CA1180312A - Process for the preparation of crystalline silicates - Google Patents
Process for the preparation of crystalline silicatesInfo
- Publication number
- CA1180312A CA1180312A CA000407161A CA407161A CA1180312A CA 1180312 A CA1180312 A CA 1180312A CA 000407161 A CA000407161 A CA 000407161A CA 407161 A CA407161 A CA 407161A CA 1180312 A CA1180312 A CA 1180312A
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- sio2
- molar ratio
- aluminium
- compounds
- 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
- 238000002360 preparation method Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 13
- 150000004760 silicates Chemical class 0.000 title description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000000203 mixture Substances 0.000 claims abstract description 100
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 53
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 49
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 48
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 48
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 48
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 48
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 59
- 229910052742 iron Inorganic materials 0.000 claims description 37
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 32
- -1 iron silicates Chemical class 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 150000003377 silicon compounds Chemical class 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229940077746 antacid containing aluminium compound Drugs 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000003388 sodium compounds Chemical class 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 150000001339 alkali metal compounds Chemical class 0.000 claims 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000003502 gasoline Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 14
- 238000009835 boiling Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000237074 Centris Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001260 acyclic compounds Chemical class 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 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
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2884—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures the aluminium or the silicon in the network being partly replaced
-
- 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
-
- 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
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
-
- 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
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/88—Ferrosilicates; Ferroaluminosilicates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
Al-containing (C)rystalline (I)ron (S)ilicate with a SiO2/Fe2O3 mol. ratio of 75-300 and a SiO2/Al2O3 mol. ratio of less than 2000 and having a crystal structure which is similar to that of ZSM-5 is prepared from an Al-containing base mixture comprising butylamine (BUAM). The stability of a ZnO-Cr2O3/CIS catalyst mixture - on basis of CIS
prepared via the BUAM route - in the direct gasoline synthesis can be considerably increased by incorporating a small amount of an aluminium compound in the ?se mixture from which the CIS component is prepared.
Al-containing (C)rystalline (I)ron (S)ilicate with a SiO2/Fe2O3 mol. ratio of 75-300 and a SiO2/Al2O3 mol. ratio of less than 2000 and having a crystal structure which is similar to that of ZSM-5 is prepared from an Al-containing base mixture comprising butylamine (BUAM). The stability of a ZnO-Cr2O3/CIS catalyst mixture - on basis of CIS
prepared via the BUAM route - in the direct gasoline synthesis can be considerably increased by incorporating a small amount of an aluminium compound in the ?se mixture from which the CIS component is prepared.
Description
3:~
PROCESS FOR THE PREPARATION OF CRYSTALLINE
. SILICATES
The invention relates to a process for the preparation of crystalline silicates having improved catalytic properties.
Mixtures of carbon monoxide and hydrogen can be converted into aromatic hydrocarbon mixtures by the use of a mixture of two catalysts, one having the property of catalyzing the conversion of a H2/CO
mixture into oxygen-containing organic compounds, and the other being a crystalline iron silicate capable of catalyzing the conversion of oxygen-con-taining organic compounds into aromatic hydrocarbons.
The said crystalline iron silicates are characterized in that~ after one hour's calcination in air at 500C, they have the ~ollowing properties:
a) thermally stable up to a temperature o~ at least 600C;
b) an X-ray powder diffraction pattern in which the strongesi lines are the four lines listed in Table A:
3~
TA~LE A
d(~)Relative intensity 11.1 ~ 0.2 VS
10.0 ~ 0.2 VS
3.84 ~ 0.07 S
3.72 ~ 0.06 S
in which the letters used have the following meanings: VS = very strong; S = strong, and c) in the formula which represents the composition of the silicate, expressed in moles of the oxides, the SiO2~Fe203 molar ratio is 75-30C.
In the present patent application a crystalline silicate having a thermal stability of at least tC
should be taken to be a silicate whose X-ray powder diffraction pattern remains substantially unchanged upon heating to a temperature of tC.
The crystalline silicates used in the catalyst mixtures may be prepared starting from an aqueous mixture comprising the following compounds: one or more compounds of an alkali metal (M), one or more amines of the general formula R1R2R3N, in which R1 is an alkyl group and R2 and R3 are an alkyl group or a hydrogen atom, one or more silicon compounds with a high SiO2 content and one or more compounds.
comprising iron in the trivalent form. In the ~8V3 present patent application silicon compounds with a high SiO2 content should be taken to be silicon com-pounds which, a~ter drying at 120C and calcinatio~
at 500C, yield a product with a SiO2 content hi~her than 90%w. The crystalline silicates are prepared by maintaining the mixture at an elevated temperature until the crystalline silicate has formed, separating the ~tter from the mother liquor and calcining i~. In the aqueous mixture from which the silicates are prepared, the various compounds should be present in the following molar ratios, expressed - ~ith the ex-ception of the amine~ - in moles of the oxides:
M20 : SiO2 = 0.01 - 0.35, R1R2R3N : SiO2 = 0.04 - 2.0, SiO2 : Fe203 = 50 400, and H20 : SiO2 = 5 - 65.
An investigation carried out by the Applicant into the application of the above-mentioned catalyst mixtures for the preparation of aromatic hydrocarbon mixtures from H2/C0 mixtures, has shown that the presence of aluminium in the crystalline iron silicates has a great influence upon the stability of the catalyst mixtures. The catalyst mixtures have been found to have an exceptionally high stabili~y, when the crystalline iron silicate present thereïn contains such a quantity of aluminium that in the formula ~8~3~
representing the composition of the silicate expressed in moles of the oxides the SiO2/A1203 molar ratio is lower than 2000.
In the present patent application the term "crystalline iron silicate" relates both to crystal-line silicates ~lhich comprise only iron as the tri-valent metal and to crystalline silicates which, in addition to iron, comprise aluminium, provided that in the formula which represents the composition of the silicate expressed in moles of the oxides the Fe203/A1203 molar ratio is higher than 1Ø The aluminium-containing crystalline iron silicates are prepared starting from an aqueous mixture which, in addition to the aforementioned compounds, contains one or more aluminium compounds. The quantity of aluminium compounds present in the aqueous mixture should be such that the SiO2/A1203 molar ratio is 50 - 4000. The preparation of aluminium-containing crystalline iron silicates as mentioned hereinabove, starting from an aqueous mixture containing one or more amines of the general formula R1R2R3N and one or more silicon compounds having a high SiO2 content, is new.
The present patent application therefore rèlates to a process for the preparation of crystalline iron silicates, characterized in that, after one hour's ~8~3~
calcination in air at 500C~ they have the following properties:
a) thermally stable up to a temperature of at least 600C;
b) an X--ray powder diffraction pattern in which the strongest lines are the ~our lines listed in Table A, and c) in the formula which represents the composition of the silicate expressed in moles of the oxides, the SiO2~Fe203 molar ratio is 75-300~ the SiO2/A1203 molar ratio is below 2000 and the Fe203/A1203 molar ratio is higher than 1Ø
The preparation is carried out by maintaining an aqueous mixture comprising the following com-pounds: one or more compounds of an alkali metal(M), one or more amines of the general formula R1R2R3N, one or more silicon compounds having a high SiO2 content, one or more compounds in which iron is present in the trivalent form and one or more aluminium compounds, in which mixture the various compounds are present in the following molar ratios, expressed -with the exception o~ the amines - in moles of the oxides:
~ ~ ~V 3~ 2 M2o : SiO2 = 0.01 - 0-35 3 R1R2R3N : SiO2 = 0.04 - 2.0 SiO2 : Fe203 = 50 - 4, SiO2 : Al23 = 50 - 4000, and H2o : SiO2 = 5 - 65 at an elevated temperature until the crystalline silicate has formed and subsequently separating the crystalline silicate from the mother liquid and calcining it. Preferably, the H20/SiO2 molar ratio in the aqueous mixture is below 0.12.
The silicates prepared according to the in-vention are defined, among other things, by the X-ray powder diffraction pattern that they show after one hour's calcination in air at 500C. In this pattern the strongest lines should be the four lines listed in Table A. The complete X-ray powder diffraction pattern of a typical example of a silicate prepared according to the invention is given in Table B.
~lBV31~
TABLE B
d(~) Rel. int. d(~) Rel int.
11.1 loo 3.84 (D) 57 10.0 (D) 70 3. 70 ( D) 31 8.93 1 3.63 16 7.99 1 3.47 7.42 2 3.43 5 6.68 7 3.34 2 6.35 11 3.30 5 5. g7 17 3.25 5.70 7 3.05 8 5.56 lo 2.98 11 5.35 2 2.96 3 4.98 (D) 6 2.86 2 4.60 4 2.73 2 4.35 5 2.~0 2 4.25 7 2.48 3 4.07 2 2.40 2 4.00 4 (D) = doublet The prepatation of the silicates may be carried out at an atmospheri.c pressure as well as at an elevated pressure. If the reaction temperatures used lie above the boiling point of the mixture, the reaction is 5 preferably carried out in an autoclave under autogenous pressure. The silicates are preferably prepared by maintaining the mixture for at least four hours at a temperature between 90 and 300C and in particular at a temperature between 125 and 175C. After the formation of the silicates, the crystals are separated from the mother liquor, for instance by filtration, decantation or centri:~ugation. The mass of crystals is then washed with water and finally dried and calcined.
As examples of suitable compounds that can be used in the preparation of the silicates according to the in~ention may be mentioned nitrates, carbon-ates, hydroxides and oxides of alkali metals; amorphous solid silicas, silica sols, silica gels and silicic acid; oxides, hydroxides, normal salts and complex salts of trivalent iron, linear and branched alkyl-amines. In the preparation of silicates according to the invention the starting mixture is preferably an aqueous mixture in which M is present in a sodium compound and R1R2R3N is a linear primary alkylamine having 3-5 carbon atoms in the alkyl group, in particular n-butylamine.
As regards aluminium which, in the preparation of the crystalline iron silicates according to the invention, should be present in the aqueous mixture, the following may be noted. The silicon compounds with a hign SiO2 content eligible from the economical 33~'~
point of view for the preparation on a te.chnical scale of crystalline iron silicates according to the invention, usually contain a small proportion of aluminium as an impurity~ At least part of this aluminium is found in the iron silicate prepared.
This means that the use of such silicon compounds as the starting material results in crystalline iron silicates in which the formula representing the com-position of the silicate expressed in moles of the oxides, in addition to SiO2 and Fe203,also contains A1203. However, the SiO2/A1203 molar ratio is usually considerably higher than 2000. For instance, from silicon compounds with a normal aluminium con-tamination of 50-100 ppmw as the starting material, crystalline iron silicates are obtained having a SiO2/A1203 molar ratio of 5000-20,000. Regarding the .incorporation of aluminium into the aqueous mixtures from which the crystalline iron silicates are prepared according to the invention there are, basically, two possibilities. The starting mixture may be an aqueous mixture comprising a silicon com-pound which is contaminated with aluminium to such an extent that a crystalline iron silicate is obtained having the desired SiO2/A120~ molar ratio below 2000.
For instance, from silicon compounds with a high aluminium contamination - of about 1000 ppmw - as the star~ing material, crystalline iron silicates are obtained having a SiO2/A1203 molar ratio of 500-1000.
The aqueous mixture may also be made to contain such a proportion of one or more aluminium compounds that, while any quantity of aluminium already present in the silicon compound used is taken account of, a crystal-line silicate is obtained having the desired SiO2tA1203 molar ratio below 2000. Examples of suitable aluminium compounds which~ in the preparation of the crystalline iron silicates, may be incorporated into the aqueous mixture include aluminium hydroxide, aluminium sul-phate, sodium aluminate and amorphous alumina.
Silicates prepared according to the invention may be used~ among other things, as adsorbing agents and extracting agents, as drying agents, as ion ex-changers and as catalysts or catalyst carriers for use in a variety of catalytic proGesses, in particular the catalytic preparation of aromatic hydrocarbons from acyclic compounds.
If the silicates prepared according to the in-vention are to be used as catalysts or catalyst car-riers, the alkali metal content of these silic2tes should preferahly be reduced beforehand to less than 0.1 and in particular to less than 0.01%w. The reduction of ~he alh-ali metal content of the silicates may very suitably be carried out by contacting the silicates 31;~
once or several times with an aqueous solution con-taining ammonium ions. The NH4~ silicates thus ob-tained may be calcined to form the H~ silicates.
When the crystalline iron silicates are used as catalysts they may, if desired, be comblned with a binder material, such as bentonite or kaoline.
As explained hereinabove, the silicates pre-pared according to the invention find an important application in catalyst mixtures to be used for the preparation of an aromatic hydrocarbon mixture from a H2/C0 mixture. H2/C0 mixtures may be prepared by steam gasification of a carbon-containing material.
Examples of such materials are brown coal, anthracite, coke, crude mineral oil and fractions thereof and also oils obtained from tar sand and bituminous shale.
The steam gasification is preferably carried out at a temperature between 900 and 1500C and a pressure be-tween 10 and 50 bar. For the preparation of the aromatic hydrocarbon mixture the starting material is preferably a H2/C0 mixture with a H2/C0 molar ratio between 0.25 and 1Ø The preparation of the aromatic hydrocarbon mixture from a H2/C0 mixture using a catalyst mixture comprising a crystalline iron silicate prepared according to the invention, is preferably carried out at a temperature of from 200-500C and in particular of from 300-450C, a 3~
pressure of from 1-150 bar and in particular of from 5-100 bar and a space velocity of from 50-5000 and in particular of from 300-3000 Nl gas/l catalyst/hour.
The two catalysts present in the catalyst mlxture used in the preparation of the aromatic hydrocarbon mixture from a H2/C0 mixture will for the sake of brevity hereinafter he referred to as catalysts X
and Y. Catalyst X is the catalyst capable of catalyzing the conversion of a H2/C0 mixture into oxygen-contain-ing organic compounds and catalyst Y is the crystal-line iron silicate prepared according to the in-vention. ~or use as catalysts X preference is given to catalysts capable of converting a H2/C0 mixture into substantially methanol and/or dimethyl ether.
If it is the object to prepare a product substantially consisting of hydrocarbons boiling in the gasoline range, the catalyst X used may very suitably be a catalyst which comprises zinc together with chromium.
When such a catalyst is used, it is preferably chosen to be a catalyst in which the atomic percentage of zinc, calculated on the sum of zinc and chromium, is at least 60% and in particular 60-80%. If the object is to prepare not only hydrocarbons boiling in the gasoline range, hut also a fuel gas wi~h a high calorific value, the catalyst X used` may very suit-ably be a catalyst comprising zinc together with ~8V~
copper. Preference is given to the use o~ a catalyst mixture which, per part by volume of catalyst Y, com-prises 1-5 pbv of catalyst X.
The conversion described hereinabove using a mixture of a crystalline iron silicate prepared ac-cording to the invention and a catalyst capable of catalyzing the conversion of a H2/C0 mixture into oxygen-containing organic compounds, can very suit-ably be carried out as the first step of a two-step process for the conversion of H2/C0 mixtures into hydrocarbon mixtures. In this case carbon monoxide and hydrogen present in the reaction product from the first step are contacted in a second step, if desired, together with other components of this reaction product, with a catalyst comprising one or more metal components having catalytic activity for the conversion of a H2/C0 mixture lnto paraffinic hydrocarbons, which metal components have been chosen from the group formed by cobalt, nickel and ruthenium, care being taken that the feed for the second step has a H2/C0 molar ratio of 1.75-2.25.
The conversion described hereinabove, using a mixture of a crystalline iron silicate prepared ac-cording to the invention and a catalyst capable of catalyzing the conversïon of a H2/C0 mixture ïnto oxygen-containing organic compounds, can very suit-ably be. used as the first s.tep of a three-.s.tage process for preparing, inter alia, middle dlstillates from a H2/CO mixture. I.n this case carbon manoxide and hydrogen present in .the reaction product from the fi.rst step are contacted in a second step, if desired, to.gether with other components of this reaction product, with a cobalt catalyst comprising zirconium, titanium or chromium as promoter, care being taken that the feed for the second step has a H2/CO molar ratio of 1.75-2.25. An example of a suitable catalyst for use in the second step is a catalyst which comprises 10-40 pbw of cobalt and 0.25-5 pbw of zirconium, titanium or chromium per 100 pbw of silica and has been prepared by impre~nation of a silica carrier with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium~ followed by drying of the com-position, calcination at 350-700C and reduction at 200-350C. At least that part of the reaciion product from the second step whose initial boiling point lies above the final boiling polnt of.the heaviest middle distillate desired as e~d-product, is subjected in a thlrd step, to a catalytic hydro-trea`tment.
The invention is.now illustrated with the aid of the following example.
EXAMPLE
Three crystalline iron silicates (silicates 1-3) were prepared from aqueous mixtures of NaOH, C4~9N~2, ~8V3~ ;~
amorphous silica I (for silicates 2 and 3) or amorphous silica II (for si.licate 1) and, optionally, amorphous alumina (for silicate ~). Furt.her, two crystalline aluminium silicates (sIlicates 4 and 5) were prepared from aqueous mixtures of NaOH, C4H9N~ , amorphous silica I and amorphous alumina. The preparation was carried out by heating the aqueous mixtures in an autoclave with stirring and under autogenous pressure for 120 hours at 150C. After cooling of the reaction mixtures the silicates formed were filtered off, washed with water until the pH of the wash water was about 8, and dried at 120C. After one hour's cal-cination in air at 500C~ silicates 1-5 had the fol-lowing propert;es:
a) thermally stable up to a temperature of at least b) an X-ray powder diffraction pattern substantially corresponding to that given in Table B, and c) a value of the SiO2/Fe203 and SiO2/Al203 molar 20ratios as stated in Table C.
TABLE C
Silicate SiO2/Fe203 SiO2/Al203 No. molar ratio molar ratio _
PROCESS FOR THE PREPARATION OF CRYSTALLINE
. SILICATES
The invention relates to a process for the preparation of crystalline silicates having improved catalytic properties.
Mixtures of carbon monoxide and hydrogen can be converted into aromatic hydrocarbon mixtures by the use of a mixture of two catalysts, one having the property of catalyzing the conversion of a H2/CO
mixture into oxygen-containing organic compounds, and the other being a crystalline iron silicate capable of catalyzing the conversion of oxygen-con-taining organic compounds into aromatic hydrocarbons.
The said crystalline iron silicates are characterized in that~ after one hour's calcination in air at 500C, they have the ~ollowing properties:
a) thermally stable up to a temperature o~ at least 600C;
b) an X-ray powder diffraction pattern in which the strongesi lines are the four lines listed in Table A:
3~
TA~LE A
d(~)Relative intensity 11.1 ~ 0.2 VS
10.0 ~ 0.2 VS
3.84 ~ 0.07 S
3.72 ~ 0.06 S
in which the letters used have the following meanings: VS = very strong; S = strong, and c) in the formula which represents the composition of the silicate, expressed in moles of the oxides, the SiO2~Fe203 molar ratio is 75-30C.
In the present patent application a crystalline silicate having a thermal stability of at least tC
should be taken to be a silicate whose X-ray powder diffraction pattern remains substantially unchanged upon heating to a temperature of tC.
The crystalline silicates used in the catalyst mixtures may be prepared starting from an aqueous mixture comprising the following compounds: one or more compounds of an alkali metal (M), one or more amines of the general formula R1R2R3N, in which R1 is an alkyl group and R2 and R3 are an alkyl group or a hydrogen atom, one or more silicon compounds with a high SiO2 content and one or more compounds.
comprising iron in the trivalent form. In the ~8V3 present patent application silicon compounds with a high SiO2 content should be taken to be silicon com-pounds which, a~ter drying at 120C and calcinatio~
at 500C, yield a product with a SiO2 content hi~her than 90%w. The crystalline silicates are prepared by maintaining the mixture at an elevated temperature until the crystalline silicate has formed, separating the ~tter from the mother liquor and calcining i~. In the aqueous mixture from which the silicates are prepared, the various compounds should be present in the following molar ratios, expressed - ~ith the ex-ception of the amine~ - in moles of the oxides:
M20 : SiO2 = 0.01 - 0.35, R1R2R3N : SiO2 = 0.04 - 2.0, SiO2 : Fe203 = 50 400, and H20 : SiO2 = 5 - 65.
An investigation carried out by the Applicant into the application of the above-mentioned catalyst mixtures for the preparation of aromatic hydrocarbon mixtures from H2/C0 mixtures, has shown that the presence of aluminium in the crystalline iron silicates has a great influence upon the stability of the catalyst mixtures. The catalyst mixtures have been found to have an exceptionally high stabili~y, when the crystalline iron silicate present thereïn contains such a quantity of aluminium that in the formula ~8~3~
representing the composition of the silicate expressed in moles of the oxides the SiO2/A1203 molar ratio is lower than 2000.
In the present patent application the term "crystalline iron silicate" relates both to crystal-line silicates ~lhich comprise only iron as the tri-valent metal and to crystalline silicates which, in addition to iron, comprise aluminium, provided that in the formula which represents the composition of the silicate expressed in moles of the oxides the Fe203/A1203 molar ratio is higher than 1Ø The aluminium-containing crystalline iron silicates are prepared starting from an aqueous mixture which, in addition to the aforementioned compounds, contains one or more aluminium compounds. The quantity of aluminium compounds present in the aqueous mixture should be such that the SiO2/A1203 molar ratio is 50 - 4000. The preparation of aluminium-containing crystalline iron silicates as mentioned hereinabove, starting from an aqueous mixture containing one or more amines of the general formula R1R2R3N and one or more silicon compounds having a high SiO2 content, is new.
The present patent application therefore rèlates to a process for the preparation of crystalline iron silicates, characterized in that, after one hour's ~8~3~
calcination in air at 500C~ they have the following properties:
a) thermally stable up to a temperature of at least 600C;
b) an X--ray powder diffraction pattern in which the strongest lines are the ~our lines listed in Table A, and c) in the formula which represents the composition of the silicate expressed in moles of the oxides, the SiO2~Fe203 molar ratio is 75-300~ the SiO2/A1203 molar ratio is below 2000 and the Fe203/A1203 molar ratio is higher than 1Ø
The preparation is carried out by maintaining an aqueous mixture comprising the following com-pounds: one or more compounds of an alkali metal(M), one or more amines of the general formula R1R2R3N, one or more silicon compounds having a high SiO2 content, one or more compounds in which iron is present in the trivalent form and one or more aluminium compounds, in which mixture the various compounds are present in the following molar ratios, expressed -with the exception o~ the amines - in moles of the oxides:
~ ~ ~V 3~ 2 M2o : SiO2 = 0.01 - 0-35 3 R1R2R3N : SiO2 = 0.04 - 2.0 SiO2 : Fe203 = 50 - 4, SiO2 : Al23 = 50 - 4000, and H2o : SiO2 = 5 - 65 at an elevated temperature until the crystalline silicate has formed and subsequently separating the crystalline silicate from the mother liquid and calcining it. Preferably, the H20/SiO2 molar ratio in the aqueous mixture is below 0.12.
The silicates prepared according to the in-vention are defined, among other things, by the X-ray powder diffraction pattern that they show after one hour's calcination in air at 500C. In this pattern the strongest lines should be the four lines listed in Table A. The complete X-ray powder diffraction pattern of a typical example of a silicate prepared according to the invention is given in Table B.
~lBV31~
TABLE B
d(~) Rel. int. d(~) Rel int.
11.1 loo 3.84 (D) 57 10.0 (D) 70 3. 70 ( D) 31 8.93 1 3.63 16 7.99 1 3.47 7.42 2 3.43 5 6.68 7 3.34 2 6.35 11 3.30 5 5. g7 17 3.25 5.70 7 3.05 8 5.56 lo 2.98 11 5.35 2 2.96 3 4.98 (D) 6 2.86 2 4.60 4 2.73 2 4.35 5 2.~0 2 4.25 7 2.48 3 4.07 2 2.40 2 4.00 4 (D) = doublet The prepatation of the silicates may be carried out at an atmospheri.c pressure as well as at an elevated pressure. If the reaction temperatures used lie above the boiling point of the mixture, the reaction is 5 preferably carried out in an autoclave under autogenous pressure. The silicates are preferably prepared by maintaining the mixture for at least four hours at a temperature between 90 and 300C and in particular at a temperature between 125 and 175C. After the formation of the silicates, the crystals are separated from the mother liquor, for instance by filtration, decantation or centri:~ugation. The mass of crystals is then washed with water and finally dried and calcined.
As examples of suitable compounds that can be used in the preparation of the silicates according to the in~ention may be mentioned nitrates, carbon-ates, hydroxides and oxides of alkali metals; amorphous solid silicas, silica sols, silica gels and silicic acid; oxides, hydroxides, normal salts and complex salts of trivalent iron, linear and branched alkyl-amines. In the preparation of silicates according to the invention the starting mixture is preferably an aqueous mixture in which M is present in a sodium compound and R1R2R3N is a linear primary alkylamine having 3-5 carbon atoms in the alkyl group, in particular n-butylamine.
As regards aluminium which, in the preparation of the crystalline iron silicates according to the invention, should be present in the aqueous mixture, the following may be noted. The silicon compounds with a hign SiO2 content eligible from the economical 33~'~
point of view for the preparation on a te.chnical scale of crystalline iron silicates according to the invention, usually contain a small proportion of aluminium as an impurity~ At least part of this aluminium is found in the iron silicate prepared.
This means that the use of such silicon compounds as the starting material results in crystalline iron silicates in which the formula representing the com-position of the silicate expressed in moles of the oxides, in addition to SiO2 and Fe203,also contains A1203. However, the SiO2/A1203 molar ratio is usually considerably higher than 2000. For instance, from silicon compounds with a normal aluminium con-tamination of 50-100 ppmw as the starting material, crystalline iron silicates are obtained having a SiO2/A1203 molar ratio of 5000-20,000. Regarding the .incorporation of aluminium into the aqueous mixtures from which the crystalline iron silicates are prepared according to the invention there are, basically, two possibilities. The starting mixture may be an aqueous mixture comprising a silicon com-pound which is contaminated with aluminium to such an extent that a crystalline iron silicate is obtained having the desired SiO2/A120~ molar ratio below 2000.
For instance, from silicon compounds with a high aluminium contamination - of about 1000 ppmw - as the star~ing material, crystalline iron silicates are obtained having a SiO2/A1203 molar ratio of 500-1000.
The aqueous mixture may also be made to contain such a proportion of one or more aluminium compounds that, while any quantity of aluminium already present in the silicon compound used is taken account of, a crystal-line silicate is obtained having the desired SiO2tA1203 molar ratio below 2000. Examples of suitable aluminium compounds which~ in the preparation of the crystalline iron silicates, may be incorporated into the aqueous mixture include aluminium hydroxide, aluminium sul-phate, sodium aluminate and amorphous alumina.
Silicates prepared according to the invention may be used~ among other things, as adsorbing agents and extracting agents, as drying agents, as ion ex-changers and as catalysts or catalyst carriers for use in a variety of catalytic proGesses, in particular the catalytic preparation of aromatic hydrocarbons from acyclic compounds.
If the silicates prepared according to the in-vention are to be used as catalysts or catalyst car-riers, the alkali metal content of these silic2tes should preferahly be reduced beforehand to less than 0.1 and in particular to less than 0.01%w. The reduction of ~he alh-ali metal content of the silicates may very suitably be carried out by contacting the silicates 31;~
once or several times with an aqueous solution con-taining ammonium ions. The NH4~ silicates thus ob-tained may be calcined to form the H~ silicates.
When the crystalline iron silicates are used as catalysts they may, if desired, be comblned with a binder material, such as bentonite or kaoline.
As explained hereinabove, the silicates pre-pared according to the invention find an important application in catalyst mixtures to be used for the preparation of an aromatic hydrocarbon mixture from a H2/C0 mixture. H2/C0 mixtures may be prepared by steam gasification of a carbon-containing material.
Examples of such materials are brown coal, anthracite, coke, crude mineral oil and fractions thereof and also oils obtained from tar sand and bituminous shale.
The steam gasification is preferably carried out at a temperature between 900 and 1500C and a pressure be-tween 10 and 50 bar. For the preparation of the aromatic hydrocarbon mixture the starting material is preferably a H2/C0 mixture with a H2/C0 molar ratio between 0.25 and 1Ø The preparation of the aromatic hydrocarbon mixture from a H2/C0 mixture using a catalyst mixture comprising a crystalline iron silicate prepared according to the invention, is preferably carried out at a temperature of from 200-500C and in particular of from 300-450C, a 3~
pressure of from 1-150 bar and in particular of from 5-100 bar and a space velocity of from 50-5000 and in particular of from 300-3000 Nl gas/l catalyst/hour.
The two catalysts present in the catalyst mlxture used in the preparation of the aromatic hydrocarbon mixture from a H2/C0 mixture will for the sake of brevity hereinafter he referred to as catalysts X
and Y. Catalyst X is the catalyst capable of catalyzing the conversion of a H2/C0 mixture into oxygen-contain-ing organic compounds and catalyst Y is the crystal-line iron silicate prepared according to the in-vention. ~or use as catalysts X preference is given to catalysts capable of converting a H2/C0 mixture into substantially methanol and/or dimethyl ether.
If it is the object to prepare a product substantially consisting of hydrocarbons boiling in the gasoline range, the catalyst X used may very suitably be a catalyst which comprises zinc together with chromium.
When such a catalyst is used, it is preferably chosen to be a catalyst in which the atomic percentage of zinc, calculated on the sum of zinc and chromium, is at least 60% and in particular 60-80%. If the object is to prepare not only hydrocarbons boiling in the gasoline range, hut also a fuel gas wi~h a high calorific value, the catalyst X used` may very suit-ably be a catalyst comprising zinc together with ~8V~
copper. Preference is given to the use o~ a catalyst mixture which, per part by volume of catalyst Y, com-prises 1-5 pbv of catalyst X.
The conversion described hereinabove using a mixture of a crystalline iron silicate prepared ac-cording to the invention and a catalyst capable of catalyzing the conversion of a H2/C0 mixture into oxygen-containing organic compounds, can very suit-ably be carried out as the first step of a two-step process for the conversion of H2/C0 mixtures into hydrocarbon mixtures. In this case carbon monoxide and hydrogen present in the reaction product from the first step are contacted in a second step, if desired, together with other components of this reaction product, with a catalyst comprising one or more metal components having catalytic activity for the conversion of a H2/C0 mixture lnto paraffinic hydrocarbons, which metal components have been chosen from the group formed by cobalt, nickel and ruthenium, care being taken that the feed for the second step has a H2/C0 molar ratio of 1.75-2.25.
The conversion described hereinabove, using a mixture of a crystalline iron silicate prepared ac-cording to the invention and a catalyst capable of catalyzing the conversïon of a H2/C0 mixture ïnto oxygen-containing organic compounds, can very suit-ably be. used as the first s.tep of a three-.s.tage process for preparing, inter alia, middle dlstillates from a H2/CO mixture. I.n this case carbon manoxide and hydrogen present in .the reaction product from the fi.rst step are contacted in a second step, if desired, to.gether with other components of this reaction product, with a cobalt catalyst comprising zirconium, titanium or chromium as promoter, care being taken that the feed for the second step has a H2/CO molar ratio of 1.75-2.25. An example of a suitable catalyst for use in the second step is a catalyst which comprises 10-40 pbw of cobalt and 0.25-5 pbw of zirconium, titanium or chromium per 100 pbw of silica and has been prepared by impre~nation of a silica carrier with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium~ followed by drying of the com-position, calcination at 350-700C and reduction at 200-350C. At least that part of the reaciion product from the second step whose initial boiling point lies above the final boiling polnt of.the heaviest middle distillate desired as e~d-product, is subjected in a thlrd step, to a catalytic hydro-trea`tment.
The invention is.now illustrated with the aid of the following example.
EXAMPLE
Three crystalline iron silicates (silicates 1-3) were prepared from aqueous mixtures of NaOH, C4~9N~2, ~8V3~ ;~
amorphous silica I (for silicates 2 and 3) or amorphous silica II (for si.licate 1) and, optionally, amorphous alumina (for silicate ~). Furt.her, two crystalline aluminium silicates (sIlicates 4 and 5) were prepared from aqueous mixtures of NaOH, C4H9N~ , amorphous silica I and amorphous alumina. The preparation was carried out by heating the aqueous mixtures in an autoclave with stirring and under autogenous pressure for 120 hours at 150C. After cooling of the reaction mixtures the silicates formed were filtered off, washed with water until the pH of the wash water was about 8, and dried at 120C. After one hour's cal-cination in air at 500C~ silicates 1-5 had the fol-lowing propert;es:
a) thermally stable up to a temperature of at least b) an X-ray powder diffraction pattern substantially corresponding to that given in Table B, and c) a value of the SiO2/Fe203 and SiO2/Al203 molar 20ratios as stated in Table C.
TABLE C
Silicate SiO2/Fe203 SiO2/Al203 No. molar ratio molar ratio _
2 115 2570
3 130 560
4 - 540 Amorphous silica I used in the preparation of silicates 2-5 comprised 280 ppmw of aluminium and, after drying at 120C and calcination at 500C, yielded a product consistin~ of 99.9%w of SiO2. Amorphous silica II used in the preparation of silicate 1 com-prised 70 ppmw of aluminium and, after drying at 120C
and calcination at 500C, yielded a product consisting of ~9.7%w of SiO2.
The molar composition of the aqueous mixtures from which silicates 1-5 were prepared may be rendered as follows . 2 4 9 2 2 3 Y 2 3 sio2.450 H20, where x and y have the values given in Table D.
3 ~'~
TABLE D
Silicate No. x y 1 0.20 0.002 2 0.20 o.oo8 3 0.20 0.041 4 . - 0.041 - 0.075 From silicates 1-5 were prepared silicates 6-10, respectively, by boiling silicates 1-5 with a 1.0 molar NH4N03 solution, washing with water, boiling again with a 1.0 molar NH4N03 solution~ and washing, drying at 120C and calcination at 500C. Five catalyst mixtures (catalyst mixtures A-E) were sub-sequently prepared by mixing a ZnO-Cr203 composition with each of silicates 6-10. The atomic Zn percentage of the ZnO-Cr203 composition, calculated on the sum Df Zn and Cr, was 70%. All the catalyst mixtures comprised 10 pbw of the ZnO-Cr203 composition per pbw of silicate.
Catalyst mixtures A-E were tested for the preparation of an aromatic hydrocarbon mixture from a H2/C0 mixture. The test was carried out in a 50-ml reactor containing a fixed catalyst bed of 7.5 ml volume. In fi-~e experiments a H2/CO mixture having a H2/C0 molar ratio of 0.5 was passed over each of catalyst mixtures A-E at a temperature of 375C~ a pres.sure of 60 bar and a space velocity of 1000 Nl.l 1.h 1. All these experiments yielded a product the C5 fraction of which consisted more than 30%w of aromatics. Furth.er results of the experiments are given in Table E.
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, s~
C~
a) ~ Q)~
o o~ s ~. ~ o ` oo U~
I ~ ~
+ ~ O
.,~ ~ ~o o V rl ~ ~
. _._ a)- ~ o ~ c~ c~ o~
~Q
, ~ ~
+ rl a~ o . ~ ~ ~o o .
V rl ~ ~ , o , ~
~ ~ ~ V o .~ o v~ u~ =r ~ o o J~ X tQ
~ -_~ .
E~ ` u~ ~ ~ ,~ O ~ C`J O
~d ~ ~ u~
~o ~ o . h ~ r ~ ~ ~ ~ ~ O
~ `O ~ O ~ `
o ~
a~
C~ . ~ O
rl O ~1 ~ æ
.,1 ~q .
~Q
'd ~x a) o ¢ m v ~ ~3 ~ æ
.r~
I ~ ~ o ~I ~ ~ 3 x Q) a) ~i Of the silicates lis:ted in Table C onl~ crystal-line iron silicate 3 ~as prepared according to the invention. Crystalline iron silicates 1 and 2 and crystalline aluminium silicates 4 and 5 fall outside the scope of the invention. They have been included in the present patent application for comparison.
Of the experiments listed in Table E only Experiment 3 was carried out using a catalyst comprising a crystal-line iron silicate prepared according to the in-vention. Experiments 1, 2, 4 and 5 fall outside the scope of the invention. They have been included in the patent application ~or comparison. On the results given in Table E the following may be remarked:
a) The results of Experiments 1 and 2 show that catalyst mixtures comprising a crystalline iron silicate havin~ a low aluminium content (SiO2/A1203 molar ratio > 2000), show a high initial activity and a very high selectivity.
The stability of these catalyst mixtures remains susceptible o~ improvement.
b) The result of Experiment 3 shows that raising the Al-content of the crystalline iron silicate to an SiO2/A1203 molar ratio ~ 2000, yields a very substantial improvement of the stabili~y, while the high initial activity and the very high seIectivity are preserved.
c) The catalyst mixture us.ed in Experiment 4.com-prised a crystalline aluminium silicate, in which the SiO2/A1203 molar ratio was chosen such that it corresponded with:that of the crystalline iron silica~e in the catalyst mixture used in Ex-periment 3. The resul~s. of Experiment 1~ s.how. that this catalyst mixture has a low initial act.ivity and a very low s:tability.
d) The catalyst mixture used in Experiment 5 com-prised a crystalline aluminium silicate in which the SiO2/A1203 molar ratio was chosen such that with this catalyst mixture an initial activity could be attained corresponding to that of the catalyst mixture used in Experiment 3. The results of Experiment 5 show that the stability of the catalyst mixture used remains very low.
Comparison of the results of Experiments 5 and 4 shows that reduction of the SiO2/A1203 molar ratio of the crystalline aluminium silicate leads to a considerable reduction in the C5 select~
ivity of the catalyst mixture.
and calcination at 500C, yielded a product consisting of ~9.7%w of SiO2.
The molar composition of the aqueous mixtures from which silicates 1-5 were prepared may be rendered as follows . 2 4 9 2 2 3 Y 2 3 sio2.450 H20, where x and y have the values given in Table D.
3 ~'~
TABLE D
Silicate No. x y 1 0.20 0.002 2 0.20 o.oo8 3 0.20 0.041 4 . - 0.041 - 0.075 From silicates 1-5 were prepared silicates 6-10, respectively, by boiling silicates 1-5 with a 1.0 molar NH4N03 solution, washing with water, boiling again with a 1.0 molar NH4N03 solution~ and washing, drying at 120C and calcination at 500C. Five catalyst mixtures (catalyst mixtures A-E) were sub-sequently prepared by mixing a ZnO-Cr203 composition with each of silicates 6-10. The atomic Zn percentage of the ZnO-Cr203 composition, calculated on the sum Df Zn and Cr, was 70%. All the catalyst mixtures comprised 10 pbw of the ZnO-Cr203 composition per pbw of silicate.
Catalyst mixtures A-E were tested for the preparation of an aromatic hydrocarbon mixture from a H2/C0 mixture. The test was carried out in a 50-ml reactor containing a fixed catalyst bed of 7.5 ml volume. In fi-~e experiments a H2/CO mixture having a H2/C0 molar ratio of 0.5 was passed over each of catalyst mixtures A-E at a temperature of 375C~ a pres.sure of 60 bar and a space velocity of 1000 Nl.l 1.h 1. All these experiments yielded a product the C5 fraction of which consisted more than 30%w of aromatics. Furth.er results of the experiments are given in Table E.
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, s~
C~
a) ~ Q)~
o o~ s ~. ~ o ` oo U~
I ~ ~
+ ~ O
.,~ ~ ~o o V rl ~ ~
. _._ a)- ~ o ~ c~ c~ o~
~Q
, ~ ~
+ rl a~ o . ~ ~ ~o o .
V rl ~ ~ , o , ~
~ ~ ~ V o .~ o v~ u~ =r ~ o o J~ X tQ
~ -_~ .
E~ ` u~ ~ ~ ,~ O ~ C`J O
~d ~ ~ u~
~o ~ o . h ~ r ~ ~ ~ ~ ~ O
~ `O ~ O ~ `
o ~
a~
C~ . ~ O
rl O ~1 ~ æ
.,1 ~q .
~Q
'd ~x a) o ¢ m v ~ ~3 ~ æ
.r~
I ~ ~ o ~I ~ ~ 3 x Q) a) ~i Of the silicates lis:ted in Table C onl~ crystal-line iron silicate 3 ~as prepared according to the invention. Crystalline iron silicates 1 and 2 and crystalline aluminium silicates 4 and 5 fall outside the scope of the invention. They have been included in the present patent application for comparison.
Of the experiments listed in Table E only Experiment 3 was carried out using a catalyst comprising a crystal-line iron silicate prepared according to the in-vention. Experiments 1, 2, 4 and 5 fall outside the scope of the invention. They have been included in the patent application ~or comparison. On the results given in Table E the following may be remarked:
a) The results of Experiments 1 and 2 show that catalyst mixtures comprising a crystalline iron silicate havin~ a low aluminium content (SiO2/A1203 molar ratio > 2000), show a high initial activity and a very high selectivity.
The stability of these catalyst mixtures remains susceptible o~ improvement.
b) The result of Experiment 3 shows that raising the Al-content of the crystalline iron silicate to an SiO2/A1203 molar ratio ~ 2000, yields a very substantial improvement of the stabili~y, while the high initial activity and the very high seIectivity are preserved.
c) The catalyst mixture us.ed in Experiment 4.com-prised a crystalline aluminium silicate, in which the SiO2/A1203 molar ratio was chosen such that it corresponded with:that of the crystalline iron silica~e in the catalyst mixture used in Ex-periment 3. The resul~s. of Experiment 1~ s.how. that this catalyst mixture has a low initial act.ivity and a very low s:tability.
d) The catalyst mixture used in Experiment 5 com-prised a crystalline aluminium silicate in which the SiO2/A1203 molar ratio was chosen such that with this catalyst mixture an initial activity could be attained corresponding to that of the catalyst mixture used in Experiment 3. The results of Experiment 5 show that the stability of the catalyst mixture used remains very low.
Comparison of the results of Experiments 5 and 4 shows that reduction of the SiO2/A1203 molar ratio of the crystalline aluminium silicate leads to a considerable reduction in the C5 select~
ivity of the catalyst mixture.
Claims (8)
1. A process for the preparation of crystalline iron silicates which, after one hour's calcination in air at 500°C, have the following properties:
a) thermally stable up to a temperature of at least 600°C;
b) an X-ray powder diffraction pattern in which the four lines listed in Table A are the strongest lines:
TABLE A
d(.ANG.) Relative intensity 11.1 ? 0.2 VS
10.0 ? 0.2 VS
3.84 ? 0.07 S
3.72 ? 0.06 S
in which the letters. used have the following meanings: VS = very strong; S = strong, and c) in the formula which represents the composition expressed in moles of the oxides, the SiO2/Fe2O3 molar ratio is 75-300, the SiO2/Al2O3 molar ratio is lower than 2000 and the Fe2O3/A12O3 molar ratio is higher than 1.0, characterized in that an aqueous mixture comprising the following com-pounds: one or more compounds of an alkali metal (M), one or more amines of the general formula R1R2R3N, where R1 is an alkyl group and R2 and R3 are an alkyl group or a hydrogen atom, one or more silicon compounds which, after dry-ing at 120°C and calcination at 500°C, yield a product having an SiO2 content of more than 90%w, one or more compounds in which iron occurs in the trivalent form and one or more aluminium com-pounds, in which mixture the compounds are present in the following molar ratios, expressed - with the exception of the amines - in moles of the oxides:
M20 : SiO2 = 0.01-0.35, R1R2R3N : SiO2 = 0.04-2.0, SiO2 : Fe2O3 = 50-400, SiO2 : Al2O3 - 50-4000, and H2O : SiO2 = 5-65, is maintained at an elevated temperature until the crystalline silicate has formed and the latter is subsequently separated from the mother liquor and calcined.
a) thermally stable up to a temperature of at least 600°C;
b) an X-ray powder diffraction pattern in which the four lines listed in Table A are the strongest lines:
TABLE A
d(.ANG.) Relative intensity 11.1 ? 0.2 VS
10.0 ? 0.2 VS
3.84 ? 0.07 S
3.72 ? 0.06 S
in which the letters. used have the following meanings: VS = very strong; S = strong, and c) in the formula which represents the composition expressed in moles of the oxides, the SiO2/Fe2O3 molar ratio is 75-300, the SiO2/Al2O3 molar ratio is lower than 2000 and the Fe2O3/A12O3 molar ratio is higher than 1.0, characterized in that an aqueous mixture comprising the following com-pounds: one or more compounds of an alkali metal (M), one or more amines of the general formula R1R2R3N, where R1 is an alkyl group and R2 and R3 are an alkyl group or a hydrogen atom, one or more silicon compounds which, after dry-ing at 120°C and calcination at 500°C, yield a product having an SiO2 content of more than 90%w, one or more compounds in which iron occurs in the trivalent form and one or more aluminium com-pounds, in which mixture the compounds are present in the following molar ratios, expressed - with the exception of the amines - in moles of the oxides:
M20 : SiO2 = 0.01-0.35, R1R2R3N : SiO2 = 0.04-2.0, SiO2 : Fe2O3 = 50-400, SiO2 : Al2O3 - 50-4000, and H2O : SiO2 = 5-65, is maintained at an elevated temperature until the crystalline silicate has formed and the latter is subsequently separated from the mother liquor and calcined.
2. A process as claimed in claim 1, characterized in that the M2O/SiO2 molar ratio of the aqueous mixture is lower than 0.12.
3. A process as claimed in claim 1 or 2, characterized in that the alkali metal compound used is a sodium com-pound and the R1R2R3N compound used is n-butylamine.
4. A process as claimed in claim 1, characterized in that the aqueous mixture is kept for at least 4 hours at a temperature between 90 and 300°C.
5. A process as claimed in claim 1, characterized in that the required quantity of aluminium has been introduced into the aqueous mixture by the use of a heavily aluminium-contaminated silicon compound and/or by the addition of a separate aluminium compound.
6. A process for the preparation of an aromatic hydrocarbon mixture from a H2/CO mixture, characterized in that the H2/CO
mixture is contacted with a mixture of two catalysts, one of which is capable of catalyzing the conversion of a H2/CO mixture into oxygen-containing organic compounds, the other being a crystalline iron silicate as prepared in claim 1.
mixture is contacted with a mixture of two catalysts, one of which is capable of catalyzing the conversion of a H2/CO mixture into oxygen-containing organic compounds, the other being a crystalline iron silicate as prepared in claim 1.
7. A process as claimed in claim 6, characterized in that as the catalyst capable of catalyzing the conversion of a H2/CO mixture into oxygen-containing organic compounds, a composition is used which comprises zinc together with chromium or copper.
8. A process as claimed in claim 6 or 7, characterized in that the H2/CO mixture has a H2/CO molar ratio between 0.25 and 1Ø
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL8103532 | 1981-07-27 | ||
NL8103532A NL8103532A (en) | 1981-07-27 | 1981-07-27 | Prepn. of new aluminium-contg. silica-rich iron silicate cpds. - catalysts esp. for making aromatic cpds. from aliphatic oxygen cpds. |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1180312A true CA1180312A (en) | 1985-01-02 |
Family
ID=19837855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000407161A Expired CA1180312A (en) | 1981-07-27 | 1982-07-13 | Process for the preparation of crystalline silicates |
Country Status (5)
Country | Link |
---|---|
AU (1) | AU549792B2 (en) |
CA (1) | CA1180312A (en) |
NL (1) | NL8103532A (en) |
NZ (1) | NZ201367A (en) |
ZA (1) | ZA825293B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5290533A (en) * | 1985-12-19 | 1994-03-01 | Eniricerche S.P.A. | Method for production of a coated substrate with controlled surface characteristics |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8301747A (en) * | 1983-05-17 | 1984-12-17 | Shell Int Research | METHOD FOR PREPARING MIDDLE DISTILLATES. |
US4961836A (en) * | 1986-05-23 | 1990-10-09 | Exxon Research And Engineering Company | Synthesis of transition metal alumino-silicate IOZ-5 and use of it for hydrocarbon conversion |
GB8616161D0 (en) * | 1986-07-02 | 1986-08-06 | Shell Int Research | Catalyst composition |
-
1981
- 1981-07-27 NL NL8103532A patent/NL8103532A/en not_active Application Discontinuation
-
1982
- 1982-07-13 CA CA000407161A patent/CA1180312A/en not_active Expired
- 1982-07-23 NZ NZ201367A patent/NZ201367A/en unknown
- 1982-07-23 ZA ZA825293A patent/ZA825293B/en unknown
- 1982-07-23 AU AU86366/82A patent/AU549792B2/en not_active Ceased
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5290533A (en) * | 1985-12-19 | 1994-03-01 | Eniricerche S.P.A. | Method for production of a coated substrate with controlled surface characteristics |
Also Published As
Publication number | Publication date |
---|---|
NL8103532A (en) | 1983-02-16 |
AU549792B2 (en) | 1986-02-13 |
NZ201367A (en) | 1984-09-28 |
ZA825293B (en) | 1983-05-25 |
AU8636682A (en) | 1983-02-03 |
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