ? 10.
d ? 0.1.
e ? 0.
d + e = 1, and n = the valency of R
2. A process according to claim 1, characterized in that the trifunctional catalyst is composed of three separate catalysts of which the first catalyst (catalyst X) contains the metal compon-ents having catalytic activity for the conversion of a H2/CO mix-ture into substantially hydrocarbons, the second catalyst (cata-lyst Y is the crystalline silicate and the third catalyst (catalyst Z) contains the metal components having catalytic activity for the water gas shift reaction.
3. A process according to claim 2, characterized in that catalyst X is an iron or cobalt catalyst.
4. A process according to claim 2, characterized in that catalyst Z is a catalyst which contains both copper and zinc.
5. A process according to claim 2 characterized in that a trifunctional catalyst is used which consists of one kind of macroparticles, each macroparticle being built up of a large number of microparticles of each of the catalysts X, Y, and, optionally Z.
6. A process according to any of claims 1 to 3 characterized in that it is carried out at a temperature of from 200 to 500°C, a pressure of from 1 to 150 bar and a space velocity of from 50 to 5000 N1 gas/1 catalyst/h.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL7711719 | 1977-10-26 | ||
NL7711719A NL7711719A (en) | 1977-10-26 | 1977-10-26 | PROCESS FOR THE PREPARATION OF HYDROCARBONS. |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1111074A true CA1111074A (en) | 1981-10-20 |
Family
ID=19829409
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA310,511A Expired CA1111074A (en) | 1977-10-26 | 1978-09-01 | Process for preparing aromatic hydrocarbons |
Country Status (10)
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JP (1) | JPS5470230A (en) |
AU (1) | AU521103B2 (en) |
BE (1) | BE871276A (en) |
CA (1) | CA1111074A (en) |
DE (1) | DE2846254A1 (en) |
FR (1) | FR2407190A1 (en) |
GB (1) | GB2006819B (en) |
IT (1) | IT1099503B (en) |
NL (1) | NL7711719A (en) |
ZA (1) | ZA785979B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5344849A (en) * | 1990-10-31 | 1994-09-06 | Canada Chemical Corporation | Catalytic process for the production of hydrocarbons |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5612628A (en) * | 1979-07-11 | 1981-02-07 | Olympus Optical Co Ltd | Single-lens reflex camera |
NL182469C (en) * | 1979-08-02 | 1988-03-16 | Shell Int Research | METHOD FOR PREPARING CRYSTALLINE IRON SILICATES; METHOD FOR PERFORMING CATALYTIC PROCESSES |
NL184214C (en) | 1979-08-06 | 1989-05-16 | Shell Int Research | PROCESS FOR THE PREPARATION OF A HYDROCARBON MIXTURE FROM A MIXTURE CONTAINING CARBON MONOXIDE AND HYDROGEN WITH ONE HŸ2/CO MOL. CONTAINS LESS THAN 1.0 RATIO. |
NL8001342A (en) * | 1980-03-06 | 1980-07-31 | Shell Int Research | METHOD FOR PERFORMING CATALYTIC CONVERSIONS |
FR2496095B1 (en) * | 1980-12-15 | 1985-11-15 | Shell Int Research | PROCESS FOR THE PREPARATION OF A HYDROCARBON MIXTURE FROM A H2 / CO MIXTURE |
NL8101447A (en) * | 1981-03-24 | 1982-10-18 | Shell Int Research | METHOD FOR PREPARING HYDROCARBONS FROM CARBON-CONTAINING MATERIAL |
NL8102470A (en) * | 1981-05-20 | 1982-12-16 | Shell Int Research | PROCESS FOR PREPARING AN AROMATIC HYDROCARBON MIXTURE |
FR2509719A1 (en) * | 1981-07-17 | 1983-01-21 | Shell Int Research | PROCESS FOR PRODUCING HYDROCARBONS |
CA1196617A (en) * | 1982-07-14 | 1985-11-12 | George E. Morris | Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas |
-
1977
- 1977-10-26 NL NL7711719A patent/NL7711719A/en not_active Application Discontinuation
-
1978
- 1978-09-01 CA CA310,511A patent/CA1111074A/en not_active Expired
- 1978-10-16 BE BE1009099A patent/BE871276A/en not_active IP Right Cessation
- 1978-10-24 AU AU41006/78A patent/AU521103B2/en not_active Expired
- 1978-10-24 FR FR7830188A patent/FR2407190A1/en active Granted
- 1978-10-24 GB GB7841670A patent/GB2006819B/en not_active Expired
- 1978-10-24 JP JP13012878A patent/JPS5470230A/en active Pending
- 1978-10-24 ZA ZA00785979A patent/ZA785979B/en unknown
- 1978-10-24 IT IT29061/78A patent/IT1099503B/en active
- 1978-10-24 DE DE19782846254 patent/DE2846254A1/en not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5344849A (en) * | 1990-10-31 | 1994-09-06 | Canada Chemical Corporation | Catalytic process for the production of hydrocarbons |
Also Published As
Publication number | Publication date |
---|---|
FR2407190B1 (en) | 1984-02-03 |
NL7711719A (en) | 1979-05-01 |
IT1099503B (en) | 1985-09-18 |
BE871276A (en) | 1979-04-17 |
FR2407190A1 (en) | 1979-05-25 |
AU4100678A (en) | 1980-05-01 |
IT7829061A0 (en) | 1978-10-24 |
AU521103B2 (en) | 1982-03-18 |
GB2006819B (en) | 1982-03-17 |
DE2846254A1 (en) | 1979-05-03 |
JPS5470230A (en) | 1979-06-05 |
ZA785979B (en) | 1979-10-31 |
GB2006819A (en) | 1979-05-10 |
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