EP1450946A1 - Cu/zn/al - katalysator für die methanolsynthese - Google Patents
Cu/zn/al - katalysator für die methanolsyntheseInfo
- Publication number
- EP1450946A1 EP1450946A1 EP02805277A EP02805277A EP1450946A1 EP 1450946 A1 EP1450946 A1 EP 1450946A1 EP 02805277 A EP02805277 A EP 02805277A EP 02805277 A EP02805277 A EP 02805277A EP 1450946 A1 EP1450946 A1 EP 1450946A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- catalyst according
- solution
- salts
- alkali metal
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 57
- 230000015572 biosynthetic process Effects 0.000 title claims description 16
- 238000003786 synthesis reaction Methods 0.000 title claims description 15
- 239000010949 copper Substances 0.000 claims abstract description 65
- 239000011701 zinc Substances 0.000 claims abstract description 43
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000005751 Copper oxide Substances 0.000 claims abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- -1 alkali metal aluminate Chemical class 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003388 sodium compounds Chemical class 0.000 claims description 2
- 241000264877 Hippospongia communis Species 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 241000907663 Siproeta stelenes Species 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000011514 reflex Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
Definitions
- the invention relates to a Cu / Zn / Al catalyst containing copper oxide and zinc oxide as catalytically active substances and aluminum oxide as a thermostabilizing substance.
- the invention further relates to a process for the preparation of this catalyst and its use for the synthesis of methanol.
- Cu / Zn / Al catalysts which catalyze the conversion of CO, C0 2 and H 2 to methanol have been known for a long time.
- the atomic ratios between copper and zinc can vary in these known catalysts, but the copper is generally present in excess.
- part of the zinc component can be partially replaced by calcium, magnesium and / or manganese.
- the aluminum oxide used as a thermostabilizing substance can also partially be replaced by chromium oxide.
- Such catalysts are known for example from DE-A 1 956 007, 2 302 658 and 2 056 612 and from US-A-4, 279, 781.
- a corresponding catalyst for methanol synthesis is also known from EP-A-0 125 689.
- This catalyst is characterized in that the proportion of pores with a diameter in the range from 20 to 75 ⁇ is at least 20% and the proportion of pores with a diameter of more than 75 ⁇ is at most 80%.
- the Cu / Zn atomic ratio is between 2.8 and 3.8, preferably between 2.8 and 3.2, and the proportion of A1 2 0 3 is 8 to 12% by weight.
- a similar catalyst for methanol synthesis is known from DE-A-44 16 425. It has a Cu / Zn atomic ratio of 2: 1 and generally consists of 50 to 75% by weight of CuO, 15 to 35% by weight of ZnO and also contains 5 to 20% by weight of A1 2 0 3 ,
- a similar catalyst is known from JP-A-07008799. It contains about 10 to 215 parts (atomic ratio) of Zn and about 1 to 50 parts of Al or Cr per 100 parts of Cu.
- EP-A-0 152 809 discloses a catalyst for the synthesis of alcohol mixtures containing methanol and higher alcohols, which in the form of an oxidic precursor (a) copper oxide and zinc oxide (b) aluminum oxide as a thermostabilizing substance and (c) at least one alkali carbonate or contains alkali oxide, the oxidic precursor having a proportion of pores with a diameter between 15 and 7.5 nm of 20 to 70% of the total volume, the alkali content being 13 to 130-10 "6 gram atom of alkali metal per gram of the oxidic precursor and the alumina component has been obtained from a colloidally distributed aluminum hydroxide (aluminum hydroxide sol or gel).
- the invention is therefore based on the object of providing Cu / Zn / Al catalysts with high specific activity, selectivity and thermal stability.
- the invention relates to a Cu / Zn / Al catalyst containing copper oxide and zinc oxide as catalytically active substances and aluminum oxide as a thermostabilizing substance, which is characterized in that the Cu / Zn atomic ratio is ⁇ 2.8, preferably between about 1, 8 and 2.7, and that the alumina component has been obtained at least partially from an aluminum hydroxide sol.
- the proportion of the aluminum oxide component corresponds essentially to the proportion in the known catalysts.
- the catalyst according to the invention has a higher activity in methanol synthesis, in particular at temperatures of less than 250 ° C., and a higher thermal stability than the catalyst according to EP-A-125 689, the aluminum hydroxide sol being responsible for increasing the thermal stability. This suppresses the coalescence of the copper crystallites after the reduction.
- the aluminum oxide particles obtained from the aluminum hydroxide sol on heating probably form net-like elevations on the surface of the catalyst, between which the CuO crystallites and, after the reduction, the copper crystallites are to a certain extent in an "energy sink".
- the zinc oxide also has a stabilizing effect in that it becomes a component of the reticulated Al 2 O 3 structure on the surface of the catalyst and thus helps to prevent the Cu crystallites from growing together after the reduction.
- the zinc oxide also acts as a poison scavenger by reacting with the sulfur compounds contained in the feed.
- the size of the Cu crystallites in the reduced state is preferably about 6 to 7 nm.
- the size of the Cu crystallites was determined by means of X-ray powder diffractometry (XRD).
- XRD X-ray powder diffractometry
- the Cu (III) reflex in the range of ⁇ 43.3 ° 2 ⁇ was measured.
- the full width at half maximum and the integral intensity of the reflex were calculated using the pseudo-Voigt and Lorentz profile functions.
- the Cu crystallite size was calculated using the Scherrer function on the basis of the calculated half-width.
- the proportion of the aluminum oxide component is preferably approximately 1 to 20% by weight, in particular approximately 5 to 20% by weight.
- the catalyst In the oxidic state, the catalyst has a BET surface area of about 90 to 120 m 2 / g and a pore volume of about 320 to 500 m / g, preferably about 320 to 380 ⁇ n / g.
- the BET surface area is determined using the nitrogen single-point method in accordance with DIN 66132.
- the pore volume is determined by the mercury intrusion method based on DIN 66133.
- a commercially available product can be used as the aluminum hydroxide sol.
- the aluminum hydroxide sol can also be obtained by adding a little NH 4 OH to a dilute aluminum salt solution, avoiding heating in order to delay the conversion into crystalline aluminum metahydroxide (AlO (OH)).
- boehmite ( ⁇ -AlO (OH)) or pseudoboehmite can be treated with nitric acid and the solution obtained can be diluted, the sol being formed.
- an alkali aluminate solution can be diluted (optionally with the addition of a small amount of acid), the sol being formed.
- the oxide catalysts are generally reduced as follows.
- the tablets (10 g) are heated in a tubular reactor with a reducing gas (98% N 2 , 2% H 2 ) at a heating rate of 1 ° C / min from room temperature to 240 ° C.
- the average degree of reduction of Cu is greater than 95%.
- the invention further relates to a process for the preparation of the catalyst indicated above, which is characterized in that the corresponding hydroxocarbonates or hydroxides are obtained from a solution of Cu and Zn salts and part of the Al salts with an alkali metal carbonate or alkali metal aluminate solution precipitates, with either the solution of the Cu and Zn salts or the alkali carbonate or alkali aluminate solution containing an aluminum hydroxide sol, whereupon the precipitate obtained is separated from the precipitation solution, washed, dried, calcined and optionally reduced.
- the corresponding nitrates are preferably used as Cu and Zn salts and the corresponding sodium compounds as alkali metal carbonates or alkali metal aluminates.
- the precursor of the catalyst according to the invention obtained after the precipitation and drying has a lower proportion of hydrotalcite analog phase than the known catalyst, because the aluminum hydroxide sol no longer reacts with the formation of hydrotalcite.
- a hydrotalcite analog phase is a hydrotalcite in which the magnesium is replaced by copper and zinc. Accordingly, the proportion of the malachite phase in the dried precursor is higher than in the known catalyst.
- the malachite phase consists essentially of a basic Cu / Zn carbonate.
- a Cu / Zn mixed oxide or a mixture of CuO and ZnO is formed in a fine distribution.
- the hydrotalcite-analog phase forms a Cu / Al oxide phase which, after reduction, gives a catalyst with relatively high stability but less activity.
- the catalyst obtained from the malachite phase is active but not as stable.
- the hydrotalcite-like phase and the malachite phase can be determined by X-ray diffraction analysis of the dried precursor. These phases disappear after the thermal treatment.
- the BET surface area also depends on the Cu / Zn atomic ratio. It is generally between about 90 and 120 m 2 / g and is therefore higher than the BET surface area of the known catalyst.
- the pore volume also depends on the Cu / Zn atomic ratio. It is generally between about 320 and 500 mm 3 / g, preferably between about 320 and 380 mm 3 / g, and is therefore higher than in the known catalyst.
- the invention also relates to the use of the catalyst for methanol synthesis.
- the experiments on methanol synthesis showed that the thermal stability of the catalysts is increased as the Cu / Zn atomic ratio decreases.
- the zinc oxide acts as a placeholder, which prevents the Cu crystallites from sintering together quickly in the reduced catalyst.
- the size of the copper crystallites decreases during the methanol synthesis depending on the CO 2 partial pressure, ie the Cu crystallites grow more strongly at higher CO 2 partial pressures.
- a 15.37% by weight sodium carbonate solution with a solution volume of 143 liters was prepared with distilled water (141 liters) at 50 ° C. by adding Na 2 CO 3 (25.15 kg).
- the solution had a density of 1.154 g / ml at 38 ° C.
- the nitrate solution (containing aluminum hydroxide sol) and the soda solution were simultaneously pumped through the mixing tube into the precipitation tank at a temperature of 74 ° C.
- the temperature in the precipitation tank was 60 ° C, the pH about 6.5.
- the residence time in the precipitation container was about 5 to 10 minutes.
- the suspension is pumped continuously from the precipitation container into the aging container.
- the suspension was heated to 70.degree.
- the precipitation was 60 min. aged at 70 ° C
- the color of the precipitation changes from light blue (start of aging) to green (end of aging).
- the pH rose from 6.6 + 0.1 to 7.3 ⁇ 0.1 in the course of aging.
- the suspension was filtered after aging.
- the wet filter cake was slurried in distilled water and filtered again. This process was repeated until the Na content in the filter cake was ⁇ 350 ppm.
- the filter cake was slurried to an oxide concentration of 10% by adding water and dried in a spray dryer at an inlet temperature of 275 to 280 ° C and an outlet temperature of 105 to 115 ° C.
- the washed catalyst precursor was then calcined at 320 ° C. for 3 hours.
- the oxidic catalyst precursor was in a tubular reactor with a reducing gas (98% N 2 ; 2% H 2 ) at a heating rate of 1 ° C / min. heated from room temperature to 240 ° C.
- the average degree of reduction of the Cu was 85%.
- the size of the Cu crystallites after the reduction was 6.3 nm.
- Example 2: Cu / Zn 2.4
- Example 1 The procedure of Example 1 was repeated with the difference that the Cu / Zn ratio used was 2.4 and the pH during the precipitation was 7.0 + 0.1. The size of the Cu crystallites after the reduction was 6.8 nm.
- Example 2 The procedure of Example 2 was repeated with the difference that the Cu / Zn ratio used was 2.62. The size of the Cu crystallites after the reduction was 7.5 nm.
- Solution 1 418 g of copper nitrate and 50 g of ZnO are dissolved in 1 liter of water and 148 g of 52.5% HN0 3 and then a solution of 93.8 g of A1 (N0 3 ) 3 x 9H 2 0 in 0.5 liters of water is added.
- Solution 2 410 g of sodium carbonate were dissolved in 2 liters of water.
- the solutions were heated separately to 68 ° C. and combined with vigorous stirring in such a way that the pH was 6.7 during the precipitation.
- the precipitate was aged with stirring at 68 ° C. for one hour in the mother liquor. On- it was finally filtered off and washed free of sodium with water.
- the filter cake was dried at 120 ° C and then calcined at 280 ° C for 8 hours. The calcined product was crushed and then compressed after adding 2% by weight of graphite.
- the size of the Cu crystallites after the reduction was 8.5 nm.
- Example 1 Example 2 Example 3 Example 4
- the by-products and the ethanol content were also determined as a function of the operating time in order to determine the selectivity.
- the by-products are higher hydrocarbons (C 3 to C ⁇ 0 ), alcohols (C 2 to C 5 ), ethers, esters and ketones. These are determined by gas chromatography.
- the by-products also interfere in the ppm range if they are present in the methanol.
- the by-products in the methanol require expensive processing (distillation) of the methanol.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10160486 | 2001-12-08 | ||
DE10160486A DE10160486A1 (de) | 2001-12-08 | 2001-12-08 | Katalysator für die Methanolsynthese |
PCT/EP2002/012395 WO2003053569A1 (de) | 2001-12-08 | 2002-11-06 | Cu/zn/al - katalysator für die methanolsynthese |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1450946A1 true EP1450946A1 (de) | 2004-09-01 |
Family
ID=7708598
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02805277A Withdrawn EP1450946A1 (de) | 2001-12-08 | 2002-11-06 | Cu/zn/al - katalysator für die methanolsynthese |
Country Status (9)
Country | Link |
---|---|
US (1) | US7754651B2 (de) |
EP (1) | EP1450946A1 (de) |
JP (1) | JP4343697B2 (de) |
AU (1) | AU2002357496A1 (de) |
CA (1) | CA2469531C (de) |
DE (1) | DE10160486A1 (de) |
NO (1) | NO329151B1 (de) |
WO (1) | WO2003053569A1 (de) |
ZA (1) | ZA200404331B (de) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005020630A1 (de) * | 2005-05-03 | 2006-11-23 | Süd-Chemie AG | Herstellung von Cu/Zn/Al-Katalysatoren über den Formiatweg |
DE102006061477B4 (de) | 2006-12-23 | 2019-04-04 | Süd-Chemie Ip Gmbh & Co. Kg | Verfahren zur Abtrennung und Reinigung von Feststoffen aus Suspensionen |
US20090149324A1 (en) * | 2007-12-05 | 2009-06-11 | Basf Catalysts Llc | Low temperature water gas shift catalyst |
DE102010021792B4 (de) * | 2010-05-27 | 2022-03-31 | Clariant Produkte (Deutschland) Gmbh | Katalysatoren und Verfahren zu deren Herstellung |
US8778833B2 (en) | 2010-11-11 | 2014-07-15 | Basf Corporation | Copper-zirconia catalyst and method of use and manufacture |
DE102011086451A1 (de) * | 2011-11-16 | 2013-05-16 | Süd-Chemie Ip Gmbh & Co. Kg | Methanolsynthesekatalysator auf basis von kupfer, zink und aluminium |
US9610568B2 (en) * | 2012-02-15 | 2017-04-04 | Basf Se | Catalytically active body for the synthesis of dimethyl ether from synthesis gas |
US9295978B2 (en) | 2012-02-15 | 2016-03-29 | Basf Corporation | Catalyst and method for the direct synthesis of dimethyl ether from synthesis gas |
DE102013225724A1 (de) | 2013-12-12 | 2015-06-18 | Evonik Industries Ag | Reinigung flüssiger Kohlenwasserstoffströme mittels kupferhaltiger Sorptionsmittel |
DE102014004391A1 (de) * | 2014-03-26 | 2015-10-15 | Clariant International Ltd. | Verfahren zur Herstellung von Katalysatoren mit erhöhter Festigkeit und verringertem Volumenschwund |
EP3023131A1 (de) | 2014-11-18 | 2016-05-25 | Evonik Degussa GmbH | Zweistufige Feinentschwefelung von Olefingemischen |
SG10201604013RA (en) | 2015-05-28 | 2016-12-29 | Evonik Degussa Gmbh | Hydrogen-assisted adsorption of sulphur compounds from olefin mixtures |
EP3305404A1 (de) | 2016-10-10 | 2018-04-11 | National Petrochemical Company | Kupfer/zink/aluminium-katalysator für die methanol-synthese hergestellt ausgehend von einer binären zink-aluminium-lösung |
DE102016225171A1 (de) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Tablettierter Katalysator für die Methanolsynthese mit erhöhter mechanischer Stabilität |
GB201701382D0 (en) * | 2017-01-27 | 2017-03-15 | Turner Rhodri | Catalyst suitable for methonal synthesis |
CN108568300B (zh) * | 2017-03-08 | 2020-11-24 | 中国石油化工股份有限公司 | 一种铜锌铝催化剂及其制备方法 |
CN113509936A (zh) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | 负载于复合凝胶载体上的甲醇合成催化剂的制备方法 |
AU2021334758A1 (en) * | 2020-08-31 | 2023-05-04 | Sumitomo Chemical Company, Limited | Methanol production method |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE743652A (de) | 1968-12-26 | 1970-05-28 | ||
GB1296212A (de) * | 1969-03-04 | 1972-11-15 | ||
DE2056612C3 (de) | 1970-11-18 | 1979-09-13 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Methanol |
GB1405012A (en) * | 1972-01-21 | 1975-09-03 | Ici Ltd | Method of making composition convertible to a catalyst precursor and catalyst and methanol synthesis using the catalyst |
US4279781A (en) * | 1979-10-09 | 1981-07-21 | United Catalysts Inc. | Catalyst for the synthesis of methanol |
DE3317725A1 (de) * | 1983-05-16 | 1984-11-22 | Süd-Chemie AG, 8000 München | Katalysator fuer die methanolsynthese |
DE3403491A1 (de) * | 1984-02-02 | 1985-08-14 | Süd-Chemie AG, 8000 München | Katalysator zur synthese von methanol und hoehere alkohole enthaltenden alkoholgemischen |
FR2647367B1 (fr) * | 1989-04-24 | 1991-08-30 | Inst Francais Du Petrole | Procede de preparation de precurseurs de catalyseurs contenant du cuivre, de l'aluminium et du zinc, utilisables pour la synthese et la decomposition du methanol |
EP0482753B1 (de) * | 1990-09-18 | 1996-12-04 | Csir | Katalysator für die Methanolsynthese |
JP3327630B2 (ja) | 1993-06-23 | 2002-09-24 | 関西電力株式会社 | メタノール合成用触媒の製造方法 |
DE4416425A1 (de) * | 1994-05-10 | 1995-11-16 | Metallgesellschaft Ag | Verfahren zur Erzeugung von Methanol |
US5990040A (en) * | 1995-01-11 | 1999-11-23 | United Catalysts Inc. | Promoted and stabilized copper oxide and zinc oxide catalyst and preparation |
-
2001
- 2001-12-08 DE DE10160486A patent/DE10160486A1/de not_active Ceased
-
2002
- 2002-11-06 EP EP02805277A patent/EP1450946A1/de not_active Withdrawn
- 2002-11-06 JP JP2003554322A patent/JP4343697B2/ja not_active Expired - Fee Related
- 2002-11-06 AU AU2002357496A patent/AU2002357496A1/en not_active Abandoned
- 2002-11-06 CA CA2469531A patent/CA2469531C/en not_active Expired - Fee Related
- 2002-11-06 WO PCT/EP2002/012395 patent/WO2003053569A1/de active Application Filing
- 2002-11-06 US US10/497,865 patent/US7754651B2/en not_active Expired - Fee Related
-
2004
- 2004-06-02 ZA ZA2004/04331A patent/ZA200404331B/en unknown
- 2004-06-22 NO NO20042614A patent/NO329151B1/no not_active IP Right Cessation
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO03053569A1 * |
Also Published As
Publication number | Publication date |
---|---|
NO20042614L (no) | 2004-06-22 |
US7754651B2 (en) | 2010-07-13 |
DE10160486A1 (de) | 2003-06-12 |
WO2003053569A1 (de) | 2003-07-03 |
CA2469531A1 (en) | 2003-07-03 |
US20050080148A1 (en) | 2005-04-14 |
JP4343697B2 (ja) | 2009-10-14 |
JP2005537119A (ja) | 2005-12-08 |
ZA200404331B (en) | 2005-08-31 |
CA2469531C (en) | 2011-05-17 |
NO329151B1 (no) | 2010-08-30 |
AU2002357496A1 (en) | 2003-07-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1450946A1 (de) | Cu/zn/al - katalysator für die methanolsynthese | |
EP0125689B1 (de) | Katalysator für die Methanolsynthese | |
EP1877336B1 (de) | Herstellung von cu/zn/al-katalysatoren über den formiatweg | |
EP0152809B1 (de) | Katalysator zur Synthese von Methanol und höhere Alkohole enthaltenden Alkoholgemischen | |
DE69709658T2 (de) | Saurer katalysator in fester form und verfahren zur herstellung desselben | |
DE69912113T2 (de) | Herstellung ungesättigter säuren oder von säureestern und dafür geeignete katalysatoren | |
EP0528305B2 (de) | Kupfer-Zinkoxid-Aluminiumoxid enthaltende Katalysatoren | |
DE60015345T2 (de) | Verfahren zur herstellung von quasi-kristallinen boehmiten | |
DE69721944T2 (de) | Katalysator für Dimethylether, Verfahren zur Katalysatorherstellung und Verfahren zur Herstellung von Dimethylether | |
DE19781988B4 (de) | Verfahren zur Herstellung von Methacrylsäureestern oder Acrylsäureestern | |
DE102012019123B4 (de) | Hydrierkatalysator und Verfahren zu dessen Herstellung durch die Verwendung von unkalziniertem Ausgangsmaterial | |
DE3017501A1 (de) | Katalysator fuer die herstellung von aethylen | |
DD299623A5 (de) | Nickel/silizium katalysator und verfahren und herstellung davon | |
WO2003053575A1 (de) | Katalysator für die methanolsynthese und andere reaktionen | |
EP0850212A1 (de) | Verfahren zur herstellung von methanol und katalysator dafür | |
EP2070898B1 (de) | Katalysator zur Oxichlorierung | |
DD208973A5 (de) | Verfahren zur herstellung von dimethylether | |
EP1050523A1 (de) | Verfahren zur Addition von Hydroxylgruppen enthaltenden Verbindungen an Alkine und Allene unter Verwendung eines Hemimorphit-Katalysators | |
DE4142900A1 (de) | Verwendung von kupferoxid-aluminiumoxid-magnesiumoxid-katalysatoren zur konvertierung von kohlenmonoxid | |
WO1994018118A1 (de) | Chromfreier katalysator auf basis eisenoxid zur konvertierung von kohlenmonoxid | |
EP0993431B1 (de) | Verfahren zur herstellung von enolethern | |
EP2297039B1 (de) | Verfahren zur herstellung kupfer- und chromhaltiger mischoxide | |
DE10033951B4 (de) | Verwendung eines heterogenen Katalysators für die Veresterung | |
DE102010021792A1 (de) | Katalysatoren und Verfahren zu deren Herstellung | |
DE2513683A1 (de) | Katalysatoren fuer die herstellung von isopren und ihre verwendung |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20040617 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SUED-CHEMIE IP GMBH & CO. KG |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SUED-CHEMIE IP GMBH & CO. KG |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B01J 23/80 20060101AFI20030708BHEP Ipc: C07C 29/00 20060101ALI20030708BHEP |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20190702 |