CN1568228A - 用于将马来酸酐氢化成四氢呋喃的多孔催化剂 - Google Patents
用于将马来酸酐氢化成四氢呋喃的多孔催化剂 Download PDFInfo
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- CN1568228A CN1568228A CNA018203213A CN01820321A CN1568228A CN 1568228 A CN1568228 A CN 1568228A CN A018203213 A CNA018203213 A CN A018203213A CN 01820321 A CN01820321 A CN 01820321A CN 1568228 A CN1568228 A CN 1568228A
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- catalyst
- pore volume
- hydrogenation
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 30
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title description 62
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011148 porous material Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
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- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 229960004643 cupric oxide Drugs 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
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- 239000011701 zinc Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
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- 230000000996 additive effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
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- 239000005749 Copper compound Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
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- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 18
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- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
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- 239000002253 acid Substances 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
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- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229960005137 succinic acid Drugs 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 3
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011157 data evaluation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/64—Pore diameter
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
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- 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
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- 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)
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- 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
本发明涉及一种特别适用于将马来酸酐和其衍生物氢化成THF或其衍生物的氢化催化剂。所述氢化催化剂含有氧化铜和至少一种其它金属或其化合物,选自Al、Si、Zn、La、Ce、IIIA至VIIIA族元素和IA和IIA族元素,该催化剂具有对于孔直径>50nm的孔体积是≥0.01ml/g,直径>50nm的大孔的孔体积与直径>4nm的孔的总孔体积之比是>10%。
Description
本发明涉及一种通过在选自马来酸和琥珀酸和这些酸的衍生物中的基质的气相中进行催化氢化来制备未取代的或被烷基取代的γ-丁内酯和四氢呋喃的方法。在本发明中,所述衍生物是酯和酸酐,它们象这些酸本身一样可以带有一个或多个烷基取代基。使用具有特定孔隙度的催化剂。
通过气相氢化马来酸酐(MA)制备γ-丁内酯(GBL)和四氢呋喃(THF)是多年来公知的反应。用于进行该催化反应的许多催化剂体系描述在文献中。许多这些催化剂体系是含铬的。根据催化剂的组成和选择的反应参数,使用这些催化剂获得了不同的产物分布。
除了MA以外,马来酸本身、琥珀酸及其酸酐以及这些酸的酯也可以作为用于制备GBL和THF的原料。如果要制备带有烷基取代基的GBL和THF,则可以使用与上述酸、酯和酸酐对应的被烷基取代的物质。
US 3065243公开了一种其中亚铬酸铜用作催化剂的方法。根据其中的描述和实例,该反应导致形成相当量的琥珀酸酐(SA),必须将其循环。如所知的那样,通常出现的工艺问题是由于形成的SA或琥珀酸结晶而随后导致管线阻塞。
公开了其它用于氢化MA的亚铬酸铜催化剂,例如在US 3580930、US 4006165、EP-A 638 565和WO 99/38856中。根据这些出版物,可以使用其中所述的催化剂获得高产率的GBL。在每种情况下仅仅形成痕量的THF。但是,由于许多原因,通常希望有大量THF。
能够实现该目的的方法描述在US 5072009中。根据该专利使用的催化剂具有通式Cu1ZnbAlcMdOx,其中M是至少一种选自元素周期表的IIA和IIIA、VA、VIII、Ag、Au族元素、IIIB至VIIB族以及镧系和锕系元素中的元素,b是0.001-500,c是0.001-500,d是0至<200,x对应于根据化合价标准必要的氧原子数目。尽管据说根据该专利使用的催化剂不含任何铬,但是所有实施例都描述了含铬的催化剂。根据这些实施例,所得的最大THF产率是96%,氢化反应在20-40巴下进行。
用于MA的氢化的两阶段催化剂体系描述在US 5149836中。用于第一阶段的催化剂是不含铬的,而用于第二阶段的催化剂是基于Cu-Zn-Cr氧化物。
所有上述催化剂体系的主要缺点是存在氧化铬,应该避免这种物质,因为它们的毒性高。用于通过氢化MA制备GBL的不含铬的催化剂体系也描述在现有技术中。这些催化剂的例子可以参见WO 99/35139(Cu-Zn氧化物)、WO 95/22539(Cu-Zn-Cr)和US 5122495(Cu-Zn-Al氧化物)。所有这些催化剂体系使得有可能达到高的GBL产率,达到98%,但仅仅形成痕量的THF(如果有的话)。尽管显然可以通过提高反应温度或通过在反应器内更长的停留时间来促进形成THF,但是同时增加了不希望的副产物例如丁醇、丁烷、乙醇或乙烷的比例。
仅仅由氧化铜和氧化铝制成的、用于将MA氢化成GBL的催化剂描述在WO 97/24346中。该催化剂也存在与前段中列出的出版物中所述催化剂同样的缺点,即仅仅形成少量或痕量的THF。
具有如WO 97/24346所述的主要相同组成的催化剂、即基于Cu-Al氧化物的使用也描述在JP 2 233 631中。该发明的目的是以这样的方式进行MA的氢化,其中THF和1,4-丁二醇作为主要产物形成,和如果有的话,仅仅形成少量GBL。这通过使用基于混合Cu-Al氧化物的催化剂并遵守特定的反应条件来获得。使用该方法获得的典型混合物包含约15-20%摩尔的1,4-丁二醇和60-80%摩尔的THF,根据一个实施例,THF的量甚至提高到99%摩尔。这通过使用大量过量的GBL作为溶剂来获得。但是,如果不使用溶剂,则THF产率显著地降低到约75%的值。
在上述出版物中公开的所有催化剂的共同特征是它们具有均一的结构。存在的组分彼此之间紧密混合,所以结构变成基本上均匀的,催化剂基本上没有具有不同结构的组分。
相比之下,EP-A 0 404 408描述了一种用于MA的氢化的催化剂,其结构一般不同于上述文献中的催化剂结构。催化活性物质基本上对应于在上述US 5072009中公开的物质。然后将该物质涂在基本上惰性的、至少部分多孔且具有外表面的载体上。催化活性物质粘合在载体的外表面上。与未涂在载体上且获得THF作为主要产物的相应催化剂相比,该载附催化剂获得GBL作为优选的产物,以及大量SA作为副产物。在该描述中说明,当使用如US 5079009中公开的全活性催化剂形式的相同活性物质时,随着成形催化剂尺寸的增加,有利于THF的形成。但是当使用涂布的催化剂(其中催化活性物质以薄层的形式涂在载体上)时,达到较高的GBL产率。
在多孔材料期刊(Journal of Porous Materials),2(1995),79-84页中,Castiglioni等人报告了通过反复压制来降低氧化铜/氧化铝催化剂的孔隙度。以这种方式压制得到了在MA的氢化中对THF具有较高选择性的催化剂,同时GBL的形成减少。
通常知道在涂布的催化剂中的催化活性组分的孔中,使各反应组分的扩散路径比由相同物质构成的全活性催化剂的情况短。对于使用不同孔隙度的催化剂来氢化马来酸酐,迄今发现的结果教导本领域技术人员在催化剂中的短扩散路径有利于形成GBL,而长扩散路径促进形成THF。这看来是有理的,因为在先形成作为随后产物的GBL的同时,在氢化中形成THF。
令人惊奇的是,现在已经可能开发基于氧化铜并具有高比例的大孔且在MA的氢化中对THF具有高选择性的催化剂。
基于氧化铜并具有特定孔隙度的催化剂及其作为氢化催化剂的用途是本身公知的。
所以,US 5155086描述了含有氧化铜、氧化锌和氧化铝的粉状催化剂,其中总孔体积的至少40%被直径为120-1000埃的孔占据。这些催化剂适用于将羧酸和羧酸酯氢化成醇,和将酮和醛氢化成醇。其中没有描述MA向THF的氢化。
EP-A 604 792描述了基于每100重量份氧化铜含有40-130重量份氧化锌和2-50重量份氧化铝以及1-40重量份氧化钠的催化剂,其总表面积是50-100m2/g(由BET方法测定),其中75-95%的总表面积被半径为9-1000毫米的孔占据,其余的表面积被半径小于9毫米的孔占据。这种催化剂用于氢化有机化合物,特别是用于将饱和和不饱和的醛、酮、羧酸或羧酸酯氢化成饱和的醇。其中没有描述MA向THF的氢化。
最后,WO 97/34694描述了氧化铜/氧化铝氢化催化剂,其可以是挤出物形式或是压片的形式。挤出物的孔体积是0.15-0.6ml/g,双模态孔半径分布在约100埃和1000-2000埃处具有最大值,而压片的孔体积是0.2-0.6ml/g,双模态孔半径分布在约100埃和500-2000埃处具有最大值。在这里,也没有描述MA向THF的氢化。
根据本发明使用的催化剂与现有技术描述的催化剂不同。本发明的催化剂含有氧化铜和至少一种其它金属或化合物,优选是氧化物,选自Al、Si、Zn、La、Ce、IIIA至VIIIA族元素和IA和IIA族元素。此外,催化剂固体具有对于孔直径>50nm的孔体积是≥0.01ml/g,直径>50nm的大孔的孔体积与直径>4nm的孔的总孔体积之比是>10%。
在本发明中,元素周期表的各族按照旧IUPAC命名法指定。
本发明的催化剂能氢化C4-二羧酸和/或其衍生物,形成作为主要产物的THF,产率显著高于90%,通常接近100%。
在本发明中,术语“C4-二羧酸和其衍生物”指可未取代或带有一个或多个C1-C4烷基取代基的马来酸或琥珀酸,以及这些未取代或被烷基取代的酸的酸酐和酯。这种酸的一个例子是柠康酸。优选使用MA作为待氢化的原料。
制得的THF也可以带有一个或多个烷基取代基,这取决于所用的原料。以这种方式被取代的THF将在下文中称为THF衍生物。
本发明的催化剂含有作为基本材料的氧化铜,其与至少一种其它金属或化合物、优选氧化物混合。使用选自Al、Si、Zn、Ce、IIIA至VIIIA族元素和IA和IIA族元素的金属或其化合物,优选氧化物。
优选使用二氧化硅、氧化锌、氧化铝、氧化锆和/或二氧化钛。特别优选基于氧化铜/氧化铝和氧化铜/氧化锌/氧化铝的不含铬的体系。
本发明的催化剂的氧化铜含量是≥10%重量,优选≥25%重量。
为了显示在氢化活性方面的所需性能,本发明的催化剂必须具有在孔隙度方面的特定性能。用作成形体的催化剂具有对于孔直径>50nm的孔体积≥0.01ml/g,优选对于孔直径>100nm的孔体积≥0.025ml/g,特别是对于孔直径>200nm的孔体积≥0.05ml/g。这些值根据DIN 66133通过压汞法来测定。孔直径的数据评价为4纳米至300微米。
此外,特定大孔隙度的存在是重要的。因此,在成形体中,直径>50nm的大孔的孔体积与直径>4nm的孔的总孔体积之比应该>10%。该比率优选>20%,特别是>30%。
催化剂组合物通过本领域技术人员公知的方法来制备。优选这样的方法,其中氧化铜以细分的形式与其它组分充分混合获得。这优选通过沉淀反应来实现。在这里,溶于溶剂中的铜化合物在溶解或悬浮于溶剂中的其它金属化合物的存在下在沉淀剂的作用下沉淀出来,过滤,洗涤,干燥,如果需要的话进行煅烧。
例如,相应的金属碳酸盐和/或氢氧化物可以在水溶液中沉淀,过滤,洗涤,干燥,如果需要的话进行煅烧。金属碳酸盐和/或氢氧化物可以例如通过将相应的金属盐溶解在水中并加入碳酸钠溶液来获得。所用的金属盐是例如硝酸盐、硫酸盐、氯化物、乙酸盐和/或草酸盐。
本发明的催化剂是本领域技术人员公知的成形体的形式。合适的成形体的例子包括压片、环、球和挤出物。这些成形体可以通过公知的方法例如挤出、成片或聚集方法来获得。
本发明催化剂达到所需氢化活性所必须具有的孔隙度可以在其制备期间通过特定的手段来获得。这些手段的例子是加入成孔剂、添加剂,选择合适的催化剂粉末的粒径分布和孔隙度、在原料成形中合适的工艺参数,以及上述手段的组合。
合适的成孔剂是例如羧酸,例如草酸、硬脂酸和棕榈酸,以及烃类和改性烃类,例如淀粉和甲基纤维素。其它合适的成孔剂是粉状活性炭、石墨、铵盐和硝酸盐。这些物质可以在成形后被去除,例如通过对成形催化剂体的热处理来进行。
作为用于调节催化剂中永久保留的孔隙度的添加剂,可以使用例如金属氧化物、金属碳化物和金属氮化物。
催化剂粉末的适宜粒径分布和/或孔隙度可以例如通过对催化剂粉末的悬浮液进行预先热处理来实现。在催化剂的成形过程中,可以例如通过在碾磨期间输入低能量或在成片期间降低压制压力来达到较高的大孔隙度。
对于根据本发明设定催化剂孔隙度,使用预煅烧的原料和成孔剂是优选的。
作为上述制备方法的另一种选择,本发明的催化剂也可以例如通过将活性组分涂布在具有适宜孔隙度的载体上来制备。涂布可以例如通过浸渍来进行。根据本发明的催化剂也可以通过将活性组分或其前体化合物与载体组分或其前体化合物的非均相混合物成形来获得。
使用的催化剂可以进一步含有0-10%重量的助剂。在本发明中,助剂是能在催化剂制备过程中改进加工和/或能提高成形催化剂体的机械强度的有机和无机物质。这些助剂是本领域技术人员公知的,例如包括石墨、硬脂酸、硅胶和铜粉。
一般来说,在反应中使用之前,催化剂进行活化,通常是用氢气进行预处理。这通过将催化剂混合物中存在的化合物、特别是氧化铜部分还原成元素金属或在本发明催化反应中呈活性的金属的低氧化态来制备活性催化剂。
本发明的催化剂具有满意的操作寿命。虽然在该操作时间内该催化剂的活性和/或选择性降低,但是该催化剂可以通过本领域技术人员公知的方法来再生。这些包括在高温下在氢气流中对催化剂进行还原处理。还原处理可以任选地在氧化处理之前进行。在这里,含有分子氧的气体混合物,例如空气,在高温下通过催化剂床。也可以用适宜的溶剂例如甲醇、THF或GBL洗涤催化剂,然后用气流干燥。
适用于进行该反应的反应器一般是这样的反应器,其中催化剂作为固定床放置。优选壳管式反应器,使得反应中释放的热量可以被去除。在氢化中,原料、优选MA被蒸发,并与含氢气的气流一起通过该反应器。优选使用纯氢气。添加其它气态组分例如水蒸汽或一氧化碳对选择性、活性或长期稳定性具有有利的作用。原料的浓度优选在0.2-2%体积范围内。在原料的显著较高的浓度下,原料在反应器中浓缩,特别是当使用MA时,并用液体膜涂布催化剂。显著较低的浓度将降低时空产率。
反应温度是150-400℃,优选200-300℃。较高的温度促进形成副产物,而较低的温度导致催化剂活性不必要地降低。压力是0.5-100巴,优选1-50巴,特别是<20巴。设定GHSV(气体小时空速=反应气体在STP下的体积流速除以催化剂床的体积),使得达到原料的完全转化率。这帮助产物混合物的后处理并省去了循环未反应的原料。为此,GHSV设定为10-50000h-1,优选100-10000h-1。产物混合物可以通过本领域技术人员公知的方法来分离。部分未反应的氢气优选进行循环,并在氢化中再次使用。
通过以下实施例说明本发明。
实施例1:
根据本发明的催化剂的制备
将8.1升水和672克勃姆石(PuralSB,来自Condea,Al2O3含量:约72%)放入配备有搅拌器的可加热的沉淀容器中,并加热到50℃。将含有2980克Cu(NO3)2*3H2O和3560克Zn(NO3)2*6H2O的7.5升金属盐溶液以及碳酸钠的20%重量水溶液在搅拌的同时在半小时内计量加入该沉淀容器中。碳酸钠溶液的计量添加量使得沉淀容器中的pH为6.2。碳酸钠溶液的消耗量是13.8千克。所形成的悬浮液经过过滤,用水洗涤固体直至洗涤液不再含有任何硝酸盐(<25ppm)。滤饼先于120℃干燥,然后于300℃煅烧。
将1.7千克该物质与300克硝酸铵和60克石墨充分混合,压片制得直径3毫米、高度3毫米的片剂。这些片剂于500℃煅烧2小时。
实施例2:
根据本发明的催化剂的制备
将1.9千克的由实施例1制得的沉淀产物与100克硝酸铵和60克石墨充分混合,压片制得直径3毫米、高度3毫米的片剂。这些片剂于500℃煅烧2小时。
实施例3:
根据本发明的催化剂的制备
将1.7千克的由实施例1沉淀并于120℃干燥的产物于800℃煅烧,然后与300克未煅烧的沉淀产物和60克石墨充分混合,压片制得直径3毫米、高度3毫米的片剂。
对比例1:
催化剂的制备
将1.5千克的按照实施例1于120℃干燥并于300℃煅烧的沉淀产物与45克石墨充分混合,压片制得直径3毫米、高度3毫米的片剂。
实施例4-6,对比例2:
马来酸酐的制备
将100毫升的上述实施例的催化剂片剂与100毫升相同尺寸的玻璃环混合,并放入内径27毫米的管式反应器中。通过循环油加热/冷却该反应器,使反应气体从顶部向下通过该反应器。催化剂床内部具有轴向温度分布。MA作为熔体被泵送入在200℃下操作的蒸发器中,在那里在氢气流中被蒸发。MA浓度为1.2%体积的MA/氢气混合物然后通过该反应器,并在催化剂床以上预热。在所有实施例中,MA的转化是完全的。
在将MA/氢气混合物加入反应器之前,催化剂用氢气进行预处理。为此,该反应器先用200标准升/小时的氮气于大气压下吹扫,同时在1小时内加热到催化剂床中180℃的温度。氮气流量然后增加到950标准升/小时,并加入额外的50标准升/小时的氢气。在该过程中,观察到在催化剂床中在热点中温度略微升高到约250℃。热点从反应器入口迁移到反应器出口。在整个催化剂床的温度已冷却到190℃之后,氮气流量降低到900标准升/小时,氢气量增加到100标准升/小时。逐步关闭氮气流,氢气流量逐步增加到600标准升/小时。
从下表可见,与使用对比催化剂相比,使用本发明催化剂可以获得显著较高的THF选择性。
表
实施例编号 | 催化剂编号 | 4nm<d<300μm的孔体积[cm3/g] | 50nm<d<300μm的孔体积[cm3/g] | d>50nm/d>2nm的大孔比例[%] | T[℃] | SGBL[摩尔%] | STHF[摩尔%] | S其余[摩尔%] |
4 | 1 | 0.392 | 0.233 | 59% | 260 | 0 | 98 | 2 |
5 | 2 | 0.354 | 0.139 | 39% | 250 | 1 | 97 | 2 |
6 | 3 | 0.127 | 0.045 | 35% | 250 | 2 | 96 | 2 |
对比例2 | 对比例1 | 0.187 | 0.007 | 3.7% | 260 | 12 | 78 | 10 |
SXXX=选择性
Claims (10)
1、一种氢化催化剂,它含有氧化铜和至少一种选自Al、Si、Zn、La、Ce、IIIA至VIIIA族元素和IA和IIA族元素的其它金属或其化合物,优选是氧化物,该催化剂具有对于孔直径>50nm的孔体积是≥0.01ml/g,直径>50nm的大孔的孔体积与直径>4nm的孔的总孔体积之比是>10%。
2、根据权利要求1的催化剂,其中其它金属氧化物选自二氧化硅、氧化锌、氧化铝、氧化锆和/或二氧化钛,其中该催化剂特别优选选自氧化铜/氧化铝混合物和氧化铜/氧化锌/氧化铝混合物。
3、根据权利要求1或2的催化剂,其中氧化铜含量是≥10%重量,优选≥25%重量。
4、根据权利要求1-3中任一项的催化剂,其中对于孔直径>100nm的孔体积≥0.025ml/g,特别是对于孔直径>200nm的孔体积≥0.05ml/g。
5、根据权利要求1-4中任一项的催化剂,其中直径>50nm的大孔的孔体积与直径>4nm的孔的总孔体积之比是>10%,优选>20%,特别是>30%。
6、根据权利要求1-5中任一项的催化剂,它是成形体的形式,优选是压片、环、球或挤出物的形式。
7、一种制备根据权利要求1-6中任一项的催化剂的方法,包括使溶于溶剂中的铜化合物在溶解或悬浮于溶剂中的其它金属化合物的存在下和在存在或不存在其它添加剂下,在沉淀剂的作用下沉淀出来,过滤、洗涤、干燥和如果需要的话煅烧该沉淀物,然后使所得的材料成形。
8、根据权利要求7的方法,其中通过以下方式来达到孔隙度:加入成孔剂、添加剂,选择催化剂粉末的适宜粒径分布和孔隙度和/或在原料成形过程中适宜的工艺参数。
9、根据权利要求1-8中任一项的催化剂在使C4-二羧酸和/或其衍生物、优选马来酸酐在气相中氢化形成THF和/或其衍生物中用作催化剂的用途。
10、根据权利要求9的用途,其中氢化反应在150-400℃、优选100-300℃下进行,压力是0.5-100巴,优选1-50巴,特别是<20巴,GHSV是10-50000h-1,优选100-10000h-1,C4-羧酸或其衍生物的浓度是0.2-2%体积。
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CN102617518A (zh) * | 2011-01-27 | 2012-08-01 | 中科合成油技术有限公司 | 顺酐气相加氢一步法制备四氢呋喃 |
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CN106268835A (zh) * | 2015-06-08 | 2017-01-04 | 中国石油化工股份有限公司 | 一种顺丁烯二酸酐加氢制γ-丁内酯的催化剂及其制备方法 |
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DE10124962A1 (de) * | 2001-05-21 | 2002-12-05 | Basf Ag | Katalysatoren für die Reinigung von Ethylen |
DE10313702A1 (de) † | 2003-03-27 | 2004-10-07 | Basf Ag | Katalysator und Verfahren zur Hydrierung von Carbonylverbindungen |
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US7659227B2 (en) | 2006-05-22 | 2010-02-09 | University Of Notre Dame Du Lac | Catalysts for hydrogen production |
JP2010510879A (ja) | 2006-12-01 | 2010-04-08 | ビーエーエスエフ ソシエタス・ヨーロピア | 物質流からcoを除去するための吸着体及びその除去方法 |
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