CA2314690A1 - Fixed bed catalysts - Google Patents
Fixed bed catalysts Download PDFInfo
- Publication number
- CA2314690A1 CA2314690A1 CA002314690A CA2314690A CA2314690A1 CA 2314690 A1 CA2314690 A1 CA 2314690A1 CA 002314690 A CA002314690 A CA 002314690A CA 2314690 A CA2314690 A CA 2314690A CA 2314690 A1 CA2314690 A1 CA 2314690A1
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- hydrogenation
- raney
- raney metal
- catalysts according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000003054 catalyst Substances 0.000 title claims abstract description 189
- 229910052751 metal Inorganic materials 0.000 claims abstract description 65
- 239000002184 metal Substances 0.000 claims abstract description 65
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 35
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 23
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 50
- 239000000956 alloy Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 44
- 239000011230 binding agent Substances 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 150000002191 fatty alcohols Chemical class 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 238000007493 shaping process Methods 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 13
- 230000003213 activating effect Effects 0.000 claims description 12
- 150000002194 fatty esters Chemical class 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012633 leachable Substances 0.000 claims description 10
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- -1 pore-producer Substances 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 3
- 229910052804 chromium Inorganic materials 0.000 claims 3
- 239000011651 chromium Substances 0.000 claims 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 2
- 239000011976 maleic acid Substances 0.000 claims 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- 239000000243 solution Substances 0.000 description 35
- 235000011121 sodium hydroxide Nutrition 0.000 description 17
- 150000002739 metals Chemical class 0.000 description 14
- 238000007127 saponification reaction Methods 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 12
- 150000008064 anhydrides Chemical class 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- JIQVGGQJISZHSS-UHFFFAOYSA-N ethene N-octadecanoyloctadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(=O)NC(=O)CCCCCCCCCCCCCCCCC JIQVGGQJISZHSS-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical class [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- B01J25/00—Catalysts of the Raney type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/177—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of a carboxy group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Shaped Raney-type metal fixed-bed catalysts are doped with rhenium. They can be used for the hydrogenation of saturated or unsaturated or unsaturated esters to their corresponding mono or multiple hydroxyalcohols.
Description
Fixed bed Catalysts This invention relates to fixed bed catalysts and their use for the hydrogenation of saturated and unsaturated esters.
Activated metal catalysts are known in the field of chemical engineering as Raney catalysts. They are used, largely in powder form, for a large number of hydrogenation, dehydrogenation, isomerization reductive alkylation, reductive amination, and hydration reactions of organic compounds. These powdered catalysts are prepared from an alloy of a catalytically active metal, also referred to herein as a catalyst metal, with a further alloying component which is soluble in alkalis. Mainly nickel, cobalt, copper, or iron are used as catalyst metals. Aluminum is generally used as the alloying component which is soluble in alkalis, but other components may also be used, in particular zinc and silicon or mixtures of these with aluminum.
Powdered catalysts have the disadvantage that they can be used only in a batch process and, after the catalytic reaction, have to be separated from the reaction medium by costly sedimentation and/or filtration. Therefore a variety of processes for preparing moulded items which lead to activated metal fixed-bed catalysts after extraction of the aluminum have been disclosed. Thus, for example, coarse particulate Raney alloys, i.e., Raney alloys which have only been coarsely milled, are obtainable and these can be activated by a treatment with caustic soda solution.
Extraction and activation then occurs only in a surface layer the thickness of which can be adjusted by the conditions used during extraction.
A substantial disadvantage of catalysts prepared by these prior methods are the poor mechanical stability of the activated outer layer. Since only this outer layer of the catalysts is the catalytically active, abrasion leads to rapid deactivation and renewed activation of deeper lying layers of alloy using caustic soda solution then leads at best to partial reactivation.
It is known that Re doped Pd (DE 25 19 817 A1)or Re doped Ru (WO 96/27436) supported catalysts are used for the production of gamma butyrolactone (GBL), tetrahydrofuran (THF), or 1,4-butanediol (BDO) by either maleic.acid or malefic anhydride hydrogenation. These systems work as either powder or fixed bed catalysts at pressures of 138 barr or higher and temperatures of 250°C or higher. In this respect, a system that performs this reaction at milder conditions would be a strong advantage. Copper-chromite is another catalyst system that has used for ester hydrogenation with some success (DE 39 03 029 A1).
The document EP 0 648 534 A1 describes shaped, activated Raney metal fixed-bed catalysts (Metalyst~) and their preparation. This technology avoids the disadvantages described above, e.g., the poor mechanical stability resulting from activating an outer layer. To prepare these catalysts, a mixture of powers consisting of a catalyst alloy and a binder are used, where the catalyst alloy contains at least one catalytically active catalyst metal and an extractable alloying component. The pure catalyst metals or mixtures thereof which do not contain extractable components are used as binder. The use of the binder in. an amount of 0.5 to 20 weight percent with respect to the catalyst alloy, is essential in order to achieve sufficient mechanical stability after activation. After shaping the catalyst alloy and the binder with conventional shaping aids and pore producers, the freshly prepared items which are obtained are calcined at temperatures below 850°C. As a result of sintering processes in the finely divided binder, this produces solid compounds between the individual granules of the catalysts alloy. These compounds, in contrast to catalyst alloys, are non-extractable or only extractable to a small extent so that a mechanically stable structure is obtained even after activation without endangering the strength of the shaped item.
An object of the present invention is therefore to provide fixed bed activated base metal catalysts that hydrogenate saturated and unsaturated esters at milder conditions than existing technologies with better activities and selectivities.
The fixed bed catalysts according to the invention show the advantage that Re doped metal catalysts can perform the hydrogenation of meleic acid or malefic anhydride to gamma butyrolactone, tetrahydrofuran or 1,4-butanediole at a temperature of 200°C and a pressure of 80 bar. Additionally these catalysts were able to hydrogenate fatty esters to the corresponding fatty alcohols at higher activities and selectivities than the standard copper chromite catalysts.
An object of the present invention is a shaped, activated Raney metal fixed-bed catalyst, said catalyst produced by a method consisting essentially of preparing a mixture of powders consisting essentially of at least one catalyst alloy and at least one binder, and a moistening agent, and optionally an additive selected from the group consisting of a shaping aid, lubricant, plasticizer, pore-producer, and mixtures thereof, wherein said catalyst alloy consists essentially of at least one Raney process metal as catalytically active catalyst metal, a leachable alloy component and optionally a promoter, wherein said binder consists essentially of at least one pure Raney process metal, homogenizing said mixture, shaping said mixture to give a molded catalyst precursor which still is not activated, calcining said molded catalyst precursor at a temperature below 850°C to obtain a sintered catalyst precursor, and activating said sintered catalyst precursor by leaching said leachable alloy component with alkali until the leached and thereby activated outer layer has an adjustable thickness corresponding upto 70$ or more of the molded form being activated, and subsequently washing the final catalyst; doping said catalyst with rhenium as a promoter after said activating and washing by introducing said catalyst into a Rhenium solution. The pH of the Re solution may or may not beadjusted, and the temperature of the doping solution can vary from lower than room temperature to substantial hygher temperatures. Moreover, the rhenium may be added to the unactivated alloy, the binder, or introduced in any other fashion that allows for it presence in the catalyst. The Re content can range from 0, O1 ~ Re to 15 ~ Re.
Preferred Raney process metals are nickel, cobalt, copper, or combination thereof and the leachable alloying components used are aluminum, zinc, silicon, or combintions thereof. These are generally leached in alkali such as NaOH. The ratio by weight of Raney process metal to leachable alloying component in the catalyst alloy is in the range from 10:90 to 90:10, as is usual with Raney alloys: The Raney process metal used as binder, in a real practical application, does not have to be the same as the catalyst metal present in the catalyst alloy. Rather, the possibility is opened up to combining different Raney process metals with each other as well as with promoter metals, in the catalyst alloy and as binder, offering a further important degree of freedom when adjusting the catalytic properties to the particular catalytic process.
Thus the binder used in the present invention can be nickel, cobalt, copper, iron, and optionally promoter metals. Generally any of the metals used for making Raney metal catalysts are suitable. The binder metal is used in an unleachable and unadulterated form.
Catalyst alloy and binder are processed in the form of powders, typically with the addition of moistening agents and optionally with the addition of conventional additives such as shaping aids, lubricants, plasticizers, and optionally pore-producers to give a moldable material. Any materials conventionally used for these purposes may be used as the shaping aid, lubricant, plasticizer and pore-producer. A number of suitable materials for this purpose are mentioned in the following U.S. Pat. Nos. (all of which 5 are incorporated by references in their entirety):
4,826,799; 3,404,551; and 3,351,495. Waxes such as, for example wax C micropowder PM from Hoechst AG, greases such as magnesium or aluminum stearates, or polymers which contain carbohydrates such as tylose (methylcellulose) are preferably used for the above purposes.
The solids in the mixture are carefully homogenized in suitable conventional mixers or kneaders with the addition of a moistening agent. Water, alcohols, glycols, polyether glycols or mixtures thereof are suitable as moistening agents as is well known in the art.
The primary particle size ranges of the powders of catalyst alloy and binder used are essentially unchanged during homogenization. That is, no milling takes place.
The purpose of this preliminary treatment with the moistening agent and additives is to prepare the mixture for the subsequent shaping process. Extrusion, pelleting and compression may be used for example for the shaping process employing conventional equipment known for such purposes.
The type and sequence of incorporation of additives depends on the shaping process to be used. Extrusion requires a plastic material with a specific viscosity, whereas a material which is free-flowing and which can be readily metered out is required for pelleting. The techniques to be used for this purpose, such as, for example, agglomeration to produce a free-flowing powder or adjustment to the correct viscosity for extrusion, are known as a matter of routine to the person skilled in the art. It is only important that the primary particle size ranges of the catalyst powder and binder powder are essentially unchanged by the preliminary treatment.
Any shapes which are conventional in the catalyst field are suitable as molded items. Spheres, rings, spoked rings or pellets may be produced, depending on the requirements of the particular application.
The final molded items are optionally dried to constant weight at temperatures between 80°C and 120°C and then calcined at temperatures below 850°C preferably between i0 500°C and 700°C, in air in continuous or batch operated kilns, such as rotary kilns or stationary kilns. The organic additives then burn off and leave behind a corresponding pore system.
The pore structure and pore volume of the catalysts can be varied over a wide range by suitable selection of the pore-producing additives. The final pore structure which is developed and the pore volume are also affected by the particle sizes of the powders of catalyst alloy and binder employed.
The structure of the molded item can be adapted to the requirements for the particular catalytic process by appropriate selection of the parameters mentioned.
During calcination of the molded items, the catalyst alloy powder and binder powder sinter together and provide the molded items with high mechanical stability and good resistance to abrasion. Typically, the hardness of cylindrical pellets after calcination is between 200 and 300 N (measured radially in accordance with ASTM D 4179-82) .
After calcination the molded items are activated by leaching the aluminum using caustic soda solution. A 20g strength sodium hydroxide solution warmed to 80°C can be used for this purpose. In this case, treatment for 2 hours leads to an active outer layer with a thickness of about 0.1 to 1 mm. Surprisingly, it has been shown that the hardness is actually slightly increased by leaching, in the case of pellets to values of more than 300 N.
These properties are closely connected with the pure Raney process metal used as binder which is not dissolved out during leaching and thus in the sintered product forms stable bonds between the individual alloyed particles.
According to german patent DE 197 218 98.9 (Freund, Berweiler, Bender and Kempf; 1998) the use of a metallic binders for the production of Metalyst~ can be avoided if the phase domains of the alloy are sufficiently small enough. The-size of the phase domains can be controlled by the cooling rate and cooling method of the alloy. Hence, the use of a binder in the invention of this patent is optional and the technology of DE 197 218 98.9 is applicable to the catalyst invented in this patent.
The choice of metals used as binder may contribute to the catalytic activity. Restricting the temperature of calcination to values below 850°C prevents the formation of alpha-aluminum oxide as shown by X-ray diffraction analysis of the calcined material. Any y-aluminum oxide which is formed is dissolved out of the catalyst structure when activating the catalyst with caustic soda solution.
The lack of a-aluminum oxide in the catalyst becomes clearly noticeable on activation. Whereas catalysts according to the present invention can be activated under quite mild conditions (20$ NaOH, 80°C) within only 2 hours, the temperature of the alkaline solution has to be raised and the activation time extended when activating catalysts bonded with a-aluminum oxide (according to U.S. Pat. No.
4,826,799) in order to obtain an active outer layer of the same thickness.
To prepare the catalyst according to the present invention, the average particle sizes of the catalyst alloy powder and of the binder, and also the ratio by weight of catalyst alloy powder to binder, can be varied over a wide range.
Since the binder does also contribute to the catalytic activity, but it cannot be activated by extracting aluminum, its possible contribution to the catalytic activity is limited. Therefore its proportion in the catalyst should be kept as small as possible.
Ratios by weight of catalyst alloy powder to binder in the range 100:20 to 100:0.5 have proven to be useful. It has also been shown that the particle size of the binder should be smaller than the particle size of the catalyst alloy powder. Particles of binder can then be regarded as small bridges between the larger alloyed particles. It was found that the hardness of the final catalyst structure increased within certain limits with decreasing particle size of the binder. Reasonable activity values are obtained when the powder of the catalyst alloy has an average particle size between 10 and 500 Vim.
In the case of doping with rhenium, it is expedient to carry out doping only after activating the catalyst. For this, the final catalyst is introduced into a rhenium solution (e.g.,perrhenic and). The amount of rhenium and the time needed for ist addition can be controlled by adjusting the pH and the temperature of the rhenium solution. A specific amount of the rhenium compound is adsorbed by the catalyst, depending on the type of treatment, e.g. up to 20g by weight.
A further object of the invention is a process for preparing the shaped Raney metal fixed-bed catalyst, said process consisting essentially of preparing a mixture of powders consisting essentially of at least one catalyst alloy and optionally one binder, and a moistening agent, and optionally an additive selected from the group consisting of a shaping aid, lubricant, plasticizer, pore-producer, and mixtures thereof, wherein said catalyst alloy consists essentially of at least one Raney process metal as catalytically active component, a leachable alloy component and optionally a promoter, wherein said optional binder consists essentially of at least one Raney process metal, homogenizing said mixture, shaping said mixture to give a molded catalyst precursor which still is not activated, calcining said molded catalyst precursor at a temperature below 850°C to obtain a sintered catalyst precursor, and activating said sintered catalyst precursor by leaching 10~ said leachable alloy component with alkali until the leached and thereby activated outer layer has a thickness of 0.05 to 1 mm or higher; optionally subsequently washing the final catalyst; Rhenium as a promoter after said activating and washing by introducing said catalyst into a Rhenium solution where the properties of rhenium deposition can be controlled by the temperature and pH of the rhenium solution.
A further object of the invention is the use of the rhenium doped Raney metal fixed-bed catalyst for the hydrogenation of unsaturated and saturated esters. An example of this technology is the hydrogenation of malefic anhydide to y-butyrolactone, tetrahydrofuran, 1,4-butanediol at mild conditions. Moreover, the invention of this patent was found to be an excelent catalyst for the hydrogenation of fatty esters to fatty alcohols Comparison Example 1 A commercially available 2~Pd catalyst on 4 mm carbon extrudates is doped with 0.5~ Re by treating it in a perrhenic acid solution whose pH is adjusted to 10.5 with sodium hydroxide before introducing the catalyst to the solution. The treatment continued until no rhenium remained in the rhenium solution. The use of this catalyst according to application example 1 for malefic anhydride hydrogenation resulted in the yiels of 10.5 gamma butyrolactone, 0.0$
tetrahydrofuran and 0.0~ 1.4-butandiol after a reaction time of 5 hours.
Example 1 A free-flowing, pelletable catalyst mixture is prepared in 5 accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50oA1 alloy powder, 7.5 g of pure nickel powder(99gNi, and d50 = 21 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 4 mm and a thickness of 4 mm are compressed 10 from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20~ strength caustic soda solution for 2 hours at 80°C after calcination. This catalysts is doped to the level of 0.45 Re by exposing the catalyst for 48 h to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst.
The use of this catalyst according to application example 1 for malefic anhydride hydrogenation yielded 71.6 gamma butyrolactone, 4.7$ tetrahydrofuran, and 1.3$ 1.4-butandiol after a reaction time of 5 hours.
Comparison Example 2 Commercially available copper chromite extrudates from Mallinckrodt were used as a comparative technology for the hydrogenation of fatty esters. When used according to application example 2, this catalyst produced 20.78 fatty alcohol with a saponification number of 136.6 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was a bluish-green indicating the prescence of dissolved metals. When used according to application example 3, this catalyst produced 20.58 fatty alcohol with a saponification number of 143.5 after 1230 minutes of reaction time at 200°C.
Example 2 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50~A1 alloy powder, 7.5 g of pure nickel powder(99~Ni, and d50 = 21 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 4 mm and a thickness of 4 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20~ strength caustic soda solution for 2 hours at 80°C after calcination. This catalysts is doped to the level of 2.0$ Re by exposing the catalyst for 100 h to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst. The use of this catalyst according to application example 1 for malefic anhydride hydrogenation yielded 55~
gamma buty.rolactone, 14.2 tetrahydrofuran, and 1.3~ 1.4-butandiol after a reaction time of 5 hours.
Example 3 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50~A1 alloy powder, 7.5 g of pure nickel powder(?99~Ni, and d50 = 21 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 4 mm and a thickness of 4 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20g strength caustic soda solution for 2 hours at 80°C after calcination. This catalysts is doped to the level of 4.0~ Re by exposing the catalyst for 192 h to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst. The use of this catalyst according to application example 1 for malefic anhydride hydrogenation yielded 40~
gamma butyrolactone, 3.5~ tetrahydrofuxan, and 26.25 1.4-butandiol after a reaction 'time of 5 hours.
Example 4 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50$Ni and 50~A1 alloy powder, 7.5 g of pure nickel powder(99~Ni, and d50 = 21 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 4 mm and a thickness of 4 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20$ strength caustic soda solution for 2 hours at 80°C after calcination. This catalysts is doped to the level of 6.0~ Re by exposing the catalyst for 240 h to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst. The use of this catalyst according to application example for malefic anhydride hydrogenation yielded 25.9$
gamma butyrolactone, 3.71$ tetrahydrofuran, and 26.9 1.4-butandiol after a reaction time of 5 hours.
Example 5 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50$Cu and 50~A1 alloy powder, 430 g of pure nickel powder (d50 = 23 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm are compressed from this mixture. The shaped items are calcined for 6 h at 700°C.
The tablets are activated in 20~ strength caustic soda solution for 2 h at 80°C after calcination. When used according to application example 2, this catalyst produced 3.32 fatty alcohol with a saponification number of 176.0 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals. Although this catalyst already performs similar (if not slightly better) the activated nickel catalyst, its activity can be improved by using less binder and decreasing the severity of its calcination. Thus Re doping could improve this catalyst system at least to the same extent as the activated Ni catalyst.
Activated metal catalysts are known in the field of chemical engineering as Raney catalysts. They are used, largely in powder form, for a large number of hydrogenation, dehydrogenation, isomerization reductive alkylation, reductive amination, and hydration reactions of organic compounds. These powdered catalysts are prepared from an alloy of a catalytically active metal, also referred to herein as a catalyst metal, with a further alloying component which is soluble in alkalis. Mainly nickel, cobalt, copper, or iron are used as catalyst metals. Aluminum is generally used as the alloying component which is soluble in alkalis, but other components may also be used, in particular zinc and silicon or mixtures of these with aluminum.
Powdered catalysts have the disadvantage that they can be used only in a batch process and, after the catalytic reaction, have to be separated from the reaction medium by costly sedimentation and/or filtration. Therefore a variety of processes for preparing moulded items which lead to activated metal fixed-bed catalysts after extraction of the aluminum have been disclosed. Thus, for example, coarse particulate Raney alloys, i.e., Raney alloys which have only been coarsely milled, are obtainable and these can be activated by a treatment with caustic soda solution.
Extraction and activation then occurs only in a surface layer the thickness of which can be adjusted by the conditions used during extraction.
A substantial disadvantage of catalysts prepared by these prior methods are the poor mechanical stability of the activated outer layer. Since only this outer layer of the catalysts is the catalytically active, abrasion leads to rapid deactivation and renewed activation of deeper lying layers of alloy using caustic soda solution then leads at best to partial reactivation.
It is known that Re doped Pd (DE 25 19 817 A1)or Re doped Ru (WO 96/27436) supported catalysts are used for the production of gamma butyrolactone (GBL), tetrahydrofuran (THF), or 1,4-butanediol (BDO) by either maleic.acid or malefic anhydride hydrogenation. These systems work as either powder or fixed bed catalysts at pressures of 138 barr or higher and temperatures of 250°C or higher. In this respect, a system that performs this reaction at milder conditions would be a strong advantage. Copper-chromite is another catalyst system that has used for ester hydrogenation with some success (DE 39 03 029 A1).
The document EP 0 648 534 A1 describes shaped, activated Raney metal fixed-bed catalysts (Metalyst~) and their preparation. This technology avoids the disadvantages described above, e.g., the poor mechanical stability resulting from activating an outer layer. To prepare these catalysts, a mixture of powers consisting of a catalyst alloy and a binder are used, where the catalyst alloy contains at least one catalytically active catalyst metal and an extractable alloying component. The pure catalyst metals or mixtures thereof which do not contain extractable components are used as binder. The use of the binder in. an amount of 0.5 to 20 weight percent with respect to the catalyst alloy, is essential in order to achieve sufficient mechanical stability after activation. After shaping the catalyst alloy and the binder with conventional shaping aids and pore producers, the freshly prepared items which are obtained are calcined at temperatures below 850°C. As a result of sintering processes in the finely divided binder, this produces solid compounds between the individual granules of the catalysts alloy. These compounds, in contrast to catalyst alloys, are non-extractable or only extractable to a small extent so that a mechanically stable structure is obtained even after activation without endangering the strength of the shaped item.
An object of the present invention is therefore to provide fixed bed activated base metal catalysts that hydrogenate saturated and unsaturated esters at milder conditions than existing technologies with better activities and selectivities.
The fixed bed catalysts according to the invention show the advantage that Re doped metal catalysts can perform the hydrogenation of meleic acid or malefic anhydride to gamma butyrolactone, tetrahydrofuran or 1,4-butanediole at a temperature of 200°C and a pressure of 80 bar. Additionally these catalysts were able to hydrogenate fatty esters to the corresponding fatty alcohols at higher activities and selectivities than the standard copper chromite catalysts.
An object of the present invention is a shaped, activated Raney metal fixed-bed catalyst, said catalyst produced by a method consisting essentially of preparing a mixture of powders consisting essentially of at least one catalyst alloy and at least one binder, and a moistening agent, and optionally an additive selected from the group consisting of a shaping aid, lubricant, plasticizer, pore-producer, and mixtures thereof, wherein said catalyst alloy consists essentially of at least one Raney process metal as catalytically active catalyst metal, a leachable alloy component and optionally a promoter, wherein said binder consists essentially of at least one pure Raney process metal, homogenizing said mixture, shaping said mixture to give a molded catalyst precursor which still is not activated, calcining said molded catalyst precursor at a temperature below 850°C to obtain a sintered catalyst precursor, and activating said sintered catalyst precursor by leaching said leachable alloy component with alkali until the leached and thereby activated outer layer has an adjustable thickness corresponding upto 70$ or more of the molded form being activated, and subsequently washing the final catalyst; doping said catalyst with rhenium as a promoter after said activating and washing by introducing said catalyst into a Rhenium solution. The pH of the Re solution may or may not beadjusted, and the temperature of the doping solution can vary from lower than room temperature to substantial hygher temperatures. Moreover, the rhenium may be added to the unactivated alloy, the binder, or introduced in any other fashion that allows for it presence in the catalyst. The Re content can range from 0, O1 ~ Re to 15 ~ Re.
Preferred Raney process metals are nickel, cobalt, copper, or combination thereof and the leachable alloying components used are aluminum, zinc, silicon, or combintions thereof. These are generally leached in alkali such as NaOH. The ratio by weight of Raney process metal to leachable alloying component in the catalyst alloy is in the range from 10:90 to 90:10, as is usual with Raney alloys: The Raney process metal used as binder, in a real practical application, does not have to be the same as the catalyst metal present in the catalyst alloy. Rather, the possibility is opened up to combining different Raney process metals with each other as well as with promoter metals, in the catalyst alloy and as binder, offering a further important degree of freedom when adjusting the catalytic properties to the particular catalytic process.
Thus the binder used in the present invention can be nickel, cobalt, copper, iron, and optionally promoter metals. Generally any of the metals used for making Raney metal catalysts are suitable. The binder metal is used in an unleachable and unadulterated form.
Catalyst alloy and binder are processed in the form of powders, typically with the addition of moistening agents and optionally with the addition of conventional additives such as shaping aids, lubricants, plasticizers, and optionally pore-producers to give a moldable material. Any materials conventionally used for these purposes may be used as the shaping aid, lubricant, plasticizer and pore-producer. A number of suitable materials for this purpose are mentioned in the following U.S. Pat. Nos. (all of which 5 are incorporated by references in their entirety):
4,826,799; 3,404,551; and 3,351,495. Waxes such as, for example wax C micropowder PM from Hoechst AG, greases such as magnesium or aluminum stearates, or polymers which contain carbohydrates such as tylose (methylcellulose) are preferably used for the above purposes.
The solids in the mixture are carefully homogenized in suitable conventional mixers or kneaders with the addition of a moistening agent. Water, alcohols, glycols, polyether glycols or mixtures thereof are suitable as moistening agents as is well known in the art.
The primary particle size ranges of the powders of catalyst alloy and binder used are essentially unchanged during homogenization. That is, no milling takes place.
The purpose of this preliminary treatment with the moistening agent and additives is to prepare the mixture for the subsequent shaping process. Extrusion, pelleting and compression may be used for example for the shaping process employing conventional equipment known for such purposes.
The type and sequence of incorporation of additives depends on the shaping process to be used. Extrusion requires a plastic material with a specific viscosity, whereas a material which is free-flowing and which can be readily metered out is required for pelleting. The techniques to be used for this purpose, such as, for example, agglomeration to produce a free-flowing powder or adjustment to the correct viscosity for extrusion, are known as a matter of routine to the person skilled in the art. It is only important that the primary particle size ranges of the catalyst powder and binder powder are essentially unchanged by the preliminary treatment.
Any shapes which are conventional in the catalyst field are suitable as molded items. Spheres, rings, spoked rings or pellets may be produced, depending on the requirements of the particular application.
The final molded items are optionally dried to constant weight at temperatures between 80°C and 120°C and then calcined at temperatures below 850°C preferably between i0 500°C and 700°C, in air in continuous or batch operated kilns, such as rotary kilns or stationary kilns. The organic additives then burn off and leave behind a corresponding pore system.
The pore structure and pore volume of the catalysts can be varied over a wide range by suitable selection of the pore-producing additives. The final pore structure which is developed and the pore volume are also affected by the particle sizes of the powders of catalyst alloy and binder employed.
The structure of the molded item can be adapted to the requirements for the particular catalytic process by appropriate selection of the parameters mentioned.
During calcination of the molded items, the catalyst alloy powder and binder powder sinter together and provide the molded items with high mechanical stability and good resistance to abrasion. Typically, the hardness of cylindrical pellets after calcination is between 200 and 300 N (measured radially in accordance with ASTM D 4179-82) .
After calcination the molded items are activated by leaching the aluminum using caustic soda solution. A 20g strength sodium hydroxide solution warmed to 80°C can be used for this purpose. In this case, treatment for 2 hours leads to an active outer layer with a thickness of about 0.1 to 1 mm. Surprisingly, it has been shown that the hardness is actually slightly increased by leaching, in the case of pellets to values of more than 300 N.
These properties are closely connected with the pure Raney process metal used as binder which is not dissolved out during leaching and thus in the sintered product forms stable bonds between the individual alloyed particles.
According to german patent DE 197 218 98.9 (Freund, Berweiler, Bender and Kempf; 1998) the use of a metallic binders for the production of Metalyst~ can be avoided if the phase domains of the alloy are sufficiently small enough. The-size of the phase domains can be controlled by the cooling rate and cooling method of the alloy. Hence, the use of a binder in the invention of this patent is optional and the technology of DE 197 218 98.9 is applicable to the catalyst invented in this patent.
The choice of metals used as binder may contribute to the catalytic activity. Restricting the temperature of calcination to values below 850°C prevents the formation of alpha-aluminum oxide as shown by X-ray diffraction analysis of the calcined material. Any y-aluminum oxide which is formed is dissolved out of the catalyst structure when activating the catalyst with caustic soda solution.
The lack of a-aluminum oxide in the catalyst becomes clearly noticeable on activation. Whereas catalysts according to the present invention can be activated under quite mild conditions (20$ NaOH, 80°C) within only 2 hours, the temperature of the alkaline solution has to be raised and the activation time extended when activating catalysts bonded with a-aluminum oxide (according to U.S. Pat. No.
4,826,799) in order to obtain an active outer layer of the same thickness.
To prepare the catalyst according to the present invention, the average particle sizes of the catalyst alloy powder and of the binder, and also the ratio by weight of catalyst alloy powder to binder, can be varied over a wide range.
Since the binder does also contribute to the catalytic activity, but it cannot be activated by extracting aluminum, its possible contribution to the catalytic activity is limited. Therefore its proportion in the catalyst should be kept as small as possible.
Ratios by weight of catalyst alloy powder to binder in the range 100:20 to 100:0.5 have proven to be useful. It has also been shown that the particle size of the binder should be smaller than the particle size of the catalyst alloy powder. Particles of binder can then be regarded as small bridges between the larger alloyed particles. It was found that the hardness of the final catalyst structure increased within certain limits with decreasing particle size of the binder. Reasonable activity values are obtained when the powder of the catalyst alloy has an average particle size between 10 and 500 Vim.
In the case of doping with rhenium, it is expedient to carry out doping only after activating the catalyst. For this, the final catalyst is introduced into a rhenium solution (e.g.,perrhenic and). The amount of rhenium and the time needed for ist addition can be controlled by adjusting the pH and the temperature of the rhenium solution. A specific amount of the rhenium compound is adsorbed by the catalyst, depending on the type of treatment, e.g. up to 20g by weight.
A further object of the invention is a process for preparing the shaped Raney metal fixed-bed catalyst, said process consisting essentially of preparing a mixture of powders consisting essentially of at least one catalyst alloy and optionally one binder, and a moistening agent, and optionally an additive selected from the group consisting of a shaping aid, lubricant, plasticizer, pore-producer, and mixtures thereof, wherein said catalyst alloy consists essentially of at least one Raney process metal as catalytically active component, a leachable alloy component and optionally a promoter, wherein said optional binder consists essentially of at least one Raney process metal, homogenizing said mixture, shaping said mixture to give a molded catalyst precursor which still is not activated, calcining said molded catalyst precursor at a temperature below 850°C to obtain a sintered catalyst precursor, and activating said sintered catalyst precursor by leaching 10~ said leachable alloy component with alkali until the leached and thereby activated outer layer has a thickness of 0.05 to 1 mm or higher; optionally subsequently washing the final catalyst; Rhenium as a promoter after said activating and washing by introducing said catalyst into a Rhenium solution where the properties of rhenium deposition can be controlled by the temperature and pH of the rhenium solution.
A further object of the invention is the use of the rhenium doped Raney metal fixed-bed catalyst for the hydrogenation of unsaturated and saturated esters. An example of this technology is the hydrogenation of malefic anhydide to y-butyrolactone, tetrahydrofuran, 1,4-butanediol at mild conditions. Moreover, the invention of this patent was found to be an excelent catalyst for the hydrogenation of fatty esters to fatty alcohols Comparison Example 1 A commercially available 2~Pd catalyst on 4 mm carbon extrudates is doped with 0.5~ Re by treating it in a perrhenic acid solution whose pH is adjusted to 10.5 with sodium hydroxide before introducing the catalyst to the solution. The treatment continued until no rhenium remained in the rhenium solution. The use of this catalyst according to application example 1 for malefic anhydride hydrogenation resulted in the yiels of 10.5 gamma butyrolactone, 0.0$
tetrahydrofuran and 0.0~ 1.4-butandiol after a reaction time of 5 hours.
Example 1 A free-flowing, pelletable catalyst mixture is prepared in 5 accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50oA1 alloy powder, 7.5 g of pure nickel powder(99gNi, and d50 = 21 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 4 mm and a thickness of 4 mm are compressed 10 from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20~ strength caustic soda solution for 2 hours at 80°C after calcination. This catalysts is doped to the level of 0.45 Re by exposing the catalyst for 48 h to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst.
The use of this catalyst according to application example 1 for malefic anhydride hydrogenation yielded 71.6 gamma butyrolactone, 4.7$ tetrahydrofuran, and 1.3$ 1.4-butandiol after a reaction time of 5 hours.
Comparison Example 2 Commercially available copper chromite extrudates from Mallinckrodt were used as a comparative technology for the hydrogenation of fatty esters. When used according to application example 2, this catalyst produced 20.78 fatty alcohol with a saponification number of 136.6 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was a bluish-green indicating the prescence of dissolved metals. When used according to application example 3, this catalyst produced 20.58 fatty alcohol with a saponification number of 143.5 after 1230 minutes of reaction time at 200°C.
Example 2 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50~A1 alloy powder, 7.5 g of pure nickel powder(99~Ni, and d50 = 21 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 4 mm and a thickness of 4 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20~ strength caustic soda solution for 2 hours at 80°C after calcination. This catalysts is doped to the level of 2.0$ Re by exposing the catalyst for 100 h to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst. The use of this catalyst according to application example 1 for malefic anhydride hydrogenation yielded 55~
gamma buty.rolactone, 14.2 tetrahydrofuran, and 1.3~ 1.4-butandiol after a reaction time of 5 hours.
Example 3 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50~A1 alloy powder, 7.5 g of pure nickel powder(?99~Ni, and d50 = 21 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 4 mm and a thickness of 4 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20g strength caustic soda solution for 2 hours at 80°C after calcination. This catalysts is doped to the level of 4.0~ Re by exposing the catalyst for 192 h to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst. The use of this catalyst according to application example 1 for malefic anhydride hydrogenation yielded 40~
gamma butyrolactone, 3.5~ tetrahydrofuxan, and 26.25 1.4-butandiol after a reaction 'time of 5 hours.
Example 4 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50$Ni and 50~A1 alloy powder, 7.5 g of pure nickel powder(99~Ni, and d50 = 21 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 4 mm and a thickness of 4 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20$ strength caustic soda solution for 2 hours at 80°C after calcination. This catalysts is doped to the level of 6.0~ Re by exposing the catalyst for 240 h to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst. The use of this catalyst according to application example for malefic anhydride hydrogenation yielded 25.9$
gamma butyrolactone, 3.71$ tetrahydrofuran, and 26.9 1.4-butandiol after a reaction time of 5 hours.
Example 5 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50$Cu and 50~A1 alloy powder, 430 g of pure nickel powder (d50 = 23 um), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm are compressed from this mixture. The shaped items are calcined for 6 h at 700°C.
The tablets are activated in 20~ strength caustic soda solution for 2 h at 80°C after calcination. When used according to application example 2, this catalyst produced 3.32 fatty alcohol with a saponification number of 176.0 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals. Although this catalyst already performs similar (if not slightly better) the activated nickel catalyst, its activity can be improved by using less binder and decreasing the severity of its calcination. Thus Re doping could improve this catalyst system at least to the same extent as the activated Ni catalyst.
Comparison Example 3 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50%A1 alloy powder, 7.5 g of pure nickel powder (99oNi, and d50 =
2lum), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20~ strength caustic soda solution for 2 h at 80°C after calcination. When used according to application example 2, this catalyst produced 1.92$ fatty alcohol with a saponification number of 174.2 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals.
Example 6 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50~A1 alloy powder, 7.5 g of pure nickel powder (99~Ni, and d50 =
2lpm), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm az;e compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20$ strength caustic soda solution for 2 h at 80°C after calcination.
This catalyst is doped to a level of 3.0~ Re by exposing the catalyst for 72 hours to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst. When used according to application example 2, this catalyst produced 25.398 fatty alcohol with a saponification number of 107.9 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals.
When used according to application example 3, this catalyst produced 63.85s fatty alcohol with a saponification number of 61.2 after 1230 minutes of reaction time at 200°C.
Comparison Example 4 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 Al for a catalyst consisting of 1000 g of 40.O~Ni, 58.5~A1, 1.O~Cr, and 0.5~Fe alloy powder; 7.5 g of pure nickel powder (99~Ni, and d50 = 2lum); and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20~ strength caustic soda solution for 2 h at 80°C after calcination. When used according to application example 2, this catalyst produced 6.72$ fatty alcohol with a saponification number of 160.7 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals.
Example 7 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 40.0$Ni, 58.5~A1, 1.0$Cr, and 0.5$Fe alloy powder; 7.5 g of pure nickel powder (99$Ni, and d50 = 2lum); and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20$ strength caustic soda solution for 2 h at 80°C after calcination. This catalyst is doped to a level of 3.0~ Re by exposing the catalyst for 72 hours to a stirred perrhenic acid solution that is adjusted to the pH
of 10.5 before adding the catalyst. When used according to application example 2, this catalyst produced 34.2$ fatty alcohol with a saponification number of 98.8 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals.
Application example 1 The catalytic activity of the catalysts from comparison 5 example 1 and from examples 1 to 4 are compared by their ability to hydrogenate malefic anhydride. For this purpose, 7 g of malefic anhydride and 250 g of 1,4-dioxane are placed in a stirred autoclave with a capacity of 0.5 1 and outfitted with a gas stirrer spinning at 1000 rpm. The 10 amount of grams of catalyst is suspended each time in the stirred autoclave using a catalyst basket so that the catalyst material is thoroughly washed by the reactant/solvent mixture before hydrogen is introduced.
This hydrogenation is performed at a hydrogen pressure of 15 80 bar, the temperature of 200°C, and the reaction is stopped after 5 hours. Samples are withdrawn after 2 and 5 h and analyzed by gas chromatography to calculate the catalysts activity and selectivity. The results of these tests are given in table 3.
Application Example 2 The catalytic activity of the catalysts from comparison examples 2-4 and examples 5-7 are compared to each other by their ability to hydrogenate a mixture of saturated and unsaturated C-16 and C-18 esters to the fatty alcohols.
The reactant was a commercial feed consisting of approximately 70~ C-18 and 30~ C-16 methyl esters with about 60~ of the total feedstock being unsaturated. The feed also contained a very small amount of C-12, C-14, and C-20 methyl esters where the sum total of these other esters is less than 1~. The hydrogenation of 500 ml of the above mentioned fatty ester feedstock is carried out with 72 g of catalyst at 200 bar and 230°C in a 11 stirred autoclave outfitted with a bubble-stirrer and a catalyst basket. A sample is taken out after 300 minutes of reaction for analysis by gas chromatography and determination of its saponification number. The saponification number is determined by mixing 2.0 g (~ 0.1 mg) of the hydrogenation sample with 50 ml of an ethanolic 0.5 N KOH solution and refluxing it at the solution's boiling point for 60 minutes. A 1.0~ phenolphthalien solution is then given to the warm solution and it is titrated with a standard 0.5 N
HCl solution to determine the remaining amount of KOH. A
blind experiment without the hydrogenation sample is carried out at the same time under the same conditions for reference. The saponification number is equal to the mg of KOH that is needed to saponify one gram of the fatty ester mixture where a higher number indicates that the mixture contains a higher percentage of ester. In the comparisons used here, a higher saponification number means that less of the fatty ester was converted to the corresponding fatty alcohol duing the hydrogenation. The data for these experiments are listed in Table 1.
Application Example 2 The catalytic activity of the catalysts from comparison example 2 and example 6 are also compared to each other by their ability to hydrogenate the mixture of saturated and unsaturated C-16 and C-18 esters mentioned above in application example 2 to alcohols at the same conditions with the exception being the reaction temperature of 200°C.
The sample times for this experiment are 300 and 1230 minutes for analysis by gas chromatography and determination of the saponification number (as described above). The data of these experiments are listed in table 2.
N
+~
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-o ~ O ~ ~ o o m O C7 ~ '-I I~ lW I7 ~ ~ l0 N
~ ~
b C7 rl O N
y -I ~~'f'-I v-1 O r1 v-1 M O M O
fd ?i O O O O O ~ O
d~P
b N FC
.C O
~" rl ., U U
-,-1-r1 ~-.'~
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R, Q' 'N ~ N ~ X17 N ~ N ~ N ~!7 4-1 O N -rl O .v.~f~ H
4-~ is O s~
s~ 'L5 O sa ~ ~ ~ 0 0 0 -.-IO
U ~ O ~ N ~' to !~
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v1 H E-~
2lum), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20~ strength caustic soda solution for 2 h at 80°C after calcination. When used according to application example 2, this catalyst produced 1.92$ fatty alcohol with a saponification number of 174.2 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals.
Example 6 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 50~Ni and 50~A1 alloy powder, 7.5 g of pure nickel powder (99~Ni, and d50 =
2lpm), and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm az;e compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20$ strength caustic soda solution for 2 h at 80°C after calcination.
This catalyst is doped to a level of 3.0~ Re by exposing the catalyst for 72 hours to a stirred perrhenic acid solution that is adjusted to the pH of 10.5 before adding the catalyst. When used according to application example 2, this catalyst produced 25.398 fatty alcohol with a saponification number of 107.9 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals.
When used according to application example 3, this catalyst produced 63.85s fatty alcohol with a saponification number of 61.2 after 1230 minutes of reaction time at 200°C.
Comparison Example 4 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 Al for a catalyst consisting of 1000 g of 40.O~Ni, 58.5~A1, 1.O~Cr, and 0.5~Fe alloy powder; 7.5 g of pure nickel powder (99~Ni, and d50 = 2lum); and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20~ strength caustic soda solution for 2 h at 80°C after calcination. When used according to application example 2, this catalyst produced 6.72$ fatty alcohol with a saponification number of 160.7 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals.
Example 7 A free-flowing, pelletable catalyst mixture is prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst consisting of 1000 g of 40.0$Ni, 58.5~A1, 1.0$Cr, and 0.5$Fe alloy powder; 7.5 g of pure nickel powder (99$Ni, and d50 = 2lum); and 50 g of ethylene bis-stearoylamide. Tablets with the diameter of 3 mm and a thickness of 3 mm are compressed from this mixture. The shaped items are calcined for 2 h at 700°C. The tablets are activated in 20$ strength caustic soda solution for 2 h at 80°C after calcination. This catalyst is doped to a level of 3.0~ Re by exposing the catalyst for 72 hours to a stirred perrhenic acid solution that is adjusted to the pH
of 10.5 before adding the catalyst. When used according to application example 2, this catalyst produced 34.2$ fatty alcohol with a saponification number of 98.8 after 300 minutes of reaction time at 230°C. The color of the reactant at this time was white indicating the absence of dissolved metals.
Application example 1 The catalytic activity of the catalysts from comparison 5 example 1 and from examples 1 to 4 are compared by their ability to hydrogenate malefic anhydride. For this purpose, 7 g of malefic anhydride and 250 g of 1,4-dioxane are placed in a stirred autoclave with a capacity of 0.5 1 and outfitted with a gas stirrer spinning at 1000 rpm. The 10 amount of grams of catalyst is suspended each time in the stirred autoclave using a catalyst basket so that the catalyst material is thoroughly washed by the reactant/solvent mixture before hydrogen is introduced.
This hydrogenation is performed at a hydrogen pressure of 15 80 bar, the temperature of 200°C, and the reaction is stopped after 5 hours. Samples are withdrawn after 2 and 5 h and analyzed by gas chromatography to calculate the catalysts activity and selectivity. The results of these tests are given in table 3.
Application Example 2 The catalytic activity of the catalysts from comparison examples 2-4 and examples 5-7 are compared to each other by their ability to hydrogenate a mixture of saturated and unsaturated C-16 and C-18 esters to the fatty alcohols.
The reactant was a commercial feed consisting of approximately 70~ C-18 and 30~ C-16 methyl esters with about 60~ of the total feedstock being unsaturated. The feed also contained a very small amount of C-12, C-14, and C-20 methyl esters where the sum total of these other esters is less than 1~. The hydrogenation of 500 ml of the above mentioned fatty ester feedstock is carried out with 72 g of catalyst at 200 bar and 230°C in a 11 stirred autoclave outfitted with a bubble-stirrer and a catalyst basket. A sample is taken out after 300 minutes of reaction for analysis by gas chromatography and determination of its saponification number. The saponification number is determined by mixing 2.0 g (~ 0.1 mg) of the hydrogenation sample with 50 ml of an ethanolic 0.5 N KOH solution and refluxing it at the solution's boiling point for 60 minutes. A 1.0~ phenolphthalien solution is then given to the warm solution and it is titrated with a standard 0.5 N
HCl solution to determine the remaining amount of KOH. A
blind experiment without the hydrogenation sample is carried out at the same time under the same conditions for reference. The saponification number is equal to the mg of KOH that is needed to saponify one gram of the fatty ester mixture where a higher number indicates that the mixture contains a higher percentage of ester. In the comparisons used here, a higher saponification number means that less of the fatty ester was converted to the corresponding fatty alcohol duing the hydrogenation. The data for these experiments are listed in Table 1.
Application Example 2 The catalytic activity of the catalysts from comparison example 2 and example 6 are also compared to each other by their ability to hydrogenate the mixture of saturated and unsaturated C-16 and C-18 esters mentioned above in application example 2 to alcohols at the same conditions with the exception being the reaction temperature of 200°C.
The sample times for this experiment are 300 and 1230 minutes for analysis by gas chromatography and determination of the saponification number (as described above). The data of these experiments are listed in table 2.
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Claims (35)
1. A shaped, activated Raney metal fixed-bed catalyst, said catalyst produced by a method consisting essentially of preparing a mixture of powders consisting essentially of at least one catalyst alloy and at least one binder, and a moistening agent, and optionally an additive selected from the group consisting of a shaping aid, lubricant, plasticizer, pore-producer, and mixtures thereof, wherein said catalyst alloy consists essentially of at least one Raney process metal as catalytically active catalyst metal, a leachable alloy component and optionally a promoter, wherein said binder consists essentially of at least one pure Raney process metal, homogenizing said mixture, shaping said mixture to give a molded catalyst precursor which still is not activated, calcining said molded catalyst precursor at a temperature below 850°C to obtain a sintered catalyst precursor, and activating said sintered catalyst precursor by leaching said leachable alloy component with alkali until the leached and thereby activated outer layer has a thickness of 0.05 to 1 mm, and subsequently washing the final catalyst; doping said catalyst with rhenium as a promoter after said activating by introducing said catalyst into a perrhenic acid solution or solutions of other Re salts, for a sufficient period of time to fix all of the rhenium onto the catalyst.
2. Process for preparing the shaped Raney metal fixed-bed catalyst according to claim 1, said process consisting essentially of preparing a mixture of powders consisting essentially of at least one catalyst alloy and at least one binder, and a moistening agent, and optionally an additive selected from the group consisting of a shaping aid, lubricant, plasticizer, pore-producer, and mixtures thereof, wherein said catalyst alloy consists essentially of at least one Raney process metal as catalytically active component, a leachable alloy component and optionally a promoter, wherein said binder consists essentially of at least one Raney process metal, homogenizing said mixture, shaping said mixture to give a molded catalyst precursor which still is not activated, calcining said molded catalyst precursor at a temperature below 850°C to obtain a sintered catalyst precursor, and activating said sintered catalyst precursor by leaching said leachable alloy component with alkali until the leached and thereby activated outer layer has a thickness of 0.05 to 1 mm; optionally subsequently washing the final catalyst; characterized in that the catalyst is doped with rhenium as a promoter after said activating by introducing said catalyst into a perrhenc acid, solution whose pH was initialy adjusted for a sufficient period of time to fix all of the rhenium on the catalyst.
3. The catalysts according to claims 1 and 2 where a binder is not required for a stable formed body and the resulting catalyst is doped with Re by introducing the activated catalyst into a perrhenic acid solution for a sufficient amount of time.
4. The catalysts according to claims 1-3 where the Re is added as part of the binder system.
5. The catalysts according to claims 1-3 where the Re is added as part of the alloy.
6. The catalysts according to claims 1-5 where the Re content is from 0.01% Re to 30% Re.
7. The catalysts according to claims 1-5 where the Re content is from 0.01% Re to 10% Re.
8. The catalysts according to claims 1-7 where the Raney metal is Ni.
9. The catalysts according to claims 1-7 where the Raney metal is Cu.
10. The catalysts according to claims 1-9 where the Raney metal is additionally doped with 0.01-5% chromium in combination with 0.01-5% iron either before or after the Re promotion.
11. The catalysts according to claims 1-10 where the Raney metal is nickel and it is additionally doped with 0.01- 5% chromium in combination with 0.01-5% iron either before or after the Re promotion.
12. The catalysts according to claims 1-10 where the Raney metal is additionally doped with 0.01-5% chromium before or atter the Re promotion.
13. The catalysts according to claims 1-10 where the Raney metal is additionally doped with 0.01-5% iron either before or after the Re promotion.
14. The catalysts according to claims 1-10 where the Raney metal is additionally doped with other promoters such as Ti, Zr, V, Ta, Mo, W, Ru, Pd, Pt, Cu, Zn, or Co either before or after the Re promotion.
15. The catalysts according to claims 1-14 where the deposition of Re is controlled by the pH of the doping solution.
16. The catalysts according to claims 1-3 and 11 where the deposition of Re is controlled by the pH of the doping solution.
17. The catalysts according to claims 1-14 where the deposition of Re is controlled by the temperature of the doping solution.
18. The catalysts according to claims 1-14 where the deposition of Re is controlled by both the pH and the temperature of the doping solution.
19. The catalysts according to claims 1-3 and 11 where the deposition of Re is controlled by the temperature of the doping solution.
20. The catalysts according to claims 1-3 and 11 where the deposition of Re is controlled by both the pH and the temperature of the doping solution.
21. Use of the Raney metal fixed-bed catalyst according to claim 1 for the hydrogenation of saturated or unsaturated esters to their corresponding mono or multiple hydroxy saturated alcohols.
22. The use of the Raney metal fixed-bed catalyst according to claims 1-3 and 11 for the hydrogenation of saturated or unsaturated esters to their corresponding mono or multiple hydroxy saturated alcohols.
23. The use of the Raney metal fixed-bed catalyst according to claims 1-20 for the hydrogenation of saturated or unsaturated esters to their corresponding mono or multiple hydroxy saturated alcohols.
24. The use of the Raney metal fixed-bed catalyst according to claims 1-3 and 11 for the partial hydrogenation of saturated or unsaturated esters to their corresponding ,mono or multiple hydroxy alcohols.
25. The use of the Raney metal fixed-bed catalyst according to claims 1-20 for the partial hydrogenation of saturated or unsaturated esters to their corresponding mono or multiple hydroxy alcohols.
26. The use of the Raney metal fixed-bed catalyst according to claims 1-3 and 11 for the hydrogenation of maleic anhydride to gamma-butyrolactone, tetrahydrofuran, and 1,4-butanediol
27. The use of the Raney metal fixed-bed catalyst according to claims 1-20 for the hydrogenation of maleic anhydride to gamma-butyrolactone, tetrahydrofuran, and 1,4-butanediol.
28. The use of the Raney metal fixed-bed catalyst according to claims 1-3 and 11 for the hydrogenation of fatty esters to fatty alcohols.
29. The use of the Raney metal fixed-bed catalyst according to claims 1-20 for the hydrogenation of fatty esters to fatty alcohols.
30. The use of the Raney metal fixed-bed catalyst according to claims 1-3 and 11 for the hydrogenation of C-12 to C-20 fatty esters to fatty alcohols.
31. The use of the Raney metal fixed-bed catalyst according to claims 1-20 for the hydrogenation of C-12 to C-20 fatty esters to fatty alcohols.
32. The use of the Raney metal fixed-bed catalyst according to claims 1-3 and 11 for the hydrogenation of C-16 to C-18 fatty esters to fatty alcohols.
33. The use of the Raney metal fixed-bed catalyst according to claims 1-20 for the hydrogenation of C-16 to C-18 fatty esters to fatty alcohols.
34. The use of the Raney metal fixed-bed catalyst according to claims 1-3 and 11 for the hydrogenation of maleic acid to gamma-butyrolactone, tetrahydrofuran, and 1,4-butanediol.
35. The use of the Raney metal fixed-bed catalyst according to claims 1-20 for the hydrogenation of maleic acid to gamma-butyrolactone, tetrahydrofuran, and 1,4-butanediol.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19936135A DE19936135A1 (en) | 1999-07-31 | 1999-07-31 | Fixed bed catalyst for hydrogenation of saturated or unsaturated esters to mono- or multiple hydroxy alcohols, is obtained by doping rhenium to Raney metal type metal fixed bed catalyst |
| DE19936135.5 | 1999-07-31 | ||
| US09/368,571 | 1999-08-05 | ||
| US09/368,571 US6284703B1 (en) | 1999-07-31 | 1999-08-05 | Fixed bed catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2314690A1 true CA2314690A1 (en) | 2001-01-31 |
Family
ID=26054445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002314690A Abandoned CA2314690A1 (en) | 1999-07-31 | 2000-07-28 | Fixed bed catalysts |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6489521B2 (en) |
| JP (1) | JP2001079410A (en) |
| KR (1) | KR20010061921A (en) |
| BR (1) | BR0003231A (en) |
| CA (1) | CA2314690A1 (en) |
| CZ (1) | CZ20002741A3 (en) |
| HU (1) | HUP0003006A3 (en) |
| ID (1) | ID26688A (en) |
| MX (1) | MXPA00007338A (en) |
| NO (1) | NO20003877L (en) |
| PL (1) | PL341783A1 (en) |
| TW (1) | TW553772B (en) |
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| WO2011054781A1 (en) | 2009-11-03 | 2011-05-12 | Basf Se | Thermoplastic compositions having improved flowability |
| EP2377844A2 (en) | 2004-06-21 | 2011-10-19 | Basf Se | Cyclohexane polycarboxylic acid derivatives containing adjuvants |
| WO2011151301A1 (en) | 2010-06-01 | 2011-12-08 | Basf Se | Method for producing expandable styrene polymer compositions |
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| EP1127613A1 (en) * | 2000-02-18 | 2001-08-29 | Degussa AG | Shaped fixed bed copper-Raney catalyst to be used in the dehydrogenation of alcohols |
| US7375053B2 (en) * | 2003-04-07 | 2008-05-20 | W. R. Grace & Co.- Conn. | Nickel and cobalt plated sponge catalysts |
| US20050100494A1 (en) | 2003-11-06 | 2005-05-12 | George Yaluris | Ferrierite compositions for reducing NOx emissions during fluid catalytic cracking |
| US20050100493A1 (en) * | 2003-11-06 | 2005-05-12 | George Yaluris | Ferrierite compositions for reducing NOx emissions during fluid catalytic cracking |
| US6919489B1 (en) | 2004-03-03 | 2005-07-19 | Eastman Chemical Company | Process for a cyclohexanedimethanol using raney metal catalysts |
| US20050232839A1 (en) | 2004-04-15 | 2005-10-20 | George Yaluris | Compositions and processes for reducing NOx emissions during fluid catalytic cracking |
| US7304011B2 (en) * | 2004-04-15 | 2007-12-04 | W.R. Grace & Co. -Conn. | Compositions and processes for reducing NOx emissions during fluid catalytic cracking |
| US20060068986A1 (en) * | 2004-09-27 | 2006-03-30 | Dimascio Felice | Catalyst elements and methods of making and using |
| US20060110311A1 (en) * | 2004-11-03 | 2006-05-25 | Dimascio Felice | Catalyst composite and methods of making and using |
| WO2006050742A1 (en) * | 2004-11-10 | 2006-05-18 | Degussa Gmbh | The fixed bed hydrogenation of fatty nitriles to fatty amines |
| US20080214387A1 (en) * | 2004-11-12 | 2008-09-04 | Daniel Ostgard | Process For Modifying Catalysts and the Use of the Catalysts |
| KR101382014B1 (en) * | 2005-04-27 | 2014-04-04 | 더블유.알. 그레이스 앤드 캄파니-콘. | Compositions and processes for reducing nox emissions during fluid catalytic cracking |
| US20060292059A1 (en) * | 2005-06-22 | 2006-12-28 | Dimascio Felice | Catalyst element and use thereof |
| US8735635B2 (en) | 2009-02-25 | 2014-05-27 | W. R. Grace & Co.-Conn. | Process for making 1, 2-propane diol from hydrogenation of glycerol |
| US20110011772A1 (en) * | 2009-07-15 | 2011-01-20 | Stephen Raymond Schmidt | Nickel and Cobalt Plated Sponge Catalysts |
| ES3010651T3 (en) | 2015-01-30 | 2025-04-04 | Evonik Operations Gmbh | Method for the preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| TWI787215B (en) | 2016-11-22 | 2022-12-21 | 美商Ｗ Ｒ 康格雷氏公司 | Catalysts with reduced attrition and method for manufacturing the same |
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| US4043946A (en) | 1976-07-30 | 1977-08-23 | The United States Of America As Represented By The Secretary Of The Interior | Production of supported Raney nickel catalysts by reactive diffusion |
| US4089812A (en) | 1976-07-30 | 1978-05-16 | The United States Of America As Represented By The Secretary Of The Interior | Massive catalyst |
| DE3537247A1 (en) | 1985-10-19 | 1987-04-23 | Bayer Ag | USE OF MODIFIED RANEY CATALYSTS FOR PRODUCING AROMATIC DIAMINO COMPOUNDS |
| US4895994A (en) | 1988-04-14 | 1990-01-23 | W. R. Grace & Co.-Conn. | Shaped catalysts and processes |
| US4826799A (en) | 1988-04-14 | 1989-05-02 | W. R. Grace & Co.-Conn. | Shaped catalyst and process for making it |
| DE4335360A1 (en) | 1993-10-16 | 1995-04-20 | Degussa | Activated metal fixed bed catalyst according to Raney and process for its preparation |
| DE4446907A1 (en) | 1994-12-27 | 1996-07-04 | Basf Ag | Process for the preparation of a hydrogenation catalyst |
| TW340806B (en) | 1995-03-28 | 1998-09-21 | Mitsui Toatsu Chemicals | Modified Raney catalyst and process for preparation thereof |
| DE19640554A1 (en) | 1996-10-01 | 1998-04-02 | Basf Ag | Process for the production of phthalides |
| DE19721897A1 (en) | 1997-05-26 | 1998-12-03 | Degussa | Molded metal fixed bed catalyst, process for its production and its use |
-
2000
- 2000-07-25 TW TW089114786A patent/TW553772B/en active
- 2000-07-26 CZ CZ20002741A patent/CZ20002741A3/en unknown
- 2000-07-27 ID IDP20000634D patent/ID26688A/en unknown
- 2000-07-27 MX MXPA00007338A patent/MXPA00007338A/en unknown
- 2000-07-28 NO NO20003877A patent/NO20003877L/en not_active Application Discontinuation
- 2000-07-28 JP JP2000229531A patent/JP2001079410A/en active Pending
- 2000-07-28 KR KR1020000043745A patent/KR20010061921A/en not_active Withdrawn
- 2000-07-28 CA CA002314690A patent/CA2314690A1/en not_active Abandoned
- 2000-07-28 HU HU0003006A patent/HUP0003006A3/en unknown
- 2000-07-31 PL PL00341783A patent/PL341783A1/en unknown
- 2000-07-31 BR BR0003231-0A patent/BR0003231A/en not_active Application Discontinuation
-
2001
- 2001-07-17 US US09/905,931 patent/US6489521B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2377844A2 (en) | 2004-06-21 | 2011-10-19 | Basf Se | Cyclohexane polycarboxylic acid derivatives containing adjuvants |
| WO2011054781A1 (en) | 2009-11-03 | 2011-05-12 | Basf Se | Thermoplastic compositions having improved flowability |
| WO2011151301A1 (en) | 2010-06-01 | 2011-12-08 | Basf Se | Method for producing expandable styrene polymer compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| ID26688A (en) | 2001-02-01 |
| MXPA00007338A (en) | 2002-08-06 |
| NO20003877D0 (en) | 2000-07-28 |
| US6489521B2 (en) | 2002-12-03 |
| BR0003231A (en) | 2001-03-13 |
| NO20003877L (en) | 2001-02-01 |
| JP2001079410A (en) | 2001-03-27 |
| HUP0003006A2 (en) | 2001-12-28 |
| HU0003006D0 (en) | 2000-10-28 |
| HUP0003006A3 (en) | 2002-04-29 |
| KR20010061921A (en) | 2001-07-07 |
| PL341783A1 (en) | 2001-02-12 |
| US20020037808A1 (en) | 2002-03-28 |
| TW553772B (en) | 2003-09-21 |
| CZ20002741A3 (en) | 2001-10-17 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |