CN104220411A - 乳酸催化转化成丙烯酸 - Google Patents
乳酸催化转化成丙烯酸 Download PDFInfo
- Publication number
- CN104220411A CN104220411A CN201380019315.4A CN201380019315A CN104220411A CN 104220411 A CN104220411 A CN 104220411A CN 201380019315 A CN201380019315 A CN 201380019315A CN 104220411 A CN104220411 A CN 104220411A
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- Prior art keywords
- catalyzer
- mixed phosphate
- acid
- phosphate salt
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Links
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title abstract description 167
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title abstract description 83
- 239000004310 lactic acid Substances 0.000 title abstract description 82
- 235000014655 lactic acid Nutrition 0.000 title abstract description 82
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title abstract description 44
- 238000006243 chemical reaction Methods 0.000 title abstract description 17
- 230000003197 catalytic effect Effects 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 131
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 64
- 150000003016 phosphoric acids Chemical class 0.000 claims description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 229910002651 NO3 Inorganic materials 0.000 claims description 21
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 14
- 239000000969 carrier Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 25
- 239000000203 mixture Substances 0.000 abstract description 21
- 239000006227 byproduct Substances 0.000 abstract description 20
- 230000018044 dehydration Effects 0.000 abstract description 9
- 238000006297 dehydration reaction Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 34
- 239000000047 product Substances 0.000 description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 235000012239 silicon dioxide Nutrition 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- 239000010453 quartz Substances 0.000 description 20
- 239000008246 gaseous mixture Substances 0.000 description 18
- 235000019260 propionic acid Nutrition 0.000 description 15
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 14
- 230000008859 change Effects 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- 239000010452 phosphate Substances 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 230000009466 transformation Effects 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000007704 transition Effects 0.000 description 10
- 230000006641 stabilisation Effects 0.000 description 9
- 238000011105 stabilization Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910052788 barium Inorganic materials 0.000 description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 7
- 229910001864 baryta Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005480 shot peening Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920000247 superabsorbent polymer Polymers 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- WTVNUJRNSNVFID-UHFFFAOYSA-N 2-hydroxypropanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)C(O)=O WTVNUJRNSNVFID-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 2
- 229940043256 calcium pyrophosphate Drugs 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000012217 deletion Methods 0.000 description 2
- 230000037430 deletion Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 229940107700 pyruvic acid Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 238000004441 surface measurement Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- WMFHUUKYIUOHRA-UHFFFAOYSA-N (3-phenoxyphenyl)methanamine;hydrochloride Chemical compound Cl.NCC1=CC=CC(OC=2C=CC=CC=2)=C1 WMFHUUKYIUOHRA-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020335 Na3 PO4.12H2 O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000000340 Solanum pseudocapsicum Nutrition 0.000 description 1
- 235000001978 Withania somnifera Nutrition 0.000 description 1
- 240000004482 Withania somnifera Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000010829 isocratic elution Methods 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- -1 phosphate salt compound Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012898 sample dilution Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F13/534—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having an inhomogeneous composition through the thickness of the pad
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- 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
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- B01J27/14—Phosphorus; Compounds thereof
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Abstract
本文公开了乳酸催化脱水成丙烯酸,其特征在于乳酸转化率高,对于丙烯酸的选择性高,丙烯酸的收率高,并且相应地对于非期望的副产物的选择性及摩尔收率低。这是用特定类的催化剂实现的,所述催化剂由含金属的磷酸盐的混合物所限定,这些含金属的磷酸盐共同提供具有非常高的碱性密度和低酸性密度的催化剂。此外,据信该催化剂具有长时期的稳定性及活性,这对于现有技术中的此类脱水过程来说是前所未见的。
Description
背景技术
技术领域
本发明一般地涉及乳酸转化成丙烯酸以及适用于此的催化剂。更具体地,本发明涉及乳酸催化脱水成丙烯酸,以及能够实现此目的而不显著地将乳酸转化成非期望的副产物(例如像丙酸和乙酸)的催化剂。
丙烯酸具有多种工业用途,通常以聚合物的形式消耗。继而,这些聚合物常用于生产(除了别的以外)粘合剂、粘结剂、涂料、漆料、抛光剂和超吸收性聚合物,后者用于一次性吸收制品,包括例如尿布和卫生用品。丙烯酸通常由石油源制备。例如,丙烯酸一直通过丙烯的催化氧化制备。由石油源制备丙烯酸的这些及其它方法描述于“Kirk-Othmer Encyclopedia ofChemical Technology,第1卷第342-69页”(第5版,John Wiley&Sons,Inc.,2004)中。
然而,由非基于石油的来源诸如乳酸制备丙烯酸逐渐受到关注。第4,729,978和4,786,756号美国专利一般性地描述了乳酸转化成丙烯酸。这些专利教导到,通过使乳酸和水与浸有磷酸盐(分别如磷酸二氢钾或磷酸氢二钾盐KH2PO4或K2HPO4或者磷酸铝)的金属氧化物载体接触可实现转化。这些浸渍的载体是酸性催化剂,并且至少‘978专利强调了载体表面上的酸性位点的数目和强度似乎影响向丙烯酸的选择性和转化率。
最近的研究进一步集中在对用于将乳酸转化成丙烯酸的酸性催化剂进行改性。这项研究包括有关用磷酸钾盐改性的酸性催化剂(硫酸钙和硫酸铜)的研究以及反应温度和载体进料气体的选择对丙烯酸的转化率和选择性的影响。参见Lin等人(2008)Can.J.Chem.Eng.86:1047-53。然而研究表明,研究人员能够获得的丙烯酸的最佳摩尔收率为63.7%,并且这只是在借助于二氧化碳作为载气的情况下获得的,并且接触时间(88秒)对于任何实用的商业生产过程来说是太高了。更近期的研究表明,磷酸盐和硝酸盐可有利地改变酸性催化剂的表面酸度以抑制乳酸脱羰/脱羧成乙醛,后者常常是非期望的转化副产物。参见Huang等人(2010)Ind.Eng.Chem.Res.49:9082;还参见Weiji等人(2011)ACS Catal.1:32-41。
然而,尽管有这些教导,但所有这项研究的数据仍显示出有高量的非期望副产物,诸如乙醛和丙酸。据信α-羟基基团相对于乳酸上的羧酸根基团的接近程度是产生这些副产物的原因,这些副产物还可能包括一氧化碳、二氧化碳、2,3-戊二酮和乳酸的低聚物。副产物可沉积在催化剂上,导致催化剂的污染以及过早和快速的失活,例如在Lin等人的出版物中所指出的那样。此外,这些副产物一旦沉积,则它们可催化所述过程的非期望的其它反应,诸如聚合反应。
除了沉积在催化剂上之外,这些副产物即使仅以少量存在时也会在例如生产超吸收性聚合物中增加处理丙烯酸(当存在于反应产物流出物中时)的额外成本。并且有关生产这些聚合物的文献中大量叙述了当所生产的丙烯酸当中仅仅存在少量的杂质(如乙酸和丙酸)时将其去除的可能的解决方案,这些解决方案可能会是昂贵的。例如,第6,541,665 B1号美国专利描述了通过结晶、蒸馏和回收来纯化含丙酸、呋喃、水、乙酸和醛类的丙烯酸。‘665专利报告了5阶段结晶(两个纯化阶段和三个汽提阶段)可有效地由(除了别的之外)含2600百万分率(按重量计)(ppm)乙酸和358ppm丙酸的99.48%丙烯酸混合物获得99.94%丙烯酸。类似地,第2011/0257355号美国专利申请公开描述了自来源于甘油脱水/氧化的粗反应混合物(含丙烯酸)以单次结晶去除丙酸以获得99%丙烯酸的方法。有必要采用这些纯化方法以获得在例如生产超吸收性聚合物的下游用途中所必需的高纯丙烯酸。因此,如果可以的话,只要能够采用这些纯化方法的话,消除杂质当然是有价值的。
但是,迄今为止,通过诸如上面所提到的近期文献中描述的方法由乳酸生产丙烯酸导致产生显著量的非期望的副产物,副产物的量确实太高,甚至无法利用前述章节中确定的纯化方法。当然,这些方法中的低丙烯酸选择性还导致原料的损失,并最终导致生产成本增加。因此,将乳酸转化成丙烯酸的这些方法在商业上都不大可行。
发明内容
现已发现,可以在没有上面提到的缺点的情况下以高摩尔收率由乳酸制备丙烯酸。这种丙烯酸的生产方式伴随着乳酸的高转化率、对丙烯酸的高选择性和丙烯酸的高收率,并且相应地对非期望的副产物的低选择性和摩尔收率。这种生产方式是用特定类的催化剂实现的,并且在一定的工艺条件下采用。然而所述方法结果得到的丙烯酸产品足以供常规的工业使用,并且可以不需要目前本领域中所需的复杂纯化。
本文公开了合适催化剂的各种实施例。一个实施例是包括至少两种不同的选自式(I)、(II)、(III)和(IV)的磷酸盐的混合磷酸盐催化剂:
ZH2PO4 (I)
X2-aHPO4, (II)
X3(PO4)2-b (III)
X2+cP2O7, (IV)。
在此实施例中,Z是第I族金属。进一步地,在式(II)至(IV)每个中,每个X独立地为第I族或第II族金属。一些附带条件进一步限定混合磷酸盐催化剂。具体地,在式(II)中,当X是第I族金属时,a是0,并且当X是第II族金属时,a是1。进一步地,在式(III)中,当X是第I族金属时,b是1,并且当X是第II族金属时,b是0。更进一步,在式(IV)中,当X是第I族金属时,c是2,并且当X是第II族金属时,c是0。
混合磷酸盐催化剂的另一实施例还包括至少两种不同的磷酸盐。然而,这里一种磷酸盐为磷酸(H3PO4)与式(V)的硝酸盐的沉淀产物:
X(NO3)2-b (V)。
另一种磷酸盐选自上面给出的式(I)、(II)、(III)和(IV)。式(V)中的变量X和b如上面针对式(III)所定义。更具体地,在式(III)和(V)的每个中,当X是第I族金属时,b是1,并且当X是第II族金属时,b是0。
在另一实施例中,混合磷酸盐催化剂还是包括至少两种不同的磷酸盐。然而这里的至少两种不同的磷酸盐是磷酸(H3PO4)与如上所定义的两种不同的式(V)的硝酸盐的共沉淀的产物。
这些催化剂可用在乳酸转化成丙烯酸的各种实施例中。根据一个实施例,制备丙烯酸的方法包括在足以由乳酸以至少50%的摩尔收率产生丙烯酸的条件下使包括水和乳酸的气态混合物与混合磷酸盐催化剂接触。混合磷酸盐催化剂包含至少两种不同磷酸盐的混合物,并且混合磷酸盐催化剂具有约0.35mmol/m2或更小的表面酸性密度和至少约2mmol/m2的表面碱性密度。
制备丙烯酸的替代实施例包括乳酸的气相催化脱水,方式是使包括乳酸和水的气态混合物与混合磷酸盐催化剂接触,所述混合磷酸盐催化剂包含至少两种不同的选自如上所定义的式(I)、(II)、(III)和(IV)的磷酸盐。制备丙烯酸的另一实施例包括乳酸的气相催化脱水,方式是使包括乳酸和水的气态混合物与混合磷酸盐催化剂接触,所述混合磷酸盐催化剂也包括至少两种不同的磷酸盐。但这里至少一种磷酸盐是磷酸(H3PO4)与上文所定义的式(V)的硝酸盐的沉淀产物,并且另一种磷酸盐选自如上所定义的式(I)、(II)、(III)和(IV)。在制备丙烯酸的另一实施例中,所述方法包括乳酸的气相催化脱水,方式是使包括乳酸和水的气态混合物与混合磷酸盐催化剂接触,所述混合磷酸盐催化剂还是包括至少两种不同的磷酸盐。这里的混合磷酸盐催化剂包含至少两种不同的磷酸盐,所述至少两种不同的磷酸盐是磷酸(H3PO4)与如上所定义的两种不同的式(V)的硝酸盐的共沉淀的产物。
本领域技术人员结合例子、附图及所附权利要求,通过阅读以下的具体实施方式可显而易见本发明的其它特征。
附图说明
为了更完整地理解本发明,应参考以下具体实施方式和唯一的附图,所述附图以图表的方式示出根据下面给出的例子的副产物的组成和乳酸转化成丙烯酸中存在的每种物质的量。
虽然所公开的催化剂及方法容许各种形式的实施例,但在附图中示出了(并且在下文中将描述)本发明的具体实施例,要理解的是所公开的内容旨在为示例性的,并非旨在将本发明限制于本文描述和示出的具体实施例。
具体实施方式
可以在没有本领域中普遍存在的缺点的情况下以高摩尔收率由乳酸制备丙烯酸。这种生产方式伴随着乳酸的高转化率、对丙烯酸的高选择性、丙烯酸的高收率,并且相应地对非期望的副产物的低选择性和摩尔收率。这种生产方式是用特定类的催化剂实现的,并且在一定的工艺条件下采用。然而所述方法结果得到的丙烯酸产品足以供常规的工业使用,并且可以不需要目前本领域中所需的复杂纯化。
催化剂
下面就由乳酸制备丙烯酸来讨论催化剂的功能效力。所述催化剂为具备某些物理特性并且由特定类化学物质所限定的混合磷酸盐催化剂。
混合磷酸盐催化剂的一个实施例包括至少两种不同的选自式(I)、(II)、(III)和(IV)的磷酸盐:
ZH2PO4 (I)
X2-aHPO4, (II)
X3(PO4)2-b (III)
X2+cP2O7, (IV)。
在此实施例中,Z是第I族金属。进一步地,在式(II)至(IV)每个中,每个X独立地为第I族或第II族金属。一些附带条件进一步限定混合磷酸盐催化剂。具体地,在式(II)中,当X是第I族金属时,a是0,并且当X是第II族金属时,a是1。进一步地,在式(III)中,当X是第I族金属时,b是1,并且当X是第II族金属时,b是0。更进一步,在式(IV)中,当X是第I族金属时,c是2,并且当X是第II族金属时,c是0。
本催化剂的某些实施例包括:式(II)的磷酸盐,其中X是钾(K);式(III)的磷酸盐,其中X是钡(Ba);和/或式(IV)的磷酸盐,其中X是钙(Ca)。因此,催化剂可包括K2HPO4和Ba3(PO4)2。作为另外的选择,催化剂可包括K2HPO4和Ca2P2O7。
一般地,这种混合磷酸盐催化剂的制备方式是,简单地通过将至少两种磷酸盐物理混合到一起,并此后煅烧混合物,以及任选进行过筛,以形成适合用于将乳酸转化成丙烯酸的催化剂,如下面进一步详述的那样。
混合磷酸盐催化剂的另一实施例也包括至少两种不同的磷酸盐。然而这里的一种磷酸盐是磷酸(H3PO4)与式(V)的硝酸盐的沉淀产物:
X(NO3)2-b (V)。
另一种磷酸盐选自上面给出的式(I)、(II)、(III)和(IV)。式(V)中的变量X和b如上面针对式(III)所定义。更具体地,在式(III)和(V)每个中,当X是第I族金属时,b是1,并且当X是第II族金属时,b是0。
本催化剂的某些实施例不仅包括上面提到的沉淀产物,而且还包括式(II)的磷酸盐(其中X是钾)和/或式(III)的磷酸盐(其中X是钡)。因此,催化剂可包括K2HPO4和磷酸与Ba(NO3)2的沉淀产物。
一般地,这种混合磷酸盐催化剂的制备方式是,通过将硝酸盐的水溶液与一种或多种磷酸盐混合,并且此后加磷酸并干燥材料的组合,以驱除硝酸并产生含至少两种磷酸盐的催化剂混合产品。在煅烧和任选的过筛之后,混合磷酸盐适合用于将乳酸转化成丙烯酸,如下面进一步详述的那样。
在另一实施例中,混合磷酸盐催化剂还是包括至少两种不同的磷酸盐。然而这里的至少两种不同的磷酸盐是磷酸(H3PO4)与如上所定义的两种不同的式(V)的硝酸盐的共沉淀的产物。
一般地,这种混合磷酸盐催化剂的制备方式是,通过将两种硝酸盐与水混合以形成相同的硝酸盐的水性溶液,并且此后加磷酸并干燥材料的组合,以驱除硝酸并产生含至少两种磷酸盐的催化剂混合产品。在煅烧和任选的过筛之后,混合磷酸盐适合用于将乳酸转化成丙烯酸,如下面进一步详述的那样。
在上述混合磷酸盐催化剂的各种实施例中,不同磷酸盐的金属可以是相同的。作为另外的选择,金属也可以是彼此不同的,但当是这种情况时,则金属优选具有相差30皮米(pm)或更少的原子半径。例如,当金属不同时,则优选它们选自(a)钾和钙,(b)锂(Li)和镁(Mg),(c)钙和钡,(d)钠(Na)和钙,以及(e)钾和锶(Sr)。
当混合磷酸盐催化剂包含两种不同的磷酸盐时,优选两种金属以相对于彼此为约1:9至约9:1的(摩尔)比率存在。例如,当混合磷酸盐催化剂包含磷酸氢二钾(K2HPO4)和作为磷酸(H3PO4)与硝酸钡(Ba(NO3)2)的沉淀产物的磷酸盐时,钾和钡优选以K:Ba为约2:3的摩尔比存在。
混合磷酸盐催化剂还可以包括负载不同磷酸盐的载体。优选地,载体选自高和低表面积的二氧化硅、二氧化硅溶胶、二氧化硅凝胶、氧化铝、氧化铝硅酸盐、碳化硅、硅藻土、二氧化钛、石英、金刚石、碳、氧化锆、氧化镁、氧化铈、氧化铌、以及这些的混合物。更优选地,载体相对于预期接触催化剂的反应混合物是惰性的。因此就本文中明确描述的反应来说,载体优选为低表面积二氧化硅或氧化锆(例如,氧化锆陶瓷喷丸)。当存在载体时,其存在量基于催化剂的总重量为约5重量%至约90重量%。
优选将催化剂在约250℃至约450℃的温度下煅烧约一小时至约四小时。更优选地,将催化剂在450℃下煅烧四小时(每分钟2℃跃变)。必要时可以在类似的条件下使催化剂再生。煅烧之后,优选对催化剂进行过筛以提供更均匀的产品。优选地,将催化剂筛成中值粒度为约100微米(μm)至约200μm。进一步地,优选催化剂颗粒的粒度分布包括小于约3,更优选小于约2,并且最优选小于约1.5的颗粒跨度。如本文所用,术语“中值粒度”是指这样的颗粒的直径,颗粒总体积的50%的直径低于或高于此直径。此中值粒度表示为Dv,0.50。虽然本领域的技术人员已知许多方法和机器可用于将颗粒分成离散的尺寸,但是筛分法是测定粒度和粒度分布的最容易、最便宜和普通的方法之一。测定颗粒粒度分布的替代方法是采用光散射。如本文所用,术语“颗粒跨度”是指给定颗粒样品的统计表示,并且可按如下方式计算。首先,如上所述计算中值粒度Dv,0.50。然后通过类似的方法确定分出10%体积分数的颗粒样品的粒度Dv,0.10,并且然后确定分出90%体积分数的颗粒样品的粒度Dv,0.90。则颗粒跨度等于(Dv,0.90-Dv,0.10)/Dv,0.50。
重要的是,就生产丙烯酸来说,已经确定的是,由于某些物理特性的原因,本文描述的混合磷酸盐催化剂在功能上远优于本领域中任何别的催化剂。具体地,混合磷酸盐催化剂优选具有约0.35毫摩尔/平方米(mmol/m2)或更小,更优选为约0.001mmol/m2至约0.35mmol/m2的表面酸性密度。优选通过直到400℃的氨程序升温脱附法(氨TPD)测量表面酸性密度,以mmol/g表示,并使用通过BET法测得的催化剂表面积(以m2/g表示)转换成mmol/m2。进一步地,混合磷酸盐催化剂优选具有至少约2mmol/m2,更优选为约20mmol/m2至约100mmol/m2,并且甚至更优选为约30mmol/m2至约80mmol/m2的表面碱性密度。优选通过直到400℃的二氧化碳程序升温脱附法(CO2 TPD)测量表面碱性密度,以mmol/g表示,并使用通过BET法测得的催化剂表面积(以m2/g表示)转换成mmol/m2。
制备丙烯酸的方法
上述催化剂的实施例可用于由含乳酸和水的反应混合物制备丙烯酸。这种方法的一个具体的实施例包括在足以由乳酸以至少50%的摩尔收率产生丙烯酸的条件下使包括水和乳酸的气态混合物与混合磷酸盐催化剂接触。混合磷酸盐催化剂包含至少两种不同磷酸盐的混合物,并且混合磷酸盐催化剂具有约0.35mmol/m2或更小的表面酸性密度和至少约2mmol/m2的表面碱性密度。在优选的实施例中,混合磷酸盐催化剂具有约20mmol/m2至约100mmol/m2且甚至更优选为约30mmol/m2至约80mmol/m2的表面碱性密度。在优选的实施例中,所述条件足以由乳酸以至少50%的摩尔收率,更优选至少约70%,并且甚至更优选至少约80%的摩尔收率产生丙烯酸。在其它优选的实施例中,所述条件足以导致对丙烯酸的选择性为至少约65%,更优选为至少约75%,并且甚至更优选为至少约90%。
不受任何理论的约束,据信与混合物的规则基于纯磷酸盐的表面碱性密度值可能预测的情况相比,混合磷酸盐化合物导致表面碱度非常高(即,高碱性催化剂),并且高度碱性的催化剂是高丙烯酸收率、高的乳酸转化率、高的丙烯酸选择性以及本领域中常见的副产物转化的低选择性的原因。之所以如此是因为与酸促过程相关联的反应性中间体得以被避免或减至最少。
接触催化剂的气态混合物优选还包括惰性气体,即在所述方法的条件下另外对反应混合物和催化剂为惰性的气体。优选惰性气体选自氮、氦、氖、氩以及它们的混合物。更优选地,惰性气体选自氮、氦以及它们的混合物。
因此,接触催化剂的气态混合物可包含在催化剂的上游的单独的载气进料以及液体,所述液体由乳酸及在某些实施例中乳酸的衍生物以及丙交酯、乳酸二聚物、乳酸的盐和乳酸烷基酯中的一种或多种的水溶液组成。乳酸衍生物包括乳酸低聚物和乳酸的聚合产物中的一种或多种。然而优选地,所述液体包括基于液体的总重量为约5重量%至约95重量%,更优选为约10重量%至约50重量%,并且甚至更优选为约17重量%至约25重量%的乳酸。还优选的是,基于液体的总重量,液体混合物含有小于约30重量%的乳酸衍生物,更优选小于约10重量%,并且甚至更优选小于约5重量%的乳酸衍生物。
在足以形成接触催化剂的气态混合物的温度下将液体与载气合并。气态混合物接触催化剂的条件优选包括约250℃至约450℃,更优选为约300℃至约375℃,并且甚至更优选为约325℃至约350℃的温度。基于气态混合物的总摩尔数,气态混合物优选包括约5摩尔%或更少,更优选约2.3摩尔%至约3.5摩尔%量的乳酸。可以通过载气的用量来控制乳酸的量。具体地,通过控制气体时空速度(GHSV)可控制接触催化剂的气态混合物中的乳酸的量。因此,所述条件优选包括约2200/小时(h-1)至约7900h-1,更优选约3500h-1的GHSV。
优选在包括石英衬里的内表面的反应器中实施所述方法。作为另外的选择,可以在不锈钢(SS)反应器或由哈氏合金、因科镍合金、硼硅酸盐或人造蓝宝石构造的反应器中实施所述方法。优选反应器具有约50至约100,优选为约75的纵横比(长度/直径)。
由前述实施例可获得的有益效果为副产物的低摩尔收率。例如,所述条件足以由气态混合物中存在的乳酸产生小于约6%,更优选小于约1%摩尔收率的丙酸。类似地,所述条件足以由气态混合物中存在的乳酸产生小于约2%,更优选小于约0.5%摩尔收率的乙酸、丙酮酸、1,2-丙二醇和2,3-戊二酮中的每一种。类似地,所述条件足以由气态混合物中存在的乳酸产生小于约8%,更优选小于约4%,并且甚至更优选小于约3%摩尔收率的乙醛。这些被认为是迄今为止尚达小于的低收率。然而这些有益效果实际上是可获得的,由下文所示例子进一步展示。
制备丙烯酸的替代实施例包括乳酸的气相催化脱水,方式是使包括乳酸和水的气态混合物与混合磷酸盐催化剂接触,所述混合磷酸盐催化剂包含至少两种不同的选自如上所定义的式(I)、(II)、(III)和(IV)的磷酸盐。制备丙烯酸的另一实施例包括乳酸的气相催化脱水,方式是使包括乳酸和水的气态混合物与混合磷酸盐催化剂接触,所述混合磷酸盐催化剂也包括至少两种不同的磷酸盐。但这里至少一种磷酸盐是磷酸(H3PO4)与上文所定义的式(V)的硝酸盐的沉淀产物,并且另一种磷酸盐选自如上所定义的式(I)、(II)、(III)和(IV)。在制备丙烯酸的另一实施例中,所述方法包括乳酸的气相催化脱水,方式是使包括乳酸和水的气态混合物与混合磷酸盐催化剂接触,所述混合磷酸盐催化剂还是包括至少两种不同的磷酸盐。这里的混合磷酸盐催化剂包含至少两种不同的磷酸盐,所述至少两种不同的磷酸盐是磷酸(H3PO4)与如上所定义的两种不同的式(V)的硝酸盐的共沉淀的产物。
实例
给出下述实例是为了举例说明本发明,而不是旨在限制其范围。实例1至4描述根据上述各实施例制备五种不同的混合磷酸盐催化剂。实例5描述不是根据本发明制备催化剂。实例6描述采用实例1至5中所述的催化剂将乳酸转化成丙烯酸的实验室规模实验及其结果。实例7描述根据本发明测定催化剂活性的实验,并列出由该实验获得的数据。实例8描述采用实例1中所述的催化剂将乳酸转化成丙烯酸的实验室规模实验,其中反应器材质有所不同。实例9描述在不存在催化剂的情况下进行的实验,用以显示石英反应器中的进料稳定化(相对于不锈钢反应器。
实例1
在室温下将硝酸钡Ba(NO3)2的水溶液(0.08克/毫升(g/ml)的原液85.36毫升(ml),0.026mol,99.999%,得自Aldrich#202754)加到磷酸氢二钾K2HPO4(1.517克(g),0.0087mol,≥98%,得自Aldrich#P3786)中以得到含钾(K,M1)和钡(Ba,M2)金属的白色浆料,M1:M2摩尔比为40:60。将磷酸H3PO4(85重量%的,2.45ml,d=1.684g/ml,0.036mol,得自Acros#295700010)滴加到浆料中。然后在具有空气流的通风烘箱中将含酸浆料在50℃下缓慢干燥10小时,然后在80℃下缓慢干燥10小时(0.5℃/分钟跃变),直到发生催化剂的完全沉淀。加热在120℃下继续进行2小时(0.5℃/分钟跃变),接着在450℃下煅烧4小时(2℃/分钟跃变)。煅烧后将催化剂过筛成约100mm至约200mm。根据前述程序制备两批这种催化剂。两批催化剂在下文中被称为“催化剂‘A’和催化剂‘B’”。
实例2
将磷酸钠Na3PO4(85.68g,0.522mol,96%的,得自Aldrich,#342483)溶于580ml去离子水,并用浓氢氧化铵(一般来源)将pH调节到由pH计测定为7。将Ba(NO3)2(121.07g,0.463mol,99.999%的,得自Aldrich#202754)溶于1220ml去离子水以形成硝酸钡溶液。在35℃下加热辅助溶解。将硝酸钡溶液滴加到Na3PO4溶液中,同时搅拌并加热到60℃,在添加期间形成白色浆料。持续监测pH,并且滴加浓氢氧化铵以保持pH 7。在60℃下的加热和搅拌持续60分钟,此时将固体过滤并用去离子水彻底地进行洗涤。将固体悬浮于2L去离子水中,并且再次过滤,并且用去离子水充分洗涤。在通风烘箱中,将滤饼在120℃下干燥5小时(1℃/分钟跃变),接着在350℃下煅烧4小时(2℃/分钟跃变)。煅烧后将磷酸钡过筛成约100mm至约200mm。压迫细粒并根据需要重新过筛。
将所制备的磷酸钡Ba3(PO4)2(13.104g,0.0218mol)与事先过筛成约100mm至约200mm的磷酸氢二钾K2HPO4(1.896g,0.0109mol,得自Fisher#P5240/53)混合以得到含钾(M1)和钡(M2)金属的混合物,M1:M2摩尔比为25:75。手动混合固体并在封闭的瓶中摇动,接着在通风烘箱中在50℃下加热2小时,在80℃下加热(0.5℃/分钟跃变)2小时,然后在120℃下加热2小时(0.5℃/分钟跃变)。此后,将催化剂在450℃下煅烧4小时(0.2℃/分钟跃变)。煅烧后将催化剂重新过筛成约100mm至约200mm。此催化剂在下文中被称为“催化剂‘C’”。
实例3
根据Hong等人Applied Catalysis A:General,2011,396,194-200中描述的方法制备焦磷酸钙(Ca2P2O7)。将水合氯化钙CaCl2·2H2O(39.46g,0.268mol,于100ml去离子水中)的水溶液缓慢地加(7ml/min)到焦磷酸钠Na4P2O7(32.44g,0.122mol,通过在50℃下加热在250ml去离子水中制备)的溶液中,同时在室温下连续搅拌1小时。过滤所得到的白色浆料并在350ml去离子水中分散两次,并且再次过滤以产生滤饼。在具有空气流的通风烘箱中将滤饼在80℃下干燥6小时,接着在500℃下煅烧6小时。将所述催化剂筛分至约100μm至约200μm。
将所制备的焦磷酸钙Ca2P2O7(1.4738g,5.80mmol)与事先过筛成约100mm至约200mm的磷酸二氢钾KH2PO4(0.5262g,3.87mmol,得自Aldrich)混合以得到含钾(M1)和钙(M2)金属的混合物,M1:M2摩尔比为25:75。手动混合固体并在封闭的瓶中摇动,接着根据实例4中描述的程序进行煅烧。煅烧后将催化剂重新过筛成约100mm至约200mm。此催化剂在下文中被称为“催化剂‘D’”。
实例4(比较例)
制备一些另外的催化剂,在本文中被称为催化剂“E”、“F”和“G”,并用于比较的目的,这些催化剂的描述如下:
制备不是根据本发明的磷酸钡催化剂(催化剂“E”)并用于比较的目的。将水合正磷酸钠Na3PO4.12H2O(19.4566g,0.0511mol,≥98%,得自Aldrich#71911)溶于125ml去离子水,并用被加热的磁力搅拌器(IKA RCT)加热到60℃。将Ba(NO3)2(19.8866g,0.0761mol,99.999%的,得自Aldrich)溶于250ml去离子水以形成硝酸钡溶液。在35℃下加热辅助溶解。将硝酸钡溶液滴加到Na3PO4溶液中,同时以每分钟300转(rpm)搅拌并加热到60℃,在添加期间形成白色浆料。使用pH计监测混合物的pH。pH初始为12.68,并在添加硝酸钡溶液后下降到11.82。在60℃下的加热和搅拌持续78分钟,此时将固体过滤。将固体悬浮在250ml去离子水中并再次过滤。将此过程重复五次,直到最终pH低于9以获得滤饼。在通风烘箱中,将滤饼在95℃下干燥1小时,此后在120℃下过夜,接着在450℃炉中煅烧4小时(2℃/分钟跃变)。煅烧后将催化剂过筛成约100mm至约200mm。此催化剂在下文中被称为“催化剂‘E’”。
催化剂“F”为根据Hong等人Applied Catalysis A:General,2011,396,194-200制备的混合磷酸盐催化剂。
催化剂“G”为磷酸钾(K2HPO4),以产品名称“#P3786,≥98%”得自Sigma Aldrich。
实例5
采用催化剂“A”至“K”中的每一种将含乳酸和水的反应混合物转化成丙烯酸。
反应器及分析法
这些转化中的每一者均在流动反应器系统中进行,所述流动反应器系统具有温度和质量流量控制器,并且对其供给单独的液体和气体进料,带有用于混合的区段。将分子氮(N2)连同氦(He)一起送入反应器,添加氦(He)是作为用于气相色谱(GC)分析的内标物。将乳酸水溶液(20重量%的L-乳酸)送到反应器的顶部,同时控制泵压力(~360psi)以克服来自催化剂床的任何压降。使用纵横比(即,长度/直径)为75的不锈钢反应器,并且在一些情况下使用这样的石英反应器。
使用各种催化剂床和气体进料流量,产生一系列空速(本文中列出)。所述反应器流出物还连接至另一个氮气稀释管线,所述管线将流出物稀释两倍。氦气内标将该稀释中的任何变化归一化以供分析目的。冷凝的产物由冷却至6.5℃至10℃之间的液体取样体系收集,同时气态产物聚集于收集小瓶的顶部空间中。使用取样阀和在线气相色谱(GC)分析顶部气态产物。
使进料平衡1小时,之后2.7小时收集液体样品,并且在实验结束时由离线HPLC进行分析。在此期间,由GC将气体产物在线分析两次,并且报导平均值。在以下分析条件下通过Agilent 1200系列HPLC分析液体产物:Supelcogel-H 250毫米(mm)柱,等度洗脱液0.005M H2SO4(水溶液),二极管阵列和折射率(RI)检测器,运行时间:30分钟(min),流量:0.2ml/min,柱温:30℃,RI温度:30℃。使用三个检测器(一个FID检测器和在下文中分别被称为“TCD-A”和“TCD-B”的两个热导检测器“A”和“B”),通过Interscience Compact GC分析气态产物。气体产物按两次顺序GC色谱给出的平均值报导。
TCD-A柱为Rt-Q Bond(Restek,Bellefonte,PA),具有26m的长度和032mm的I.D.,膜厚度为10mm。有2m的前置柱。将压力设为150kPa,将分流流量设为10mL/min。将柱箱温度设为100℃,阀箱温度为50℃。将流量设为5.0mL/min,载气为氦气。TCD-B柱为分子筛MS5A(Restek,Bellefonte,PA),其具有21m的长度和10mm的膜厚度。有2m的前置柱。将压力设为200kPa,将分流流量设为10mL/min。T将柱箱温度设为70℃,阀箱温度为50℃。将流量设为2.0mL/min,载气为氩气。FID柱为RTx-624(Restek,Bellefonte,PA),其具有28m的长度和0.25mm的内径,膜厚度为14mm。有2m的前置柱。将压力设为100kPa,将分流流量设为20mL/min。柱箱温度设为45℃,阀箱温度设为50℃。
基于碳进行气相计算;Nml/min=在标准温度和压力下的流速;RF=响应因子:
CO流出计算基于TCD-B数据,使用He作为内标物:
CO流出(mmol/min)=[(TCD-B CO面积/TCD-B He面积)*(He流入(Nml/min))]/22.4
CO2流出计算基于TCD-A,使用He作为内标物:
CO2流出(mmol/min)=[(TCD-A CO2面积/TCD-B He面积)*(TCD-ARF CO2)*(He流入(Nml/min))]/22.4
使用以下来确定乙醛(AcH)流出,即FID柱中测量的AcH峰面积(FIDAcH面积)、TCD-B柱中测量的He面积(TCD-B He面积)、将FID上的CH4与TCD-B上的He相关联的响应因子(RF CH4/He)、将FID柱上的AcH与CH4相关联的相对响应因子(RRF AcH/CH4)、每个反应器的内标物He流量(He流入)、乙醛的碳数目(2)和理想气体转换因子(22.4):
乙醛(AcH)GC流出(mmol/min)=[(FID AcH面积/TCD-B He面积)*(RFCH4/He)*(RRF AcH/CH4)*(He流入(Nml/min)]/(2*22.4)
使用HPLC面积进行液相计算:
产物流出(mol/min)=[(HPLC面积/HPLC RF(g-1))/HPLC采集时间(min)]*[样品稀释度/HPLC注射体积]*[样品重量(g)/产物MW(g/mol)]
液体质量平衡(%)=[液体产物重量/LA重量于]*100
基于总碳计算总流出:
总流出(mol/min):(2/3)*[C2H4流出(mol/min)]+(2/3)*[C2H6流出(mol/min)]+[C3H6流出(mol/min)]+[C3H8流出(mol/min)]+(2/3)*[AcH流出(mol/min)]+(4/3)*[C4流出(mol/min)]+[LA流出(mol/min)]+[丙酮酸流出(mol/min)]+(2/3)*[乙酸流出(mol/min)]+[1,2-丙二醇流出(mol/min)]+[PA流出(mol/min)]+[AA流出(mol/min)]+(5/3)*[2,3-戊二酮流出(mol/min)]+(1/3)*[CO流出(mol/min)]+(1/3)*[CO2流出(mol/min)]
转化率(%)=[LA流入(mol/min)-LA流出(mol/min)]/[LA流入(mol/min)]*100
收率(%)=[产物流出(mol/min)/LA流入(mol/min)]*100
总摩尔平衡或TMB(%)=[总流出(mol/min)/LA流入(mol/min)]*100
注意在收率计算中考虑了进料及产物密度。修正丙烯酸收率以考虑可变的流量。在大多数情况下,这种变化是±5%:
对于TMB修正丙烯酸(AA)收率以考虑反应器中略高或略低的流量。
修正到TMB的AA收率(%):[AA收率/总摩尔平衡]*100
选择性(%)=[收率/转化率]*100
GHSV=[总气体流速/催化剂床体积]。
根据ASTM D 4820-99测定BET表面积。
在AutoChem II 2920化学吸附分析仪(Micromeritics,Norcross,GA)上进行程序升温脱附(TPD)以获得催化剂的酸性和碱性位点。在He下将样品在400℃下预处理30分钟。在40℃下进行30分钟CO2吸附。在40℃下进行30分钟CO2物理脱附。NH3吸附在120℃下进行30分钟。CO2和NH3化学脱附使温度以10℃/min跃变到400℃,并将样品保持于400℃达30分钟。
反应器进料。
将来源于生物质的乳酸(88重量%,得自Purac(Lincolnshire,IL))的溶液(113.6g)溶于蒸馏水(386.4g)以得到具有预计的20重量%的乳酸浓度的溶液。将此溶液在100℃下回流30小时。使所得混合物冷却,并且经由HPLC(上述),相对于已知重量的标准物进行分析。
实验结果
下表5给出用每种催化剂进行反应时的GHSV。所有列出的收率均为摩尔收率(除非另外指出)并且是在222分钟的反应时间过后测定的。在气相中进行这些反应,并且除另指出外,使用在350℃下操作的石英反应器,没有载体(填料)。表中,“LA”指乳酸;“AA”指丙烯酸;“AA收率”指自乳酸的丙烯酸的摩尔收率;“PA收率”指自乳酸的丙酸的摩尔收率;并且“N.D.”表示该值未测定。
表1
用催化剂“G”进行的实验是在不锈钢反应器中进行的。用催化剂“F”进行的实验中的反应器温度为400℃。表中列出的有关催化剂“F”的特性(BET、表面碱性和酸性密度)的数据得自Hong等人.AppliedCatalysis A:General,2011,396,194–200。
由表5中的结果可方便地比较使用根据本发明的催化剂(即,催化剂“A”至“D”)和使用不是根据本发明的催化剂(即,催化剂“E”至“G”)时从乳酸到丙烯酸的转化率。除其它方面之外,在相同或类似的反应条件下,与任何其它的催化剂(即,催化剂“E”至“G”)相比,根据本发明的催化剂(即,催化剂“A”至“D”)将更多的乳酸转化成丙烯酸。进一步地,在相同或类似的反应条件下,根据本发明的催化剂导致对丙烯酸的选择性远高于不是根据本发明的催化剂(即,催化剂“E”至“G”)的情况,而对丙酸的选择性远低于后者的情况。在唯一的附图中相对于其它杂质进一步示出了选择性。催化剂“A”至“D”在被认为是进料稳定化所必需的这些高的空速下也具有较好的性能。催化剂“G”或K2HPO4具有比催化剂“A”至“D”低的选择性,表明钡和钾的存在对于高丙烯酸选择性来说是必要的。
上表5给出了五种催化剂的特性,并且方便地比较了根据本发明的催化剂(即,催化剂“A”和“B”)、一些不是根据本发明的催化剂(即,催化剂“E”至“G”)的表面积、表面碱性密度和表面酸性密度。根据本发明的催化剂具有的碱性密度值远高于单独的催化剂“E”的情况。类似地,根据本发明的催化剂“A”和“B”具有的表面酸性密度值类似于催化剂“E”的情况。但是,根据本发明的混合磷酸盐催化剂相对于相同密度的单一磷酸盐催化剂(例如,催化剂“E”)而言有意外高的碱度提高,据信这导致了乳酸转化率以及自乳酸的丙烯酸的选择性和收率提高。换言之,数据反映了具有高表面碱性密度的催化剂性能优于碱性密度较低的催化剂。虽然对催化剂“A”和“B”观察到了相同的选择性,但观察到的转化率有差异。据信该差异原因在于每单位面积上的碱性位点的数目,催化剂“B”的较低。
实例6
进行实验以测定根据本发明的催化剂的活性。具体地,在实例6中给出的条件下使催化剂“B”经受21.6小时的反应时间。所得到的数据列于下表6中,其中丙烯酸收率和选择性被修正到TMB,并且其中在表中,“转化”指转化率,“选择”指选择性。
表2
数据表明,催化剂稳定至少21.6小时,能够说的是,催化剂随着时间的推移似乎不会在丙烯酸收率和选择性方面有显著或不利的改变,并且类似地似乎不会在针对非期望的副产物诸如丙酸、乙酸、乙醛和二氧化碳的选择性方面出现劣化。
实例7
考虑反应器材料对乳酸向丙烯酸转化的影响,进行实验。所有试验均采用相同的反应器构造进行,但仅通过使用石英衬里的反应器或不锈钢(316)反应器而改变条件。不使用惰性填料,将反应器温度保持在350℃,并且每次实验在3,438h-1 GHSV下运转反应器。
表3
上表7中列出的数据表明反应器成分对进料稳定化可能是重要的,尽管使用石英或不锈钢也都观察到了良好的收率。数据进一步表明,在使乳酸进料稳定化而防止其分解成诸如低聚的产物方面,两种类型反应器之间的石英反应器性能较好,从而能够实现优异的催化剂性能。使用石英,虽然对催化剂“A”和“B”观察到了相同的选择性,但观察到的转化率有差异。再次地,这被认为原因在于每单位面积上的碱性位点的数目,对于催化剂“B”,其导致催化剂载量的有效降低。在不锈钢反应器中催化剂“A”和“B”性能差异被认为是由于可变的进料分解的原因。
实例8
不存在催化剂的实验进一步展示石英反应器中给料稳定性的效应。在不锈钢和石英反应器中,将空反应器与用熔融二氧化硅(SiO2)(得自SigmaAldrich(St.Louis,MO)和氧化锆陶瓷喷丸(得自Saint Gobain Zirpro(Le PontetCedex,France)填充的反应器进行比较。
表4
上表8中列出的数据表明,在高的空速下观察到非常少的气态副产物。因此可确定的是,使用石英反应器使两个重要的副反应最小化:乳酸低聚和还原成丙酸。这对于评价催化剂(这里是催化剂“A”和“B”)的真实活性是重要的。
给出以上描述仅用于帮助更清楚地理解,并且不应从中理解为不必要的限制,因为本发明范围内的修改对本领域普通技术人员而言是显而易见的。
实验结果
下表5给出用每种催化剂进行反应时的GHSV。所有列出的收率均为摩尔收率(除另指出外)并且是在222分钟的反应时间过后测定的。在气相中进行这些反应,并且除另指出外,使用在350℃下操作的石英反应器,没有载体(填料)。表中,“LA”指乳酸;“AA”指丙烯酸;“AA收率”指自乳酸的丙烯酸的摩尔收率;“PA收率”指自乳酸的丙酸的摩尔收率;并且“N.D.”表示该值未测定。
表5
用催化剂“G”进行的实验是在不锈钢反应器中进行的。用催化剂“F”进行的实验中的反应器温度为400℃。表中列出的有关催化剂“F”的特性(BET、表面碱性和酸性密度)的数据得自Hong等人Applied CatalysisA:General,2011,396,194–200。
由表5中的结果可方便地比较使用根据本发明的催化剂(即,催化剂“A”至“D”)使用不是根据本发明的催化剂(即,催化剂“E”至“G”)时从乳酸到丙烯酸的转化率。除其它方面之外,在相同或类似的反应条件下,与任何其它的催化剂(即,催化剂“E”至“G”)相比,根据本发明的催化剂(即,催化剂“A”至“D”)将更多的乳酸转化成丙烯酸。进一步地,在相同或类似的反应条件下,根据本发明的催化剂导致对丙烯酸的选择性远高于不是根据本发明的催化剂(即,催化剂“E”至“G”)的情况,而对丙酸的选择性远低于后者的情况。在唯一的附图中相对于其它杂质进一步示出了选择性。催化剂“A”至“D”在被认为是进料稳定化所必需的这些高的空速下也具有较好的性能。催化剂“G”或K2HPO4具有比催化剂“A”至“D”低的选择性,表明钡和钾的存在对于高丙烯酸选择性来说是必要的。
上表5给出了五种催化剂的特性,并且方便地比较了根据本发明的催化剂(即,催化剂“A”和“B”)、一些不是根据本发明的催化剂(即,催化剂“E”至“G”)的表面积、表面碱性密度和表面酸性密度。根据本发明的催化剂具有的碱性密度值远高于单独的催化剂“E”的情况。类似地,根据本发明的催化剂“A”和“B”具有的表面酸性密度值类似于催化剂“E”的情况。但是,根据本发明的混合磷酸盐催化剂相对于相同密度的单一磷酸盐催化剂(例如,催化剂“E”)而言有意外高的碱度提高,据信这导致了乳酸转化率以及自乳酸的丙烯酸的选择性和收率提高。换言之,数据反映了具有高表面碱性密度的催化剂性能优于碱性密度较低的催化剂。虽然对催化剂“A”和“B”观察到了相同的选择性,但观察到的转化率有差异。据信该差异原因在于每单位面积上的碱性位点的数目,催化剂“B”的较低。
实例6
进行实验以测定根据本发明的催化剂的活性。具体地,在实例6中给出的条件下使催化剂“B”经受21.6小时的反应时间。所得到的数据列于下表6中,其中丙烯酸收率和选择性被修正到TMB,并且其中在表中,“转化”指转化率,“选择”指选择性。
表6
数据表明,催化剂稳定至少21.6小时,能够说的是,催化剂随着时间的推移似乎不会在丙烯酸收率和选择性方面有显著或不利的改变,并且类似地似乎不会在针对非期望的副产物(如丙酸、乙酸、乙醛和二氧化碳)的选择性方面出现劣化。
实例7
考虑反应器材料对乳酸向丙烯酸转化的影响,进行实验。所有试验均采用相同的反应器构造进行,但仅通过使用石英衬里的反应器或不锈钢(316)反应器而改变条件。不使用惰性填料,将反应器温度保持在350℃,并且每次实验在3,438h-1 GHSV下运转反应器。
表7
上表7中列出的数据表明反应器成分对进料稳定化可能是重要的,尽管使用石英或不锈钢也都观察到了良好的收率。数据进一步表明,在使乳酸进料稳定化而防止其分解成诸如低聚的产物方面,两种类型反应器之间的石英反应器性能较好,从而能够实现优异的催化剂性能。使用石英,虽然对催化剂“A”和“B”观察到了相同的选择性,但观察到的转化率有差异。再次地,这被认为原因在于每单位面积上的碱性位点的数目,对于催化剂“B”,其导致催化剂载量的有效降低。在不锈钢反应器中催化剂“A”和“B”性能差异被认为是由于可变的进料分解的原因。
实例8
不存在催化剂的实验进一步展示石英反应器中给料稳定性的效应。在不锈钢和石英反应器中,将空反应器与用熔融二氧化硅(SiO2)(得自SigmaAldrich(St.Louis,MO)和氧化锆陶瓷喷丸(得自Saint Gobain Zirpro(Le PontetCedex,France)填充的反应器进行比较。
表8
上表8中列出的数据表明,在高的空速下观察到非常少的气态副产物。因此可确定的是,使用石英反应器使两个重要的副反应最小化:乳酸低聚和还原成丙酸。这对于评价催化剂(这里是催化剂“A”和“B”)的真实活性是重要的。
给出以上描述仅用于理解清楚,并且不应从中理解为不必要的限制,因为本发明范围内的修改对于本领域普通技术人员而言是显而易见的。
本文所公开的量纲和数值不应被理解为严格限于所述确切数值。相反,除非另外指明,每个上述量纲旨在表示所述值以及该值附近的函数等效范围。例如,所公开的量纲“40mm”旨在表示“约40mm”。
除非明确地不包括在内或换句话讲限制,本文所引用的每篇文献,包括任何交叉引用的或相关的专利或专利申请,均特此以引用方式全文并入本文。任何文献的引用不是对其作为本文所公开的或受权利要求书保护的任何发明的现有技术,或者其单独地或者与任何其它参考文献的任何组合,或者参考、提出、建议或公开任何此类发明的认可。此外,当本发明中术语的任何含义或定义与以引用方式并入的文件中术语的任何含义或定义矛盾时,应当服从在本发明中赋予该术语的含义或定义。
尽管已用具体实施例来说明和描述了本发明,但是对于那些本领域的技术人员显而易见的是,在不背离本发明的实质和范围的情况下可作出许多其它的更改和修改。因此,随附权利要求书旨在涵盖本发明范围内的所有这些改变和变型。
权利要求书(按照条约第19条的修改)
1.一种混合磷酸盐催化剂,其包含至少两种不同的选自式(I)、(II)、(III)
和(IV)的磷酸盐:
ZH2PO4 (I)
X2-a HPO4, (II)
X3(PO4)2-b (III)
X2+cP2O7, (IV)
其中Z是第I族金属,并且其中在式(II)至(IV)的每个中,每个X独立地为第I族或第II族金属,附带条件如下:
在式(II)中,当X是第I族金属时,a是0,并且当X是第II族金属时,a是1;
在式(III)中,当X是第I族金属时,b是1,并且当X是第II族金属时,b是0;并且,
在式(IV)中,当X是第I族金属时,c是2,并且当X是第II族金属时,c是0;并且进一步地,其中所述至少两种不同的磷酸盐包含以相 对于彼此为约1:9至约9:1的摩尔比存在的两种金属。
2.根据权利要求1所述的混合磷酸盐催化剂,其中所述至少两种不同的磷酸盐包括K2HPO4和Ba3(PO4)2。
3.根据权利要求1所述的混合磷酸盐催化剂,其中所述至少两种不同的磷酸盐包括K2HPO4和Ca2P2O7。
4.(删除)。
5.根据权利要求1所述的混合磷酸盐催化剂,其中所述催化剂已在约250℃至约450℃的温度下煅烧约一小时至约四小时。
6.根据权利要求1所述的混合磷酸盐催化剂,其还包含负载所述至少两种不同磷酸盐的载体。
7.根据权利要求1所述的混合磷酸盐催化剂,其具有约0.35毫摩尔/平方米(mmol/m2)或更小的表面酸性密度。
8.根据权利要求1所述的混合磷酸盐催化剂,其具有至少约2mmol/m2的表面碱性密度。
9.根据权利要求1所述的混合磷酸盐催化剂,其中一种磷酸盐为磷酸(H3PO4)与式(V)的硝酸盐的沉淀产物:
X(NO3)2-b (V),
并且其中另一种磷酸盐选自所述式(I)、(II)、(III)和(IV)。
10.根据权利要求9所述的混合磷酸盐催化剂,其中所述至少两种不同的磷酸盐包括K2HPO4和磷酸与Ba(NO3)2的沉淀产物。
11.(删除)。
12.根据权利要求9所述的混合磷酸盐催化剂,其中所述催化剂已在约250℃至约450℃的温度下煅烧约一小时至约四小时。
13.根据权利要求9所述的混合磷酸盐催化剂,其还包含负载所述至少两种不同磷酸盐的载体。
14.根据权利要求9所述的混合磷酸盐催化剂,其具有约0.35mmol/m2或更小的表面酸性密度。
15.根据权利要求9所述的混合磷酸盐催化剂,其具有至少约2mmol/m2的表面碱性密度。
Claims (15)
1.一种混合磷酸盐催化剂,其包含至少两种不同的选自式(I)、(II)、(III)
和(IV)的磷酸盐:
ZH2PO4 (I)
X2-aHPO4, (II)
X3(PO4)2-b (III)
X2+cP2O7, (IV)
其中Z是第I族金属,并且其中在式(II)至(IV)每个中,每个X独立地为第I族或第II族金属,附带条件如下:
在式(II)中,当X是第I族金属时,a是0,并且当X是第II族金属时,a是1;
在式(III)中,当X是第I族金属时,b是1,并且当X是第II族金属时,b是0;并且,
在式(IV)中,当X是第I族金属时,c是2,并且当X是第II族金属时,c是0。
2.根据权利要求1所述的混合磷酸盐催化剂,其中所述至少两种不同的磷酸盐包括K2HPO4和Ba3(PO4)2。
3.根据权利要求1所述的混合磷酸盐催化剂,其中所述至少两种不同的磷酸盐包括K2HPO4和Ca2P2O7。
4.根据权利要求1所述的混合磷酸盐催化剂,其中所述至少两种不同的磷酸盐包含以相对于彼此为约1:9至约9:1的摩尔比存在的两种金属。
5.根据权利要求1所述的混合磷酸盐催化剂,其中所述催化剂已在约250℃至约450℃的温度下煅烧约一小时至约四小时。
6.根据权利要求1所述的混合磷酸盐催化剂,其还包含负载所述至少两种不同磷酸盐的载体。
7.根据权利要求1所述的混合磷酸盐催化剂,其具有约0.35毫摩尔/平方米(mmol/m2)或更小的表面酸性密度。
8.根据权利要求1所述的混合磷酸盐催化剂,其具有至少约2mmol/m2的表面碱性密度。
9.根据权利要求1所述的混合磷酸盐催化剂,其中一种磷酸盐为磷酸((H3PO4)与式(V)的硝酸盐的沉淀产物:
X(NO3)2-b (V),
并且其中另一种磷酸盐选自所述式(I)、(II)、(III)和(IV)。
10.根据权利要求9所述的混合磷酸盐催化剂,其中所述至少两种不同的磷酸盐包括K2HPO4和磷酸与Ba(NO3)2的沉淀产物。
11.根据权利要求9所述的混合磷酸盐催化剂,其中所述至少两种不同的磷酸盐包含以相对于彼此为约1:9至约9:1的摩尔比存在的两种金属。
12.根据权利要求9所述的混合磷酸盐催化剂,其中所述催化剂已在约250℃至约450℃的温度下煅烧约一小时至约四小时。
13.根据权利要求9所述的混合磷酸盐催化剂,其还包含负载所述至少两种不同磷酸盐的载体。
14.根据权利要求9所述的混合磷酸盐催化剂,其具有约0.35mmol/m2或更小的表面酸性密度。
15.根据权利要求9所述的混合磷酸盐催化剂,其具有至少约2mmol/m2的表面碱性密度。
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