CN103816929A - Hydrotalcite-like catalyst, preparation method and application thereof - Google Patents
Hydrotalcite-like catalyst, preparation method and application thereof Download PDFInfo
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- CN103816929A CN103816929A CN201410069713.3A CN201410069713A CN103816929A CN 103816929 A CN103816929 A CN 103816929A CN 201410069713 A CN201410069713 A CN 201410069713A CN 103816929 A CN103816929 A CN 103816929A
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- catalyst
- metal salt
- methyl ester
- acid methyl
- houghite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 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 claims abstract description 35
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 34
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 238000009830 intercalation Methods 0.000 claims abstract description 17
- 230000002687 intercalation Effects 0.000 claims abstract description 17
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 23
- 229910021645 metal ion Inorganic materials 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 19
- 239000004202 carbamide Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 150000004702 methyl esters Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000001455 metallic ions Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 239000002243 precursor Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- -1 phosphotungstic acid anions Chemical class 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 23
- 238000001027 hydrothermal synthesis Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 150000002118 epoxides Chemical group 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 7
- 239000002932 luster Substances 0.000 description 7
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 4
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 4
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 4
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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Abstract
The invention discloses a hydrotalcite-like catalyst, a preparation method and application thereof, and relates to a catalyst for fatty acid methyl ester epoxidation reaction, a preparation method and application thereof. The hydrotalcite-like compound is an intercalation carrier of a catalyst, wherein the hydrotalcite is synthesized by taking divalent metal salt and trivalent metal salt or divalent metal salt and tetravalent metal salt as raw materials, and the intercalation carrier is phosphotungstic acid anions. The preparation method comprises the steps of dispersing the precursor in deionized water to form suspension and carrying out ion exchange. The catalyst is used for the epoxidation reaction of fatty acid methyl ester to synthesize epoxy fatty acid methyl ester. The catalyst keeps the inherent better catalytic performance of the LDHs, and the catalytic performance is greatly improved. The preparation method of the catalyst is simple, avoids long-time crystallization and purification, and is beneficial to reducing diffusion resistance in catalytic reaction. In the process of participating in epoxidation reaction, the catalyst has the synergistic catalytic action of a material host and an object, and shows better conversion rate and selectivity.
Description
Technical field
The present invention relates to a kind of catalysis technology of preparing of plasticizer, specifically, is a kind of catalyst for fatty acid methyl ester epoxidation reaction, preparation method and application thereof.
Background technology
Plasticizer is added in the plastic products such as polyethylene as a kind of additive, at present, plasticizer on market has 90% for O-phthalic acids plasticizer, although but traditional phthalic ester plasticizer applied range, performance are also better, but because the existence of phenyl ring has certain toxicity to humans and animals, forbid in the plastics and rubber of toy for children, medical supplies, packaging for foodstuff etc. and human body close contact.
Epoxy aliphatic acid methyl ester can effectively replace O-phthalic acids plasticizer, and because it has goods good-toughness, compatibility is good, volatility is low, animal migration good, nontoxic can contact food, light and heat is had to good stability action advantage, be subject to the extensive concern of PVC industry.In addition the chlorion of epoxy aliphatic acid methyl ester on can stability of pvc chain, epoxide group in structure can absorb the hydrogen chloride discharging because of light and heat, thereby inhibition continuous decomposition, the effect of plasticizer and stabilizing agent is played in the application that extends PVC goods simultaneously.
The traditional synthesis of epoxy aliphatic acid methyl ester is that fatty acid methyl ester, formic acid, hydrogen peroxide are mixed, with sulphuric acid catalysis, at 45～65 ℃ in tank reactor stirring reaction a few hours, reaction finishes rear stratification, remove water, then obtain epoxy aliphatic acid methyl ester by decompression distillation.This technique produces a large amount of discarded acid solutions, causes environmental pollution etching apparatus simultaneously, has greatly limited the scope of application of plasticizer epoxy aliphatic acid methyl ester, and has not met the theory of Green Chemistry.In order further to alleviate the pollution to environment raising in the process of synthesizing epoxy fatty acid methyl ester, selecting suitable catalyst is key efficient, that green is prepared epoxy aliphatic acid methyl ester.
Patent CN101235021 discloses the agent of employing heteropolyacid liquid phase catalysis, although reduced the corrosion of catalyst to equipment, but contain heavy metal in heteropolyacid liquid phase catalysis agent, can cause product heavy metal pollution, can not be used for the packaging material of food, medicine, and the auxiliary agent of toy and home decoration material; Secondly, heteropolyacid catalyst preparation is complicated, and technological process is long, and cost is higher.
Patent CN101284821 epoxy aliphatic acid methyl ester preparation method, adopts ionic-liquid catalyst.Ionic liquid is hydrophilic salts, in epoxidation process, can produce inorganic solution, reduce its catalytic effect, thereby gained epoxide number is lower.
Patent CN101139328 novel process for synthesizing epoxy aliphatic acid methyl ester, adopts magnetic catalyst.The method has realized the favourable separation of catalyst but it prepares more complicated, and preparation cost is high.
Patent CN101591588 epoxidized soybean oil or epoxyfatty acid first (second) ester preparation method, adopt organic rhenium oxide to make catalyst, and urea peroxide provides oxygen source, do not use Bronsted acid and carboxylic acid to transmit oxygen atom.This legal system is high for complicated cost.
Although above several method has improved the epoxide number of product to a certain extent, reduce the corrosion of catalyst to equipment, but the prepared catalyst of above patented method still cannot meet industrial requirements, and has the shortcomings such as structure destructible, poor catalyst stability.
Summary of the invention
The object of this invention is to provide a kind of houghite catalyst, phosphotungstic acid root anion in the assembling of hydrotalcite layers intercalation, between prepared layer, object is the intercalation LDHs material of phosphotungstic acid root.This phosphotungstic acid root intercalated houghite has kept the intrinsic good catalytic performance of LDHs, can make again its catalytic performance increase substantially simultaneously.This catalyst has good activity stability.
Further aim of the present invention is to provide the preparation method of this catalyst, and this preparation method is simple.Avoided long-time crystallization and purifying to houghite slurries in conventional synthesizing, the particle of houghite prepared by the method is less, contributes to reduce the diffusional resistance in catalytic reaction.And adopt the method for sonic oscillation to carry out intercalation to houghite presoma, be conducive to the phosphotungstic anion intercalated houghite interlayer that enters.
It is synthetic for fatty acid methyl ester epoxidation reaction that further aim of the present invention is to provide this catalyst, and this catalyst is in participation epoxidization reaction process, and body of material and object concerted catalysis effect, embody good conversion ratio and selective.
A kind of houghite catalyst, described houghite is the intercalation carrier take divalent metal salt and trivalent metal salt or divalent metal salt and tetravalent metal salt as the synthetic hydrotalcite of raw material as catalyst, intercalation carrier is phosphotungstic anion.
Described divalent metal salt is any in the nitrate, chloride of Mg, Ca, Zn; Described trivalent metal salt is the one in nitrate, the chloride of Al, Fe; Described tetravalent metal salt is the chloride of Ti.
Hydrotalcite-based compound is the complex metal hydroxide that a class has layer structure, because it has the adjustable sex change of laminate composition and the interchangeability of interlayer anion, makes it have important using value in various fields.There is soda acid center in hydrotalcite and Roasting Decomposition product surface thereof, has soda acid bi-functional, all shown good catalytic effect using it as solid acid alkali catalytic agent at many catalytic fields.Phosphotungstic acid has oxidation-reduction quality, is a kind of multi-functional environmental protection catalyst, and the advantages such as its " accurate liquid phase behavior " and multi-functional catalysis, make it have very important using value.The anion intercalated houghite of phosphotungstic acid root provides the chain carrier of more other kinds for epoxidation reaction, and the anion of intercalation has also increased the interlamellar spacing of houghite simultaneously, effectively improves the catalysis epoxidation activity of houghite catalyst.This method for preparing catalyst is simple, and catalyst activity is high, and the life-span is long, reusable, and post catalyst reaction easily separates from system, and in product, catalyst-free is residual, and environmental friendliness can better meet the requirement of current high-purity epoxy aliphatic acid methyl ester technique.
In the inventive method, the preparation method of catalyst used is as follows:
Under room temperature, in deionized water medium, divalent metal salt and trivalent metal salt or divalent metal salt and tetravalent metal salt and urea are reacted, obtain houghite presoma;
This presoma is scattered in and in deionized water, forms solid content at 7%～10% suspension, and the proportioning that is 3%～5% by forerunner's mass ratio takes phosphotungstic acid and is dissolved in this suspension, and ion-exchange obtains phosphotungstic anion intercalated houghite catalyst.
The mol ratio of described bivalent metal ion and trivalent metal ion or bivalent metal ion and quadrivalent metallic ion is 2:1～5:1, and the mol ratio of urea and above-mentioned metal ion total amount is 6:1～10:1.
At room temperature a certain amount of divalent metal salt and trivalent metal salt or divalent metal salt and tetravalent metal salt are dissolved in deionized water, are mixed with certain density solution and add in hydrothermal reaction kettle, with adding a certain amount of urea in backward this mixed solution.Hydrothermal reaction kettle is placed in to temperature-controlling heating box, at 100～150 ℃, heats 8～12h, obtain white precipitate, filter while hot, obtain houghite presoma; This presoma is scattered in and in deionized water, forms solid content at 7%～10% suspension, taking phosphotungstic acid by 3%～5% proportioning is dissolved in this suspension, at ultrasonic oscillator intermediate ion exchange 2h～4h, after filtration, according to said method exchange once again, suction filtration, be placed in baking oven and dry, obtain white phosphotungstic anion intercalated houghite catalyst.
The catalyst of preparation carries out activity rating as stated above, and process is summarized as follows:
In the there-necked flask that thermometer is housed, add fatty acid methyl ester, methyl alcohol, catalyst, is added drop-wise to excessive hydrogen peroxide in reaction system.Under uniform temperature, constant temperature abundant stirring reaction, after reaction finishes, isolate solid catalyst and product liquid by centrifuge, reuse after catalyst treatment, and liquid obtains epoxy aliphatic acid methyl ester through separatory, washing, decompression distillation after processing.
In above-mentioned activity rating scheme, catalyst amount is the amount 3%～10% of fatty acid methyl ester, H
2o
2with the ratio of the two key molal quantitys of fatty acid methyl ester are 1:1～3:1,55～75 ℃ of reaction temperatures.
Described catalyst is for fatty acid methyl ester epoxidation reaction synthesizing epoxy fatty acid methyl ester.
Fatty acid methyl ester, methyl alcohol, phosphotungstic anion intercalated houghite catalyst and excessive hydroperoxidation, separate and obtain epoxy aliphatic acid methyl ester;
The amount 3%～10% that phosphotungstic anion intercalated houghite catalyst amount is fatty acid methyl ester, H
2o
2with the ratio of the two key molal quantitys of fatty acid methyl ester are 1:1～3:1,55～75 ℃ of reaction temperatures.
Described fatty acid methyl ester is R
1-CH=CH-R
2-COOCH, R
1and R
2carbon number is 14-l6.
Beneficial effect:
Hydrotalcite-based compound is the novel catalysis material of a class, has the complex metal hydroxide of layer structure, because it has the adjustable sex change of laminate composition and the interchangeability of interlayer anion, makes it have important using value in various fields.Phosphotungstic acid is a kind of multifunctional novel catalyst, has very high catalytic activity.Phosphotungstic acid root intercalated houghite not only can provide for epoxidation reaction the chain carrier of more other kinds, and phosphotungstic acid root anion intercalation hydrotalcite has also increased the interlamellar spacing of hydrotalcite simultaneously, thereby improves catalytic activity and selective.Phosphotungstic acid root intercalated houghite has the feature of hydrotalcite and phosphotungstate concurrently simultaneously, be applied to catalysis fatty acid methyl ester epoxidation reaction, whole process is not introduced carboxylic acid and toxic solvent, overcome the problem of current liquid phase epoxidation acid corrosion, improved epoxidation productive rate, and catalyst is reusable.
Figure of description
The XRD collection of illustrative plates of Fig. 1 phosphotungstic acid intercalation zinc titanium hydrotalcite sample
The FT-IR figure of Fig. 2 phosphotungstic acid intercalation zinc titanium hydrotalcite sample
The specific embodiment
At room temperature a certain amount of magnesium nitrate and aluminum nitrate (mol ratio of magnesium-aluminum metal ion is 2:1) are dissolved in deionized water, be mixed with certain density solution and add (mol ratio of urea and metal ion total amount is 6:1) in hydrothermal reaction kettle, with adding a certain amount of urea in backward this mixed solution.Hydrothermal reaction kettle is placed in to temperature-controlling heating box, at 100 ℃, heats 8h, obtain white precipitate, filter while hot, obtain magnalium hydrotalcite presoma; This presoma is scattered in and in deionized water, forms solid content at 7% suspension, taking phosphotungstic acid by 3% proportioning is dissolved in this suspension, at ultrasonic oscillator intermediate ion exchange 2h, after filtration, according to said method exchange once again, suction filtration, be placed in baking oven and dry, obtain white phosphotungstic anion intercalated magnalium hydrotalcite catalyst.
In the there-necked flask that thermometer is housed, add methyl stearate, methyl alcohol, catalyst, is added drop-wise to excessive hydrogen peroxide in reaction system, and catalyst amount is the amount 7% of methyl stearate, H
2o
2with the ratio of methyl stearate carbon-carbon double bond molal quantity be 1.5:1.At 75 ℃, constant temperature abundant stirring reaction, after reaction finishes, isolate solid catalyst and product liquid by centrifuge, reuse after catalyst treatment, and liquid obtains methyl epoxy stearate through separatory, washing, decompression distillation after processing.Product quality indicator is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, epoxide number (%): 4.93%, acid number (mgg
-1): 0.50, flash-point (℃): 191, heating loss ((125 ℃ × 3 hours) %) :≤0.5, resistivity is (Ω m): 6.56 × 10
8.
Embodiment 2
At room temperature a certain amount of zinc sulfate and titanium sulfate are dissolved in to (mol ratio of zinc titanium metal ions is 3:1) in deionized water, be mixed with certain density solution and add (mol ratio of urea and metal ion total amount is 8:1) in hydrothermal reaction kettle, with adding a certain amount of urea in backward this mixed solution.Hydrothermal reaction kettle is placed in to temperature-controlling heating box, at 140 ℃, heats 10h, obtain white precipitate, filter while hot, obtain zinc titanium hydrotalcite precursor; This presoma is scattered in and in deionized water, forms solid content at 8% suspension, taking phosphotungstic acid by 4% proportioning is dissolved in this suspension, at ultrasonic oscillator intermediate ion exchange 2h～4h, after filtration, according to said method exchange once again, suction filtration, be placed in baking oven and dry, obtain white phosphotungstic anion intercalated zinc titanium hydrotalcite catalyst.
In the there-necked flask that thermometer is housed, add methyl hexadecanoate, methyl alcohol, catalyst, is added drop-wise to excessive hydrogen peroxide in reaction system, and catalyst amount is the amount 3% of methyl hexadecanoate, H
2o
2with the ratio of methyl hexadecanoate carbon-carbon double bond molal quantity be 1:1.At 55 ℃, constant temperature abundant stirring reaction, after reaction finishes, isolate solid catalyst and product liquid by centrifuge, reuse after catalyst treatment, and liquid obtains epoxy methyl hexadecanoate through separatory, washing, decompression distillation after processing.Product quality indicator is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, epoxide number (%): 4.93%, acid number (mgg
-1): 0.50, flash-point (℃): 191, heating loss ((125 ℃ × 3 hours) %) :≤0.5, resistivity is (Ω m): 6.56 × 10
8.
Embodiment 3
At room temperature a certain amount of zinc chloride and titanium tetrachloride are dissolved in to (mol ratio of zinc titanium metal ions is 5:1) in deionized water, be mixed with certain density solution and add (mol ratio of urea and metal ion total amount is 10:1) in hydrothermal reaction kettle, with adding a certain amount of urea in backward this mixed solution.Hydrothermal reaction kettle is placed in to temperature-controlling heating box, at 140 ℃, heats 12h, obtain white precipitate, filter while hot, obtain zinc titanium hydrotalcite precursor; This presoma is scattered in and in deionized water, forms solid content at 10% suspension, taking phosphotungstic acid by 5% proportioning is dissolved in this suspension, at ultrasonic oscillator intermediate ion exchange 3h, after filtration, according to said method exchange once again, suction filtration, be placed in baking oven and dry, obtain white phosphotungstic anion intercalated zinc titanium hydrotalcite catalyst.
In the there-necked flask that thermometer is housed, add methyl linoleate, methyl alcohol, catalyst, is added drop-wise to excessive hydrogen peroxide in reaction system, and catalyst amount is the amount 10% of methyl linoleate, H
2o
2with the ratio of methyl linoleate carbon-carbon double bond molal quantity be 3:1.At 60 ℃, constant temperature abundant stirring reaction, after reaction finishes, isolate solid catalyst and product liquid by centrifuge, reuse after catalyst treatment, and liquid obtains epoxy methyl linoleate through separatory, washing, decompression distillation after processing.Product quality indicator is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, epoxide number (%): 4.93%, acid number (mgg
-1): 0.50, flash-point (℃): 191, heating loss ((125 ℃ × 3 hours) %) :≤0.5, resistivity is (Ω m): 6.56 × 10
8.
Embodiment 4
At room temperature a certain amount of zinc chloride and titanium tetrachloride are dissolved in to (mol ratio of zinc titanium metal ions is 5:1) in deionized water, be mixed with certain density solution and add (mol ratio of urea and metal ion total amount is 10:1) in hydrothermal reaction kettle, with adding a certain amount of urea in backward this mixed solution.Hydrothermal reaction kettle is placed in to temperature-controlling heating box, at 140 ℃, heats 12h, obtain white precipitate, filter while hot, obtain zinc titanium hydrotalcite precursor; This presoma is scattered in and in deionized water, forms solid content at 10% suspension, taking phosphotungstic acid by 5% proportioning is dissolved in this suspension, at ultrasonic oscillator intermediate ion exchange 4h, after filtration, according to said method exchange once again, suction filtration, be placed in baking oven and dry, obtain white phosphotungstic anion intercalated zinc titanium hydrotalcite catalyst.
Carry out activity rating by the appreciation condition of embodiment 1, product quality indicator is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, epoxide number (%): 4.93%, acid number (mgg
-1): 0.50, flash-point (℃): 191, heating loss ((125 ℃ × 3 hours) %) :≤0.5, resistivity is (Ω m): 6.56 × 10
8.
Embodiment 5
At room temperature a certain amount of zinc chloride and titanium tetrachloride are dissolved in to (mol ratio of zinc titanium metal ions is 5:1) in deionized water, be mixed with certain density solution and add (mol ratio of urea and metal ion total amount is 10:1) in hydrothermal reaction kettle, with adding a certain amount of urea in backward this mixed solution.Hydrothermal reaction kettle is placed in to temperature-controlling heating box, at 140 ℃, heats 12h, obtain white precipitate, filter while hot, obtain zinc titanium hydrotalcite precursor; This presoma is scattered in and in deionized water, forms solid content at 10% suspension, taking phosphotungstic acid by 5% proportioning is dissolved in this suspension, at ultrasonic oscillator intermediate ion exchange 4h, after filtration, according to said method exchange once again, suction filtration, be placed in baking oven and dry, obtain white phosphotungstic anion intercalated zinc titanium hydrotalcite catalyst.
Carry out activity rating by the appreciation condition of embodiment 1, product quality indicator is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, epoxide number (%): 4.93%, acid number (mgg
-1): 0.50, flash-point (℃): 191, heating loss ((125 ℃ × 3 hours) %) :≤0.5, resistivity is (Ω m): 6.56 × 10
8.
Embodiment 6
At room temperature a certain amount of zinc chloride and titanium tetrachloride are dissolved in to (mol ratio of zinc titanium metal ions is 5:1) in deionized water, be mixed with certain density solution and add (mol ratio of urea and metal ion total amount is 10:1) in hydrothermal reaction kettle, with adding a certain amount of urea in backward this mixed solution.Hydrothermal reaction kettle is placed in to temperature-controlling heating box, at 140 ℃, heats 12h, obtain white precipitate, filter while hot, obtain zinc titanium hydrotalcite precursor; This presoma is scattered in and in deionized water, forms solid content at 10% suspension, taking phosphotungstic acid by 5% proportioning is dissolved in this suspension, at ultrasonic oscillator intermediate ion exchange 4h, after filtration, according to said method exchange once again, suction filtration, be placed in baking oven and dry, obtain white phosphotungstic anion intercalated zinc titanium hydrotalcite catalyst.
Carry out activity rating by the appreciation condition of embodiment 1, product quality indicator is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, epoxide number (%): 4.93%, acid number (mgg
-1): 0.50, flash-point (℃): 191, heating loss ((125 ℃ × 3 hours) %) :≤0.5, resistivity is (Ω m): 6.56 × 10
8.
Embodiment 7
At room temperature a certain amount of zinc chloride and titanium tetrachloride are dissolved in to (mol ratio of zinc titanium metal ions is 5:1) in deionized water, be mixed with certain density solution and add (mol ratio of urea and metal ion total amount is 10:1) in hydrothermal reaction kettle, with adding a certain amount of urea in backward this mixed solution.Hydrothermal reaction kettle is placed in to temperature-controlling heating box, at 150 ℃, heats 12h, obtain white precipitate, filter while hot, obtain zinc titanium hydrotalcite precursor; This presoma is scattered in and in deionized water, forms solid content at 10% suspension, taking phosphotungstic acid by 5% proportioning is dissolved in this suspension, at ultrasonic oscillator intermediate ion exchange 4h, after filtration, according to said method exchange once again, suction filtration, be placed in baking oven and dry, obtain white phosphotungstic anion intercalated zinc titanium hydrotalcite catalyst.
Carry out activity rating by the appreciation condition of embodiment 1, product quality indicator is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, epoxide number (%): 4.93%, acid number (mgg
-1): 0.50, flash-point (℃): 191, heating loss ((125 ℃ × 3 hours) %) :≤0.5, resistivity is (Ω m): 6.56 × 10
8.
As seen from Figure 1, phosphotungstic acid intercalation zinc titanium hydrotalcite sample is in 2 θ=11.2,22.8,34.5, the diffraction maximum at 60.2o left and right place, corresponds respectively to hydrotalcite (003) (hkl), (006), (009), the characteristic peak of (110) crystal face.By XRD data, (003) distance of utilizing Prague (Bragg) equation can calculate between hydrotalcite laminate is about 0.89nm, and reaching 1.25nm by (003) distance between the houghite laminate obtaining after phosphotungstic acid intercalation, this explanation phosphotungstic acid radical ion successfully enters between hydrotalcite laminate.
3150～3700cm in Fig. 2
-1the broad peak at place belongs to the hydrogen-oxygen key stretching vibration peak of interlayer in conjunction with water, 1620cm
-1the absworption peak at place is the bending vibration peak of the interlayer crystallization water, 1422cm
-1place's absworption peak belongs to CO
3 2-characteristic absorption peak, illustrate that phosphotungstic acid intercalation zinc titanium hydrotalcite all has the infrared signature absworption peak of hydrotalcite.The IR of phosphotungstic acid intercalation zinc titanium hydrotalcite composes at 1422cm
-1the CO at place
3 2-characteristic absorption peak intensity obviously weaken, at 1030,978,885cm
-1there is the characteristic absorption peak of phosphotungstic acid root in place, this proves that phosphotungstic acid radical ion has partly replaced the CO between hydrotalcite laminate
3 2-and between insert layer.
Claims (7)
1. a houghite catalyst, is characterized in that: described houghite is the intercalation carrier take divalent metal salt and trivalent metal salt or divalent metal salt and tetravalent metal salt as the synthetic hydrotalcite of raw material as catalyst, and intercalation carrier is phosphotungstic anion.
2. houghite catalyst according to claim 1, is characterized in that: described divalent metal salt is any in the nitrate, chloride of Mg, Ca, Zn; Described trivalent metal salt is the one in nitrate, the chloride of Al, Fe; Described tetravalent metal salt is the chloride of Ti.
3. the preparation method of houghite catalyst according to claim 1, its step is as follows:
Under room temperature, in deionized water medium, divalent metal salt and trivalent metal salt or divalent metal salt and tetravalent metal salt and urea are reacted, obtain houghite presoma;
This presoma is scattered in and in deionized water, forms solid content at 7%～10% suspension, and the phosphotungstic acid that is 3%～5% with the mass ratio of presoma is dissolved in this suspension, and ion-exchange obtains phosphotungstic anion intercalated houghite catalyst.
4. the preparation method of houghite catalyst according to claim 3, it is characterized in that: the mol ratio of described bivalent metal ion and trivalent metal ion or bivalent metal ion and quadrivalent metallic ion is 2:1～5:1, the mol ratio of urea and above-mentioned metal ion total amount is 6:1～10:1.
5. the application of houghite catalyst according to claim 1, is characterized in that: described catalyst is for fatty acid methyl ester epoxidation reaction synthesizing epoxy fatty acid methyl ester.
6. the application of houghite catalyst according to claim 5, is characterized in that: fatty acid methyl ester, and methyl alcohol, phosphotungstic anion intercalated houghite catalyst and excessive hydroperoxidation, separate and obtain epoxy aliphatic acid methyl ester;
The amount 3%～10% that phosphotungstic anion intercalated houghite catalyst amount is fatty acid methyl ester, H
2o
2with the ratio of the two key molal quantitys of fatty acid methyl ester are 1:1～3:1,55～75 ℃ of reaction temperatures.
7. according to the application of the houghite catalyst described in claim 5 or 6, it is characterized in that: described fatty acid methyl ester is R
1-CH=CH-R
2-COOCH, R
1and R
2carbon number is 14-l6.
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| CN104944451A (en) * | 2015-06-09 | 2015-09-30 | 张玉蕙 | Preparation method for heteropolyacid pillared alkaline hydrotalcite |
| CN108514888A (en) * | 2018-04-16 | 2018-09-11 | 北京化工大学 | A kind of preparation of polyacid intercalation hydrotalcite catalysis material and photocatalysis deep desulfurization of fuel oil system |
| CN109092241A (en) * | 2018-09-04 | 2018-12-28 | 东营科尔特新材料有限公司 | It magnalium zinc-base houghite adsorbent and preparation method and is applied in liquefied gas fine de-sulfur |
| CN111871415A (en) * | 2020-09-01 | 2020-11-03 | 南京工业大学 | Hydrotalcite-like precursor metal active element-loaded catalyst and application thereof |
| CN112876880A (en) * | 2021-01-18 | 2021-06-01 | 浙江嘉澳环保科技股份有限公司 | Preparation method and product of modified hydrotalcite |
| CN113277552A (en) * | 2021-05-19 | 2021-08-20 | 湘潭大学 | Titanium-based metal hydroxide and preparation method thereof |
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| CN108514888A (en) * | 2018-04-16 | 2018-09-11 | 北京化工大学 | A kind of preparation of polyacid intercalation hydrotalcite catalysis material and photocatalysis deep desulfurization of fuel oil system |
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| CN112876880A (en) * | 2021-01-18 | 2021-06-01 | 浙江嘉澳环保科技股份有限公司 | Preparation method and product of modified hydrotalcite |
| CN113277552A (en) * | 2021-05-19 | 2021-08-20 | 湘潭大学 | Titanium-based metal hydroxide and preparation method thereof |
| CN113277552B (en) * | 2021-05-19 | 2024-02-02 | 湘潭大学 | Titanium-based metal hydroxide and preparation method thereof |
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