TWI648100B - 對酸的作用具有增加之安定性的經壓錠之催化劑 - Google Patents
對酸的作用具有增加之安定性的經壓錠之催化劑 Download PDFInfo
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- TWI648100B TWI648100B TW106139869A TW106139869A TWI648100B TW I648100 B TWI648100 B TW I648100B TW 106139869 A TW106139869 A TW 106139869A TW 106139869 A TW106139869 A TW 106139869A TW I648100 B TWI648100 B TW I648100B
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- Prior art keywords
- shaped catalyst
- catalyst body
- calcium aluminate
- mixture
- hours
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 239000002253 acid Substances 0.000 title description 6
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 20
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 59
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000008188 pellet Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910018565 CuAl Inorganic materials 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910002804 graphite Inorganic materials 0.000 description 16
- 239000010439 graphite Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 238000005056 compaction Methods 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- -1 fatty acid esters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical group Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001700 katoite Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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)
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- 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
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Abstract
本發明關於一種將有機化合物中之羰基氫化之改良的催化劑,其係基於包含作為黏合劑材料之鋁酸鈣的經壓錠之成形催化劑本體,其中該成形催化劑本體包含含量在0.5至20重量%之比例的鋁酸鈣。本發明額外關於該催化劑之生產及關於其用於將有機化合物中之羰基氫化之用途。
Description
本發明關於一種將有機化合物中之羰基氫化之改良的催化劑,其係基於包含式CuAla
Mnb
Znc
Od
之材料及作為黏合劑材料之鋁酸鈣的經壓錠(tableted)之成形催化劑本體,其中該成形催化劑本體包含含量在0.5至20重量%之比例的鋁酸鈣。本發明額外關於該催化劑之生產及關於其用於將有機化合物中之羰基氫化之用途。
將諸如酯、二酯、醛或酮之有機化合物中之羰基氫化之催化方法在產業上有很大的關聯性。尤其,彼等用以將羧酸或其酯(尤指脂肪酸之酯)轉換成對應醇。 此處,基於銅組合上進一步之過渡金屬元素的系統係適於作為催化劑。催化劑通常以丸(pellet)、擠出物或顆粒之形式呈現。 WO 2004/085356描述生產將羰基化合物氫化之催化劑,其含有銅及鋁與鑭、鎢、鉬、鈦或鋯之至少一種氧化物且也將銅粉或銅片、水泥粉或石墨混入其中。 US 6,020,285描述含鈷或含鎳催化劑之生產,該催化劑額外包含具有大於2.5的Al/Ca比之鋁酸鈣。該催化劑適於次氯酸鹽的分解。 WO 98/11985揭示進一步包含具有大於4.0的Al/Ca比之鋁酸鈣以及氧化鋁及/或氧化鎂之含鈷或含鎳催化劑。該催化劑適於氧化性物質的分解。 US 7,084,312描述了基於銅、鋅及鋁之催化劑的生產,並且為此將銅、鋅及鋁的氧化物混合物與金屬銅、水泥或這兩種材料的混合物混合並成形而給出丸。該催化劑係用於將帶有羰基之有機化合物氫化。 Yakerson等人(Scientific Bases for the Preparation of Heterogeneous Catalysts, Preparation of Catalysts, p. 879 ff.)描述含水泥之金屬催化劑(諸如含鎳、含銅或含鋅催化劑)的生產。對應金屬氫氧化物碳酸鹽係用於此目的。
氫化方法的起始化合物通常具有痕量的酸性化合物。這些為例如在酯化反應中作為副產物存在的羧酸。在氫化反應的反應條件下,這些化合物攻擊催化劑並導致機械安定性降低,以及有時觀察到之催化活性金屬(其被產物流從反應器帶出,並必須從產物流中分離出來)的浸出。此外,隨著催化活性金屬的持續排放,催化劑的催化活性也降低。 含有銅及鉻之催化劑係用於此等反應。這些素來對酸的作用具有增加的安定性。由於更嚴格的環保規定,含鉻催化劑的使用係與甚至更苛刻的要求相關聯,因此需要以還是具有可相比擬的催化及物理性質的環保替代品來置換現有的CuCr系統。 因此,本發明的一個目的是提供一種將有機化合物中之羰基氫化的催化劑,其顯示出改善的機械安定性並且較不易受酸性化合物的作用影響。 此目的可藉由本發明之催化劑達成。
詳細說明 本發明關於一種呈丸形式之成形催化劑本體,其包含式CuAla
Mnb
Znc
Od
之材料及作為黏合劑材料之鋁酸鈣。 a係於範圍0至2.5,b於0.001至0.6,c於0至2.5,及d經選擇而使得實驗式的總價數為零。在特定之具體實施例中,a於範圍0.8至1.2,b於範圍0.05至0.3,c為0且d經選擇而使得實驗式的總價數為零。在又一較佳具體實施例中,a為0,b於範圍0.04至0.1,c於0.8至1.5且d經選擇而使得實驗式的總價數為零。 該等元素之氧化態為,Cu為+2,Al為+3,且Zn為+2。取決於Mn的比例,Mn之氧化態為+2、+3或+4,以其之材料中部分的Mn原子具有氧化態+2且其他者具有氧化態+3或+4,以致也可存在平均氧化態係於範圍+2至+4之結果。 鋁酸鈣為氧化物形式及/或氫氧化物形式之含有Ca及Al的化合物。例如,可存在通式x CaO·y Al2O3之煅燒鋁酸鈣或通式Cax
Aly
(OH)z
之化學式沉澱之鋁酸鈣。然而,取決於鋁酸鈣之處理,也可存在介於這兩個實驗式間的中間產物且其可同樣適於作為黏合劑材料。除了這些元素之外,進一步之元素也可存在於鋁酸鈣中。於較佳具體實施例中,鋁酸鈣以基於鋁酸鈣之重量計少於5.0重量%,較佳少於1.0重量%且特佳少於0.1重量%之重量比例含有進一步之元素。 本發明之成形催化劑本體的特徵在於其含有基於成形催化劑本體計0.5至20.0%重量比例之鋁酸鈣作為黏合劑材料。較佳地,基於該成形催化劑本體計,鋁酸鈣以0.5至10.0%重量比例存在,更佳地,以0.5至5.0%重量比例存在,甚至更佳地,以0.5至小於5.0%重量比例存在,最佳地,以0.5至3.0%重量比例存在。 用於本發明目的之鋁酸鈣的原子Ca/Al比可有變化且較佳於範圍0.9至3.5,更佳於1.0至2.0。合成生產之材料適於作為鋁酸鈣。然而,也可使用天然發生之鋁酸鈣,如水鈣鋁榴石(katoite)。 經壓錠之成形催化劑本體可採各種維度存在。丸的直徑可在範圍2至6mm且較佳在2至4mm。直徑特佳為3mm。丸的高度可在範圍2至6mm且較佳在2至4mm。高度特佳為3mm。 在使用來作為黏合劑材料前,可使鋁酸鈣經歷熱處理(煅燒)。此處理於範圍300至800℃,較佳450至750℃且特佳450至650℃之溫度進行。 於本發明的一種具體實施例中,鋁酸鈣的粒子的平均粒徑具有根據ISO 13302/2009藉由雷射粒徑分析手段量測之於範圍0.1至200µm,較佳於範圍5至50µm之d50
。在又一具體實施例中,d90
係於範圍10至300µm,較佳於範圍20至100µm。 包含式CuAla
Mnb
Znc
Od
之材料及含有基於成形催化劑本體計0.5至20.0%重量比例之鋁酸鈣作為黏合劑材料之本發明的成形催化劑本體係藉由下列發明步驟生產: a) 將含金屬混合物與鋁酸鈣、潤滑劑及水混合,該含金屬混合物含有銅、錳及選自鋅及鋁所組成群組之至少一種元素, b) 將來自步驟a)之該混合物壓錠而給出經壓錠之成形本體, c) 於範圍200至800℃之溫度將經壓錠之成形本體熱處理範圍30分鐘至4小時的時間, 其中a於範圍0至2.5,b於範圍0.001至0.6,c於範圍0至2.5,及d經選擇而使得實驗式的總價數為零。 在較佳具體實施例中,a於範圍0.8至1.2,b於範圍0.05至0.3,c為0且d經選擇而使得實驗式的總價數為零。在又一較佳具體實施例中,a為0,b於範圍0.04至0.1,c於範圍0.8至1.5且d經選擇而使得實驗式的總價數為零。 在較佳具體實施例中,基於成形催化劑本體計,鋁酸鈣的重量比例係於範圍0.5至10.0%,較佳0.5至5.0%,更佳0.5至小於5.0%,最佳0.5至3.0%。 步驟a)中所用之該含有銅、錳及選自鋅及鋁所組成群組之至少一種元素的混合物可選自氧化物、氫氧化物或碳酸酯之群組。此處較佳者為對應元素的氧化物。該等元素可呈個別化合物(諸如氧化銅及錳、鋅或鋁之氧化物)存在,或是呈混合之化合物(諸如銅、錳及選自鋅及鋁所組成群組之至少一種元素的混合氧化物)存在。 步驟a)之含金屬混合物可藉由從水溶液中沉澱出溶解的金屬離子而獲得。合適的起始化合物原則上是所有可溶於水中或鹼性或酸性水溶液中的化合物。偏好的是使用硝酸鹽、鹵化物、氧化物、硫酸鹽、乙酸鹽或甲酸鹽。 可接著視需要地使步驟a)後獲得之混合物經歷老化步驟。此處,在沒有添加進一步成分下允許該混合物靜置5分鐘至10小時,較佳5分鐘至3小時,或該混合物保持運動。老化溫度通常對應於混合物的環境溫度,但也可以經控制方式設定於範圍0℃至90℃。 接著,視需要地將步驟a)後獲得之混合物(其視需要地經老化)壓實(compacted)及/或製粒(granulated),通常在沒有熱處理下,且隨後歷經壓錠步驟b)。此係使用商用壓錠機進行,例如來自IMA Kilian的Pressima型。步驟a)後獲得之混合物含有潤滑劑。此為有助於混合物之壓錠性質的化合物。合適的潤滑劑為石墨、油或硬脂酸鹽,較佳為石墨。潤滑劑係以0.1至5.0重量%,較佳0.5至5.0重量%且特佳1.0至4.0重量%之比例添加到待壓錠之組成物中。 步驟a)後獲得之混合物額外的含有水。基於所用之含金屬混合物計,此通常以1至10重量%含量存在,較佳地2至4重量%,非常佳地3重量%。 丸的熱處理係在範圍200至800℃之溫度,較佳地300至700℃,更佳地300至500℃進行。此熱處理之持續期係在範圍30分鐘至4小時,較佳在1至3小時,且特佳在2小時。 本發明之方法所生產之丸具有80至300N,較佳100至250N,特佳120至180N之側向壓縮強度。壓錠所生產之丸較佳具有在範圍2至4mm之直徑,在範圍2至4mm之高度以及在範圍120至180N之側向壓縮強度。 本發明之成形催化劑本體的孔體積(藉由水銀孔隙率測量法之手段量測)係在範圍100至300mm3
/g,較佳150至250mm3
/g。 本發明之成形催化劑本體具有BET比表面積為20至60m2
/g,較佳30至50m2
/g。 於本發明之成形催化劑本體中,具有7.0至40.0nm半徑之孔的孔體積比例較佳為在範圍50至95%,更佳70至90%的總孔體積。 可藉由本發明之方法獲得的成形催化劑本體係在進一步之步驟中還原。 較佳藉由於還原氣氛中加熱經壓錠之成形催化劑本體來進行還原。還原氣氛特別是氫氣。還原係例如在範圍150℃至450℃,較佳在範圍180℃至250℃,特佳在範圍190℃至210℃之溫度進行。還原係例如在1小時至10天時期,較佳在2小時至72小時時期,特佳在24至48小時時期進行。在較佳具體實施例中,還原係在範圍190℃至210℃之溫度進行24至48小時時期。 在較佳具體實施例中,成形催化劑本體係在還原後濕或乾安定。在濕安定化之例中,成形催化劑本體係用液體覆蓋以盡量避免與氧接觸。合適的液體涵蓋有機液體及水,較佳有機液體。較佳之有機液體為於20℃具有蒸氣壓0.5hPa或更小者。此等合適之有機液體的實例為異癸醇、Nafol、脂肪醇、十六烷、2-乙基己醇、丙二醇及其混合物,特別是異癸醇。在乾安定化中,將氧或含氧氣體(較佳空氣)與諸如氬或氮之惰性氣體的混合物引入到還原空間中。混合物中的氧濃度較佳從約0.04體積%增加至約21體積%。例如,可將空氣與惰性氣體的混合物以開始是約0.2體積%的空氣對99.8體積%的惰性氣體之空氣對惰性氣體比引入。接著逐漸(如,連續或步進式)增加空氣對惰性氣體比直到饋入最終100體積%的空氣(對應於氧濃度約21體積%)。在不受理論束縛下,推測作為引入空氣或氧之結果,具有厚度例如0.5至50nm,較佳1至20nm,特佳1至10nm的薄氧化物層係形成在催化劑的表面上,且此保護成形催化劑本體免於進一步氧化。在乾安定化中,反應器溫度較佳為100℃或更低,特佳為20℃至70℃且最佳為30℃至50℃。還原可異位(ex situ)或在其中成形催化劑本體係作為催化劑引入之反應設備中原位(in situ)進行。 於還原後,丸形式之成形催化劑本體的側向壓縮強度具有50至250N,較佳60至200N,特佳70至150N之值。 為了判定本發明成形催化劑本體對酸的作用之安定性,使成形本體歷經酸處理並於隨後判定經處理之丸的側向壓縮強度。 本發明成形催化劑本體係適合用於將有機化合物中之羰基催化性氫化。可能之反應涵蓋二酯(尤其是馬來酸的二酯)氫化成二醇,糖氫化成多元醇,酯(尤其是脂肪酯)之氫化,脂肪酸之氫化(如,藉由酯化及隨後氫解),酮之氫化,側氧基醛氫化成側氧基醇,及糠醛之氫化。 實施例 本發明目的之燒失量的判定係藉由測定約1-2g待分析材料樣品的重量,且隨後將此樣品在室溫下加熱至900℃並在此溫度下保持3小時而進行。隨後在保護性氣氛下將樣品冷卻並量測剩餘重量。介於熱處理之前與之後重量的差對應於燒失量。 根據DIN EN 1094-5進行側向壓縮強度之判定。此處,量測統計上充分數目的丸(至少20個丸)並計算個別測量的算術平均值。此平均對應於特定樣本的側向壓縮強度。 化學元素之判定係根據DIN EN ISO 11885藉由ICP(電感耦合電漿)測量手段進行。 酸處理係藉由混合總量1.5g經壓錠之樣品與15g的乙酸(10體積%,於H2
O中)進行。將這些於室溫攪拌30分鐘。於120℃,空氣中將經壓錠之樣品乾燥10小時且隨後量測彼之側向壓縮強度。 BET比表面積係根據DIN 66131藉由氮吸附手段判定。可藉由本發明之方法獲得之催化劑較佳具有BET比表面積在範圍20至100m2
/g,尤其30至80m2
/g,且特佳40至60m2
/g。 成形催化劑本體的孔體積係根據DIN 66133藉由水銀孔隙率法量測。 鋁酸鈣於成形催化劑本體中的重量比例係藉由X-射線繞射手段判定。使用來自BRUKER之D4 Endeavor。為此目的,樣品於範圍5至90之2°Θ (步進順序0.020 2°Θ,每步進1.5秒測量時間)量測。使用CuKα1輻射(波長1.54060Å, 40kV,35mA)作為輻射。於測量期間,樣品盤繞其軸以30轉/分鐘速度旋轉。所獲得之反射強度的光譜係藉由Rietveld精修手段定量分析,並判定樣品中鋁酸鈣的比例。為了判定各別晶體相的比例,使用來自BRUKER之TOPAS軟體。 催化劑粉末的生產 藉由將1250g的Cu(NO3
)2
·3H2
O,220g的Mn(NO3
)2
· 4H2
O及1800g的Al(NO3
)3
·9H2
O溶解在9000g的蒸餾H2
O中而生產水溶液1。藉由將1720g的Na2
CO3
溶解在7500g的蒸餾H2
O中而生產水溶液2。分別將兩溶液加熱至80℃並伴隨攪拌。隨後將兩溶液稱量到沉澱容器中,並伴隨持續攪拌。兩種溶液的添加是以沉澱容器中組合之混合物的pH為7(+/-0.2)的方式進行的。將此處所形成之沉澱物濾出並以蒸餾H2
O清洗來移除黏附不純物。將濾餅重新懸浮於8l的蒸餾H2
O中並噴霧乾燥。隨後將乾燥的粉末於750℃熱處理3小時,並作為壓錠實施例的起始材料。基於燒失量後之總質量計,相對重量比例為Cu=45重量%,Mn=7重量%,及Al=18重量%。此對應於實驗式CuMn0.18
Al0.94
O2.6。 比較例1(催化劑A) 藉由混合500g的催化劑粉末與10g的石墨且隨後使混合物成形而給出具有維度3mm高度且3mm直徑之丸來生產催化劑A。在壓錠及酸處理後判定樣品的側向壓縮強度。所有丸被酸處理破壞到彼等完全以破碎形式呈現且無法判定側向壓縮強度之程度。 比較例2(催化劑B) 藉由混合500g的催化劑粉末與10g的石墨且隨後使混合物成形而給出具有維度4.5mm高度且4.5mm直徑之丸來生產催化劑B。在壓錠及酸處理後判定樣品的側向壓縮強度。所有丸被酸處理破壞到彼等完全以破碎形式呈現且無法判定側向壓縮強度之程度。 使在壓錠後獲得之材料的一部分歷經還原。為了使CuO的還原以Cu呈現,此處,樣品於2體積%的H2
與98體積%的N2
所構成之氣體混合物中以溫度200℃熱處理。隨後將樣品在氮氣下冷卻至室溫並於儲存於液體癸醇下。隨後量測此樣品的側向壓縮強度。 實施例1(催化劑1) 將500g的催化劑粉末與5g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於320℃進行熱處理。在壓錠後,在熱處理後及在酸處理後,判定樣品的側向壓縮強度。 實施例2(催化劑2) 將500g的催化劑粉末與15g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。丸隨後以蒸氣於100-150℃處理24小時。隨後於320℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 實施例3(催化劑3) 將500g的催化劑粉末與15g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度4.5mm高度且4.5mm直徑之丸。隨後於450℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 使在壓錠後獲得之材料的一部分歷經還原。為了使CuO的還原以Cu呈現,此處,樣品於2體積%的H2
與98體積%的N2
所構成之氣體混合物中以溫度200℃熱處理。隨後將樣品在氮氣下冷卻至室溫並於儲存於液體癸醇下。隨後量測此樣品的側向壓縮強度。 實施例4(催化劑4) 將500g的催化劑粉末與15g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於450℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 實施例5(催化劑5) 將500g的催化劑粉末與15g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於650℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 實施例6(催化劑6) 將500g的催化劑粉末與50g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於450℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 實施例7(催化劑7) 將500g的催化劑粉末與50g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於650℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 實施例8(催化劑8) 將500g的催化劑粉末與100g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於450℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 實施例9(催化劑9) 將500g的催化劑粉末與100g的鋁酸鈣(SECAR 71,30重量%的CaO,70重量%的Al2
O3
),10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於650℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 實施例10(催化劑10) 將實施例1中所用鋁酸鈣於650℃熱處理2小時。隨後將500g的催化劑粉末與15g之此經熱處理的鋁酸鈣,10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於450℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 實施例11(催化劑11) 將實施例1中所用鋁酸鈣於650℃熱處理2小時。隨後將500g的催化劑粉末與15g之此經熱處理的鋁酸鈣,10g的石墨及15g的蒸餾H2
0混合。隨後使混合物老化4小時並使混合物成形而給出具有維度3mm高度且3mm直徑之丸。隨後於650℃進行熱處理。在壓錠後,在熱處理後及亦在煅燒樣品之酸處理後,判定樣品的側向壓縮強度。 從表1清楚可見,根據本發明之催化劑在熱處理後具有顯著較高於比較性催化劑之側向壓縮強度。在酸處理後,所有樣品的側向壓縮強度減少,但根據本發明之樣品的側向壓縮強度仍顯著高於酸處理前之比較性催化劑(催化劑A與B)所具者。這凸顯出,即使在含酸環境的嚴峻條件下,如亦會存在於諸如酯、二酯、醛或酮之有機化合物中之羰基的氫化中的含酸環境(此係因起始材料含有含酸不純物),本發明催化劑之增加的機械安定性。藉由BET法所判定之比表面積不顯著受到本發明方法的影響。此於40‑7.0nm範圍之孔的相對孔體積而言亦同。這凸顯出,本發明之成形催化劑本體對熱處理期間熱壓力的安定性。
Claims (20)
- 一種成形催化劑本體(shaped catalyst body),其包含式CuAlaMnbZncOd之材料,其中a為範圍0至2.5之數目,b為範圍0.001至0.6之數目,及c為範圍0至2.5之數目,及d經選擇而使得該實驗式的總價數為零,其中該成形催化劑本體以丸形式存在,並含有基於該成形催化劑本體計0.5至10.0%重量比例之鋁酸鈣作為黏合劑材料。
- 如請求項1之成形催化劑本體,其中基於該成形催化劑本體計,該鋁酸鈣以0.5至5.0%重量比例存在。
- 如請求項1之成形催化劑本體,其中基於該成形催化劑本體計,該鋁酸鈣以0.5至小於5.0%重量比例存在。
- 如請求項1之成形催化劑本體,其中基於該成形催化劑本體計,該鋁酸鈣以0.5至3.0%重量比例存在。
- 如請求項1之成形催化劑本體,其中側向壓縮強度為100-300N。
- 一種生產成形催化劑本體之方法,該成形催化劑本體包含式CuAlaMnbZncOd之材料並含有基於該成形催化劑本體計0.5至20.0%重量比例之鋁酸鈣作為黏合劑材料,該方法包含下列步驟:a)將含金屬混合物與鋁酸鈣、潤滑劑及水混合,該含金屬混合物含有銅、錳及選自鋅及鋁所組成群組之至少一種元素,b)將來自步驟a)之該混合物壓錠而給出經壓錠之成形本體,c)於範圍200至800℃之溫度將該經壓錠之成形本體熱處理範圍30分鐘至4小時的時間,其中a為範圍0至2.5之數目,b為範圍0.001至0.6之數目,及c為範圍0至2.5之數目,及d經選擇而使得該實驗式的總價數為零。
- 如請求項6之方法,其中該含金屬混合物係銅、錳及鋁之混合氧化物。
- 如請求項6或7之方法,其中基於該成形催化劑本體計,該鋁酸鈣以0.5至10.0%重量比例存在。
- 如請求項8之方法,其中來自步驟a)之該混合物老化5分鐘至10小時的時間。
- 如請求項6或7之方法,其中基於該成形催化劑本體計,該鋁酸鈣以0.5至5.0%重量比例存在。
- 如請求項10之方法,其中來自步驟a)之該混合物老化5分鐘至10小時的時間。
- 如請求項6或7之方法,其中基於該成形催化劑本體計,該鋁酸鈣以0.5至小於5.0%重量比例存在。
- 如請求項12之方法,其中來自步驟a)之該混合物老化5分鐘至10小時的時間。
- 如請求項6或7之方法,其中基於該成形催化劑本體計,該鋁酸鈣以0.5至3.0%重量比例存在。
- 如請求項14之方法,其中來自步驟a)之該混合物老化5分鐘至10小時的時間。
- 如請求項6或7之方法,其中來自步驟a)之該混合物老化5分鐘至10小時的時間。
- 如請求項6或7之方法,其中該熱處理於300至500℃進行範圍1小時至3小時的時間。
- 如請求項6或7之方法,其中於步驟a)中所用該鋁酸鈣係實質上以氧化形式存在。
- 如請求項6或7之方法,其中於步驟c)後,進行該成形本體之還原。
- 一種將有機化合物中之羰基氫化之方法,其係使用如請求項1至5項中任一項之成形催化劑本體或使用藉由如請求項6至19項中任一項之方法生產之成形催化劑本體。
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