CN105612000A - 相互酯化催化剂和方法 - Google Patents
相互酯化催化剂和方法 Download PDFInfo
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- CN105612000A CN105612000A CN201480047732.4A CN201480047732A CN105612000A CN 105612000 A CN105612000 A CN 105612000A CN 201480047732 A CN201480047732 A CN 201480047732A CN 105612000 A CN105612000 A CN 105612000A
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- catalyst
- ester
- oxide
- calcium
- metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000009884 interesterification Methods 0.000 title claims description 32
- 230000008569 process Effects 0.000 title abstract description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000292 calcium oxide Substances 0.000 claims abstract description 40
- 150000002148 esters Chemical class 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 31
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 ester compounds Chemical class 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000395 magnesium oxide Substances 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 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 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 150000003626 triacylglycerols Chemical group 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 33
- 239000007787 solid Substances 0.000 description 29
- 239000002243 precursor Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- 239000003921 oil Substances 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 15
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 14
- 238000001354 calcination Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000000344 soap Substances 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003549 soybean oil Substances 0.000 description 7
- 235000012424 soybean oil Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 239000003925 fat Substances 0.000 description 6
- 235000019197 fats Nutrition 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- FETSQPAGYOVAQU-UHFFFAOYSA-N glyceryl palmitostearate Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O FETSQPAGYOVAQU-UHFFFAOYSA-N 0.000 description 5
- 229940046813 glyceryl palmitostearate Drugs 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000001639 calcium acetate Substances 0.000 description 4
- 229960005147 calcium acetate Drugs 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- 229940043430 calcium compound Drugs 0.000 description 4
- 150000001674 calcium compounds Chemical class 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000008157 edible vegetable oil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910003023 Mg-Al Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 150000002194 fatty esters Chemical class 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003346 palm kernel oil Substances 0.000 description 2
- 235000019865 palm kernel oil Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910002969 CaMnO3 Inorganic materials 0.000 description 1
- 208000004434 Calcinosis Diseases 0.000 description 1
- OYPRJOBELJOOCE-IGMARMGPSA-N Calcium-40 Chemical compound [40Ca] OYPRJOBELJOOCE-IGMARMGPSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910002226 La2O2 Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910003387 SrMnO3 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
一种由至少两种不同的酯化合物的混合物来生产酯产物的方法,其包括步骤:将至少两种不同的起始酯化合物混合在一起,以形成第一酯混合物;和将所述第一酯混合物与包含30-60%的氧化钙和至少一种第二金属氧化物的催化剂在搅拌下在至少180℃的温度接触至少1小时的时间,以形成熔点低于所述第一酯混合物的熔点的第二酯混合物。
Description
本发明涉及用于化学转化,特别是用在可用于生产可食用脂肪和油的酯化方法中的催化剂。
氢化、分馏和相互酯化是可用于改变食用油的性质,因此使它们适用于更宽范围的产品和应用的方法。氢化传统上是最流行的方法,但是甘油三酯的部分氢化会导致不想要的副反应,并且这些副反应导致形成了成分脂肪酸的反式异构体。这些所谓的反式脂肪与多种人类健康问题包括冠心病相关联。
相互酯化是在催化剂存在下,将酰基在酯例如甘油三酯分子之间转移的方法。它典型地用油的混合物:一种饱和的和一种不饱和的,在催化剂例如甲醇钠存在下进行。它是一种吸引人的氢化的替代选项,因为它不涉及脂肪酸链的化学改变,因此不产生反式异构体。许多问题来自于甲醇钠的使用;例如,在反应后不能回收催化剂,并且在从油中除去废水的过程中产生了大量废水。另外,甲醇钠对于游离脂肪酸和水非常敏感,这意味着该反应可以仅在高度精制的原料中进行,否则会发生酯水解和皂形成(皂化)。
将非均相催化剂用于这种方法将克服使用甲醇钠的一些问题,因为该催化剂会更易于从反应产物回收。US6072064描述了将包含第1A族和2A族金属氧化物的混合物的非均相催化剂用于甘油三酯的催化相互酯化,其中该氧化物中的至少一种的光学碱度是至少0.5。虽然这些催化剂看起来有效,但是我们已经发现它们在反应过程中易于形成金属皂,结果损害了它们的复用性。本发明的一个目标是提供一种催化剂和相互酯化方法,其克服了现有技术中所遇到的一些问题。
根据本发明,我们提供了一种催化剂,其包含30-60重量%(wt%)的氧化钙和40-70重量%的氧化镁。
根据本发明,一种由至少两种不同的酯化合物的混合物来生产酯产物的方法,其包括步骤:
a)将至少两种不同的起始酯化合物混合在一起,以形成第一酯混合物;和
b)使所述第一酯混合物与包含30-60%的氧化钙和至少一种第二金属氧化物的催化剂接触,以形成熔点低于所述第一酯混合物的熔点的第二酯混合物。
本发明的方法是一种相互酯化方法,其中一种酯的酰基与不同酯的酰基交换,以形成两种酯,其不同于起始的两种酯。当该起始酯中的至少一种是甘油三酯时,相互酯化产生具有羰基残基链的产物甘油三酯,其不同于起始酯的甘油三酯链,这产生了熔点不同于起始原料的产物。在本发明的一种优选的方法中,该起始酯化合物中的至少一种包括甘油三酯,其优选是植物油或动物脂肪或者其衍生物。优选该起始酯化合物中的至少一种包括C12-C24羧酸的酯。合适的起始原料包括棕榈油、大豆油、棕榈仁油、硬脂酸甘油酯例如棕榈仁硬脂酸甘油酯、油酸甘油脂例如棕榈仁油酸甘油脂、椰子油、鱼油及其衍生物。
相互酯化需要至少两种不同的酯起始化合物,不过可以使用多于两种的酯。该至少两种起始酯可以在与催化剂接触之前或者在所述接触过程中进行混合。例如,该催化剂可以在与其他酯化合物混合之前,与该起始酯化合物中的一种或多种进行混合。具体地,催化剂可以预分散在一种起始酯化合物中。在这种形式中,催化剂分散在其中的酯化合物优选在高至至少40-50℃的温度是固体材料,由此可以保护催化剂在用于反应中之前与空气接触。通过分散在脂肪或蜡状固体中来包封催化剂颗粒或粉末,是一种已知的保护催化剂的方法,特别是用于加工食用油和脂肪的催化剂。在这种情况中,为了用于本发明的方法,包封物质优选包含起始酯化合物。
在本专利说明书中,除非另外说明,全部催化剂成分的百分比指的是基于催化剂总质量的重量%(wt%)。用于本发明方法的催化剂包含30-60wt%的氧化钙,更优选35-55wt%的氧化钙。该催化剂进一步包含至少一种第二金属氧化物,优选40-70%的所述第二金属氧化物。合适的第二金属氧化物包括其他第2A族金属特别是镁的氧化物;过渡金属例如锰和锆的氧化物;氧化镧、二氧化硅、氧化铝和铝酸盐,例如铝酸锂。用于本发明方法的一种优选的催化剂包含30-60%的氧化钙和40-70%的氧化镁。催化剂可以由或者基本上由氧化钙和氧化镁和选自以下的任选的成分组成:碱金属、造粒助剂、润滑剂、粘结剂、压制助剂或者可用于形成成形催化剂颗粒的其他添加剂。CN101108350描述了一种用于合成气蒸汽重整的催化剂,其中核载体颗粒由氧化钙、氧化镁和氧化铝复合物形成,该复合物然后用铝酸镧涂覆,和用作用于镍和稀土催化剂的催化剂载体。本发明的催化剂不包括这样的催化剂,其中使用氧化钙和氧化镁来形成核、载体或承载体,无论涂覆还是未涂覆,其上沉积活性金属例如镍和稀土元素。本发明的催化剂包含30-60%的氧化钙和40-70%的氧化镁作为活性催化组分。
催化剂可以另外包含碱金属,优选钠或钾。我们已经发现,含有至多5%碱金属的催化剂会是有利的。用于本发明方法的一种特别优选的催化剂包含30-60%的氧化钙、40-70%的氧化镁和任选地至多5%的钠或钾,或者基本上由其组成。
为了用于脂肪酯的相互酯化,优选催化剂的表面积小于20m2/g,更优选≤10m2/g,特别是≤5m2/g。我们已经发现,更大的表面积可以增加反应中形成金属皂的倾向。为了产生可接受活性的催化剂,我们优选表面积是至少1m2/g,更优选至少2m2/g。
催化剂可以通过通常用于催化剂制备领域的多种不同类型的方法来制备。这样的方法包括浸渍和沉淀。氧化钙是固体材料,其与水和二氧化碳组合,以形成碳酸钙和氢氧化钙。为了形成包含高比例氧化钙的材料,必须在至少650℃(优选700℃以上)的温度在不存在氧和二氧化碳的情况下,处理氧化钙或其前体(例如硝酸钙、碳酸钙、乙酸钙或氢氧化钙)足够的时间,以将该前体或其他钙化合物完全地或部分地转化成氧化钙。由此形成的氧化钙然后应当冷却和储存,不与氧和二氧化碳接触。催化剂可以通过浸渍来制备,用氧化钙的前体的溶液浸渍第二金属氧化物的固体颗粒。可选地,可以用第二金属氧化物的前体的溶液浸渍氧化钙的固体前体。我们用前体表示钙或第二金属的化合物,其通过施加热而转化成氧化物。合适的前体,包括硝酸钙、硝酸镁和有机盐例如乙酸钙,可溶于水中以生产用于浸渍的水溶液。
催化剂可以通过不同方式的沉淀来制备。在每种情况中,使用可溶性钙化合物的溶液来沉淀氧化钙的固体前体。例如,硝酸钙或乙酸钙的溶液可以与碱例如碱金属碳酸盐或氢氧化物的溶液混合,以使氢氧化钙或碳酸钙沉淀。沉淀的固体钙化合物在煅烧步骤中转化成氧化钙。催化剂可以通过前体钙化合物与第二金属氧化物的前体的共沉淀来制备。在这种方法中,钙和第二金属的可溶性前体化合物(例如硝酸镁)的溶液一起与碱溶液接触,以使钙和第二金属的碱式盐的混合物沉淀。可选地,可以使用沉积-沉淀方法,其中可溶性钙前体的溶液与碱溶液在第二金属氧化物的固体颗粒(或其固体前体)的存在下接触。我们用固体前体表示通过热的作用而转化成第二金属氧化物的固体化合物。该转化通常在煅烧步骤中进行。全部这些沉淀方法通常是催化剂制备领域中已知的和使用的。
可选地,催化剂可以通过将氧化钙的固体颗粒或其固体前体与第二金属氧化物的固体颗粒或其固体前体混合在一起来制备。我们已经发现,一种有效的制备方法包括步骤:将氧化钙的固体颗粒或其固体前体与第二金属氧化物的固体颗粒或其固体前体与液体混合在一起,以形成浆料,然后干燥该浆料以形成混合固体的颗粒。优选在这种制备方法中使用快速干燥方法例如喷雾干燥或冷冻干燥。然后在煅烧步骤中将所形成的固体化合物转化成氧化物。固体钙和第二金属化合物的浆料可以任选地在干燥混合物之前,在研磨、碾磨或能量混合过程中施以机械能。
作为仍然进一步可选的催化剂制备方法,可以使含有钙化合物和第二金属化合物的可溶性前体的溶液干燥,以形成混合固体。快速干燥方法例如喷雾干燥或冷冻干燥方便地用于这种方法中。然后在煅烧步骤中将所形成的固体化合物转化成氧化物。
催化剂可以在浆料相方法中以粉末形式使用,或者它可以形成适用于固定床反应器中的颗粒。为了用于浆料相方法,优选提供具有一定粒度分布的催化剂颗粒,以使得d50处于0.5-50微米,特别是10-40微米的范围。对于浆料相方法的一个重要考虑是当反应完成时,颗粒必须与反应产物分离。分离通常通过过滤来完成,因此颗粒应当这样的粒度和粒度分布,以能够实现从反应介质中快速和完全的过滤。
本发明的催化剂可以包括成形颗粒,其适用于催化剂床中,即所谓的“固定床”方法。这样的颗粒通常具有大于约0.5mm,特别是大于约1mm的最小尺寸,并且尺寸范围可以是1mm-50mm或更大。固定床催化剂颗粒可以具有多种形状,包括球、环、圆柱、叶形圆柱、粒料、小片等,并且可以通过制片、挤出、造粒、涂覆到核上或者通过本领域技术人员已知的方法的其他模制形式来形成。将催化剂形成成形颗粒的方法可以包括压制和/或预压制步骤。预压制步骤可以用于改进用于形成方法的催化剂粉末的流动特性。形成方法可以包括碾磨、轧制、冲压、研磨、筛分和/或混合步骤。粘结剂、润滑剂、压制助剂或其他添加剂可以添加到催化剂或者与催化剂混合,以形成成形催化剂颗粒。例如粘结剂可以以等价于约0.1-10重量%,例如约1重量%的量添加。合适的粘结剂的例子包括硬脂酸镁和石墨。
相互酯化反应优选在0-300℃,更优选150-250℃,特别是200-250℃的温度进行。已经发现该反应在大气压下操作良好,并且预期也将在稍高或稍低的压力操作。当该反应用于食用油和脂肪的相互酯化时,需要避免酯起始原料和产物暴露于导致甘油三酯氧化的条件。这可以包括在减压下,和/或非氧化性气氛中进行该反应,或者改变温度以降低氧化的可能性。其他原料和产物可能需要保特不同的反应条件。液相方法可以在滴流床条件下进行,通常处于至多约2,例如约1的LHSV值。
本发明催化剂的一个具体优点是它们保持了它们的活性,并且在从间歇反应中取出后可以重新使用,或者在连续方法中长时间活性使用。金属催化剂与脂肪酸和酯的相互作用倾向于导致形成金属皂。金属皂是不利的,因为它们不是催化活性的,因此它们的形成涉及金属催化剂从反应损失掉。此外,它们会难以与反应产物分离,如果可分离,则倾向于粘附到工艺设备的部件,这会导致例如过滤系统效率的降低。我们已经发现,本发明的催化剂当用于本发明的相互酯化方法时,与现有技术的催化剂相比,形成金属皂的倾向降低,因此具有更长时间的活性。例如,我们已经发现,本发明的CaO-MgO催化剂可以用于五个连续的相互酯化反应,而对反应产物没有任何显著影响。这取得了明显的商业和环境益处,因为该催化剂不必这样频繁地更换。在脂肪酯反应中形成金属皂的倾向降低,还取得了对操作者而言的加工优点。
将在以下实施例中进一步描述本发明。
实施例1
将17.70g的Ca(NO3)2·4H2O和18.81g的Mn(NO3)2·4H2O溶解在273mL的软化H2O中。另外,将28.6g的Na2CO3(无水)溶解在337mL的软化H2O中,在600rpm搅拌的同时将这个溶液加热到60℃。然后将该含有钙和锰盐的溶液以滴加方式添加到Na2CO3溶液中,这使得立即形成浅棕色沉淀物。在金属盐添加完成后,将该反应在60℃放置搅拌1小时。该沉淀物然后通过过滤进行收集和重新分散在热水中。进行这个程序,以从样品中尽可能多地除去残留的钠。重新收集该沉淀物,并且将清洗步骤重复另外两次,然后将该前体在80℃干燥一整夜。
使用TAInstrumentsSDT2960仪器进行的热重分析(TGA)显示,在约725℃有较大质量损失,这表明在这个温度形成了氧化物。样品随后在800℃在空气中煅烧2小时。
使用具有Cu源的BrukerD8Advance仪器收集的X射线衍射(XRD)光谱显示,所煅烧的材料由相纯钙钛矿组成。
在PerkinElmerOptima3300RL仪器上运行的感应耦合等离子体原子发射光谱(ICP-AES)显示了28.4%的Ca、38.8%的Mn和1.8%的Na。在QuantachromeAutosorb-1仪器上收集的BET表面积数据给出2.3m2/g的表面积。
将这个实施例所述的分析方法用于表征在随后的实施例中制备的材料,除非另外说明。在使用或表征之前,将全部催化剂储存在手套箱中的氩气氛中。
实施例2
使用与实施例1相同的程序来制备材料,除了将10.6g的Sr(NO3)2和12.57g的Mn(NO3)2·4H2O溶解在273mL的H2O中,将19.1g的Na2CO3溶解在225mL的H2O中之外。XRD显示,所煅烧的材料主要包含钙钛矿相SrMnO3和存在少量SrCO3。ICP-AES数据显示该材料43.4%的Sr、29.7%的Mn和1%的Na。BET表面积是2.6m2/g。
实施例3
将20.8g的乙酸钙一水合物溶解在131.5mL的H2O中,并且将这个溶液添加到10g的氧化镁粉末(SigmaAldrich,表面积72.2m2/g)中。将所形成的浆料搅拌和在80℃加热直到干燥,然后在80℃进一步干燥一整夜。TGA数据显示了几个质量损失,并且在650℃后看起来质量损失结束。将该样品在780℃煅烧8小时,XRD显示该材料由结晶CaO和MgO组成。ICP-AES给出了Ca和Mg的预期量,分别是24.3和30.6%。记录了BET表面积10.7m2/g。CaO的总负载率等于40wt%(wtCaO/(wtCaO+wtMgO))。
实施例4
将11.8g的Ca(NO3)2·4H2O和26.93g的Mg(NO3)2·6H2O溶解在1L的H2O中。第二溶液含在溶解在1L的H2O中的29.53g的Na2CO3。该溶液的浓度因此是0.1550M(金属)和0.2786M(碱)。将两个溶液在进行磁搅拌的同时加热到60℃,然后将这两个溶液以20mL/分钟泵入闪蒸沉淀反应器,并且将该反应器内的搅拌设定为2000rpm。收集所形成的混合物,并且在室温保持1天。将该沉淀物通过过滤收集,重新制浆,用温水清洗和再次过滤。将这种清洗程序进行另外3次,然后将该沉淀物在80℃干燥一整夜。将该干燥的粉末在空气中在800℃在管式炉内煅烧2小时,然后在氩气流下冷却到室温,以避免形成大体积碳酸盐和CO2吸附到催化剂表面。
XRD显示了不具有CaCO3的相纯CaO-MgO材料。ICP-AES分析显示了34.2%的Ca、31.7%的Mg和0.4%的Na。BET表面积是12.6m2/g。
实施例5
以与实施例4所述相同的方式和相同的量来制备材料,但是将硝酸钙和硝酸镁盐溶液逐滴添加到磁搅拌的碳酸钠溶液中。添加完成时,将沉淀物在60℃老化1小时,然后过滤,用温水重新制浆和重新过滤。将该过滤过程重复另外3次,其后该沉淀物然后在80℃老化一整夜。煅烧在管式炉中在空气流下在800℃进行2小时,然后将该样品在Ar下冷却到室温。ICP-AES分析显示了33.6%的Ca、30.8%的Mg和0.6%的Na。BET表面积是12.7m2/g。
实施例6-8
使用实施例5中所述的方法,使用不同量的硝酸钙和碳酸钠来制备材料,同时保持相同的总金属浓度。通过这种方法制备了含有30wt%的CaO、50wt%的CaO和60wt%的CaO的材料,其所测量的表面积分别是54.3m2/g、7.9m2/g和6.7m2/g。
实施例9
还如实施例5所述,通过冷冻干燥代替标准干燥制备含有40wt%的CaO和MgO的材料。使用BET方法所测量的表面积是49.5m2/g。
实施例10-11
使用实施例5中所述的一般方法制备分别含有40wt%和50wt%的CaO的材料,除了通过将硝酸钙、硝酸镁和碳酸钠的所需量加倍和降水量减半,来将固体浓度增加到四倍之外。使用BET方法所记录的表面积是18.6m2/g(40wt%的CaO)和9.0m2/g(50wt%的CaO)。
实施例12
通过如下沉淀到预先形成的MgO载体上来沉积碳酸钙:将10g的MgO(重质,BDHChemicals)分散在192mL的H2O中,向其中添加22.66g的Na2CO3。将这个分散体加热到60℃。制备由在192mL的H2O中的28.07g的硝酸钙四水合物组成的溶液,并且将这个溶液以逐滴方式在搅拌下添加到MgO分散体中。观察到通过添加形成了白色沉淀物,并且将其在60℃放置搅拌1小时。通过真空过滤收集该固体,并且通过重新制浆和过滤用温水(250mL)清洗总共4次。经清洗的固体然后在80℃干燥一整夜和在空气中煅烧(800℃进行2小时,10℃/分钟升温速率),并且在Ar流下冷却。使用BET方法记录的表面积是4.8m2/g,同时ICP-AES显示29.5%的Ca、33.9%的Mg和0.69%的Na。
实施例13-18
代替重质MgO固体材料,使用MgO(轻质,来自于AlfaAesar)、LiAlO2(由AlfaAesar提供)、ZrO2、SiO2(P432)、Al2O3(PURALOXTMHP14/150)和La2O3(其通过使用碳酸钠从硝酸镧中沉淀碳酸镧前体,随后煅烧来制备)来制备具有相同的名义40wt%的CaO负载量的材料。
实施例19
通过在500mL的H2O中混合11.9g的CaCO3和10g的MgO(轻质,AlfaAesar)来制备材料(固体浓度0.044g/mL)。然后将悬浮颗粒的混合物使用BuchiB-290迷你喷雾干燥机以15mL/分钟的速率喷雾干燥,入口温度是180℃和空气流速是670L/小时。将经喷雾干燥的粉末在管式炉中在800℃在空气中煅烧2小时,然后在氩气流下冷却到室温。
实施例20-23
通过实施例19中所述的方法,通过将碳酸钠添加到钙和镁混合物中来制备含有40%的CaO和分别为0.5、1、2或5wt%的钠的材料。使用0.3842g的Na2CO3来提供在最终材料中1%的钠,并且其他的钠浓度通过改变碳酸钠的添加量来制备。
实施例24
使用实施例22的方法制备含有40%的CaO和2%的钠的材料,但是使用了715℃的煅烧温度。最终催化剂的表面积是19.5m2/g。
实施例25-29
通过实施例19-23中所述的方法制备了含有40%的CaO和分别为0、0.5、1、2或5wt%的钠的材料,但是使用LiAlO2分散体(AlfaAesar)代替MgO。
实施例30
使用实施例22的方法制备含有40%的CaO和2%的钠的材料,并且在喷雾干燥之前增加湿磨步骤。将粉末分散在50mL的H2O中,并且使用具有10mm的ZrO2珠的FritschPulverisette行星球磨机,以1∶10的粉末:珠质量比,以400rpm研磨1小时,在每15分钟后暂停10分钟。混合物然后用水补足到500mL,并且如实施例19中那样喷雾干燥。记录经煅烧材料的表面积是9.8m2/g。
实施例31
通过使乙酸钙、乙酸镁和乙酸钠的水溶液喷雾干燥来制备材料。将30g的乙酸镁四水合物、11.82g的乙酸钙一水合物和1.11g的乙酸钠三水合物溶解在300mL的水中。将所形成的溶液以9mL/分钟的速率喷雾干燥,并且入口温度是130℃和空气流速是670L/小时。粉末然后在管式炉中在800℃在空气中煅烧2小时。将该炉以10℃/分钟的速率升温到300℃,然后以5℃/分钟的速率升温到400℃和再次以10℃/分钟的速率升温到800℃,然后在氩气流下进行冷却。记录BET表面积是6.5m2/g。
对比例A
制备了包含K2CO3和MgO的相互酯化催化剂。将5g的K2CO3溶解在17mL的H2O中,并且添加到19.84g的MgO中。将该催化剂在室温干燥一整夜,然后在110℃干燥16小时。煅烧在500℃在空气中进行2小时。这个程序目的是生产如US6,072,064的实施例3所述的催化剂,用于比较的目的。
实施例32:相互酯化反应
将如实施例1-31中所述制备的材料作为相互酯化催化剂进行测试。使用粉末状催化剂在以下条件下进行浆料相相互酯化反应:
原料:重量比为4∶1的大豆油和棕榈硬脂酸甘油酯(12.5g的大豆油和3.125g的棕榈硬脂酸甘油酯)。
催化剂的量:10wt%(1.57g)
反应温度:设定温度225℃,产生的油温205℃。
反应时间:5小时
压力:大气压
搅拌速率:设定到600rpm
气氛:反应在氩气流下进行,以避免油氧化。
以1小时的间隔取油样品,并且将它们通过差示扫描量热法(DSC),使用MettlerToledoDSC822e仪器从-60℃到60℃进行分析。催化剂活性通过测定DSC峰下的部分面积来评价,并且通过假定油在-60℃是100%固体和在60℃是0%固体,可以测定在具体温度T时固体的油的百分比。熔点被认为是油是5%的固体和95%的液体的温度。各催化剂的活性然后可以通过比较反应后油混合物的熔点来进行比较。通过这种方法所测量的起始大豆油和棕榈硬脂酸甘油酯混合物的熔点是51.5℃,并且在使用甲醇钠进行相互酯化之后,该熔点下降到30.9℃。该结果显示在表1中。
对比例B
根据Jitputti等人所述的方法(J.Jitputti,B.Kitiyanan,P.Rangsunvigit,K.Bunyakiat,A.Attanatho,P.Jenvanitpanjakul,Chem.Eng.J.,2006,116,61)来制备硫酸盐化的氧化锡(SnO2-SO4 2-)。这个参考文献描述了这种材料用于甘油三酯与甲醇的酯交换的有前景的活性。测试样品用于大豆油和棕榈硬脂酸甘油酯的相互酯化,如实施例32中所述。在反应后没有发现油的熔化性质的变化,这表明对比例B没有表现出作为相互酯化催化剂的活性。
对比例C
根据Jitputti等人所述的方法(J.Jitputti,B.Kitiyanan,P.Rangsunvigit,K.Bunyakiat,A.Attanatho,P.Jenvanitpanjakul,Chem.Eng.J.,2006,116,61)来制备硫酸盐化的氧化锆(ZrO2-SO4 2-)。测试了样品用于大豆油和棕榈硬脂酸甘油酯的相互酯化,如实施例32中所述。在反应后没有发现油的熔化性质的变化,这表明对比例C没有表现出作为相互酯化催化剂的活性。
对比例D
根据S.Yan等人的公开文献(S.Yan,S.O.Salley,K.Y.S.Ng,Appl.Catal.A,2009,353,203),ZnO-La2O3是用于甘油三酯和甲醇进行酯交换生成脂肪酸甲酯和甘油的高活性催化剂。根据该作者所述的方法制备“ZnO-La2O3”样品(在所提及的公开文献和我们自己的工作中都通过XRD显示包含镧相的混合物,主要是La2O2CO3),Zn/La比是3∶1和6∶1。在根据实施例32的相互酯化方法中测试该样品,未表现出活性,在反应前和后记录熔点为51.1℃。
对比例E
Georgogianni等人(K.G.Georgogianni,A.P.Katsoulidis,P.J.Pomonis,M.G.Kontominas,FuelProcess.Technol.,2009,90,671)描述了几种混合氧化物体系,用于大豆油与甲醇的酯交换。已经发现Mg-Al水滑石(Mg/Al比3∶1)具有它们的材料中最大碱性和最大活性,在它们的反应条件下实现了大豆油向脂肪酸甲酯的96%转化率。我们根据所提及的期刊文章的说明制备了Mg/Al比为3∶1的Mg-Al水滑石催化剂。该催化剂未表现出用于实施例32所述的相互酯化方法的活性,并且在反应后油熔点保持在51.5℃未变。
对比例B-E显示,已经在先被证实对于酯交换有活性的催化剂不是有用的相互酯化催化剂。
实施例33
在反应后除去催化剂之后,通过ICP-AES分析产物油来测定在相互酯化过程中从催化剂浸出到油中的催化剂金属的量。结果显示在表2中。
表2
这表明,与CaMnO3催化剂相比,CaO-MgO催化剂具有优异的耐金属浸出性。这是特别有利的,因为金属物质存在于食用油中通常是不期望的。
表1
*对比例A的催化剂测试如所述来进行,除了催化剂负载量是2wt%和反应时间是1小时。
实施例34
催化剂样品在用于相互酯化反应之后收集,并且用于四个另外的相互酯化反应,其在用于随后的反应之前每次与油混合物分离。表3中显示了对于每次使用或“周期”,在5小时反应时间之后的熔点。对比催化剂A以2%催化剂负载量使用,并且反应时间是1小时,如上所述。
从第一反应周期中取出的对比例A的催化剂的检查显示了,它与催化剂和金属皂材料的蜡状混合物有关。金属形成皂的损失可以解释在随后的周期中催化剂活性的降低。实施例5的催化剂还显示了在周期3之后形成皂的一些证据。在实施例22的催化剂中没有观察到皂的形成,直到周期5之后。在实施例30反应中在周期4过程中注意到皂,并且测试因为该原因而停止。
表3
*备注:90分钟反应时间
实施例35(对比例)
使用碳酸铵溶液作为碱溶液来从硝酸钙溶液中沉淀出碳酸钙。将该固体通过过滤分离,清洗和干燥和在800℃煅烧来将它们转化成氧化钙。将该氧化钙固体作为催化剂用于实施例32所述的相互酯化反应中。5小时后,该反应混合物的熔点是47.1℃。
实施例36(对比例)
将用于实施例12的制备中的类型的氧化镁颗粒作为催化剂,用于实施例32中所述的相互酯化反应中。在5小时后,该反应混合物的熔点是48.2℃。
实施例37
通过将11.9g的CaCO3和10g的MgO(轻质,AlfaAesar)和1g的K2CO3在500mL的H2O中混合来制备材料(固体浓度0.044g/mL)。计算该混合物,以在该混合物中给出与实施例22的Na摩尔数相同的K摩尔数。悬浮颗粒的混合物然后使用BuchiB-290迷你喷雾干燥机以15mL/分钟的速率干燥,并且入口温度是180℃和空气流速是670L/小时。将经喷雾干燥的粉末在管式炉内在800℃在空气中煅烧2小时,然后在氩气流下冷却到室温。
将该催化剂在实施例32中所述的相互酯化反应中测试,除了该反应仅进行90分钟,而不是5小时之外。然后收集该催化剂,并且重新用于如实施例34中所述的随后的相互酯化反应(每个90分钟)。表3中显示了在每个周期之后该混合物的熔点。
实施例38
使实施例22所述的经喷雾干燥的催化剂形成粒料。将如实施例22中所述形成的CaO-MgO粉末在振动器-混合器中与作为粘合剂的1wt%的石墨进行混合。将混合物使用RollerCompactorWP120水压机进行压缩。然后将经压制的材料碾磨和筛分,以实现250-600微米的尺寸分布,并且再次在振动器混合器中与1wt%的石墨混合。混合物然后使用DottCPR-6水压机压成3mm直径和3.3mm长度的圆柱形小片。该小片的平均密度是2.35g/cm3和平均压碎强度(沿着粒料的长度施加)是6.5kgf。
催化剂粒料在Harshaw落篮式(FallingBasket)催化剂反应器中使用AutoclaveEngineers所制备的高温栓锁(boltedclosure)搅拌的间歇式反应器来测试。该测试如下来进行:将16.2g(12mL)催化剂粒料均匀装入四个样品篮中。向高压釜填充原料,其包含360g(400mL)大豆油和90g(100mL)棕榈硬脂酸甘油酯。将系统保持在0.1巴表压,其是用于该系统的最低可测压力,并且在测试期间,保持N2流通过反应器。将该高压釜加热到100℃来熔化油,并且该反应器然后在250rpm搅拌。该高压釜然后加热到210℃,在这个点将催化剂篮投入油中,并且开始反应。该反应在24小时后停止,并且油的熔点通过DSC在1.74小时-1的等价LHSV测定为36.3℃。
Claims (15)
1.由至少两种不同的酯化合物的混合物来生产酯产物的方法,其包括步骤:
a)将至少两种不同的起始酯化合物混合在一起,以形成第一酯混合物;和
b)将所述第一酯混合物与包含30-60%的氧化钙和至少一种第二金属氧化物的催化剂接触,以形成熔点低于所述第一酯混合物的熔点的第二酯混合物。
2.根据权利要求1所述的方法,其中所述起始酯中的至少一种是甘油三酯。
3.根据权利要求1或2所述的方法,其中所述起始酯化合物中的至少一种包括含有12-24个碳原子的羧酸的酯。
4.根据前述权利要求中任一项所述的方法,其中将所述催化剂预分散在所述起始酯化合物中的至少一种中。
5.根据前述权利要求中任一项所述的方法,其中所述第二金属氧化物选自非钙的第2A族金属的氧化物、过渡金属的氧化物、氧化镧、二氧化硅、氧化铝和金属铝酸盐。
6.根据权利要求5所述的方法,其中所述第二金属氧化物包括氧化镁。
7.根据前述权利要求中任一项所述的方法,其中所述催化剂进一步包含1-5%的碱金属。
8.相据前述权利要求中任一项所述的方法,其中所述催化剂的表面积小于20m2/g。
9.根据前述权利要求中任一项所述的方法,其中所述反应在0-300℃的温度进行。
10.根据前述权利要求中任一项所述的方法,其中将所述催化剂从所述第二酯混合物中分离,并且添加到第一酯混合物中以用于随后的方法中。
11.根据前述任一项权利要求的方法,其中所述催化剂包含30-60%的氧化钙、40-70%的氧化镁和0-5%的钠或钾。
12.用于相互酯化反应的催化剂,其包含30-60%的氧化钙、40-70%的氧化镁和0-5%的钠或钾。
13.根据权利要求12所述的催化剂,其由或者基本上由氧化钙和氧化镁和选自以下的任选的成分组成:碱金属、造粒助剂、润滑剂、粘结剂、压制助剂或者可用于形成成形催化剂颗粒的其他添加剂。
14.根据权利要求12或13所述的催化剂,其中所述催化剂的表面积是1-20m2/g。
15.根据权利要求12-14中任一项所述的催化剂,其为具有一定粒度分布以使得d50处于0.5-50微米范围内的粉末形式,或者为具有至少0.5mm的最小尺寸的多个成形催化剂颗粒的形式。
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