CN103657696B - Preparation method of attapulgite-based solid acid catalyst for vegetable oil epoxidation - Google Patents
Preparation method of attapulgite-based solid acid catalyst for vegetable oil epoxidation Download PDFInfo
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- CN103657696B CN103657696B CN201310670616.5A CN201310670616A CN103657696B CN 103657696 B CN103657696 B CN 103657696B CN 201310670616 A CN201310670616 A CN 201310670616A CN 103657696 B CN103657696 B CN 103657696B
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 64
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000011973 solid acid Substances 0.000 title claims abstract description 25
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 235000015112 vegetable and seed oil Nutrition 0.000 title abstract description 7
- 239000008158 vegetable oil Substances 0.000 title abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 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 24
- 238000003756 stirring Methods 0.000 claims description 24
- 150000002978 peroxides Chemical class 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000006228 supernatant Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 235000019871 vegetable fat Nutrition 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- IIEPBZZQEKNZBE-UHFFFAOYSA-M azanium trimethyl(octyl)azanium dichloride Chemical class [NH4+].[Cl-].[Cl-].CCCCCCCC[N+](C)(C)C IIEPBZZQEKNZBE-UHFFFAOYSA-M 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000006188 syrup Substances 0.000 claims description 5
- 235000020357 syrup Nutrition 0.000 claims description 5
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method of an attapulgite-based solid acid catalyst for vegetable oil epoxidation, which comprises the steps of firstly synthesizing a catalyst for oil epoxidation, namely peroxyphosphotungstic acid; then, purifying, acid modifying and organic modifying the attapulgite; and finally, loading the peroxyphosphotungstic acid by taking the organic modified attapulgite as a carrier to obtain the supported solid acid catalyst. The invention improves the performance of the peroxyphosphotungstic acid, realizes the reutilization of the peroxyphosphotungstic acid, enlarges the application range of the attapulgite and improves the added value of the attapulgite, and the attapulgite-based solid acid catalyst has the characteristics of easy separation of the catalyst and the product, no pollution, no corrosion to equipment, simple and convenient post-treatment of the product, reutilization of the catalyst, simple and convenient regeneration process and the like.
Description
Technical field
The present invention relates to a kind of solid acid catalyst for vegetable fat epoxidation reaction system, be specifically related to the preparation method of organically-modified attapulgite loaded peroxide phosphotungstic acid, belong to utilization and the peroxide phosphotungstic acid immobilization technology field of attapulgite.
Background technology
Epoxidized vegetable oil applies non-toxic, environmental friendly plasticizer comparatively early, there is very excellent plasticising and heat stabilization, being widely used in the industrial circles such as plastics, coating, novel high polymer material, rubber, is the additive that uniquely can be used for packaging material for food of united states drug management board approval.Epoxidized vegetable oil fat is mainly that raw material is prepared by epoxidation reaction by vegetable oil, and preparation method is mainly divided into solvent method and solventless method.The shortcomings such as solvent method exists difficult solvent recovery, production cycle length, poor product quality, cost is high, environmental pollution is large.Solventless method, also referred to as peroxycarboxylic acid oxidizing process, first generates peroxy acid by organic acid (formic acid, acetic acid) and hydroperoxidation, and then under sulphuric acid catalysis, vegetable oil generates epoxidized vegetable oil.But this technique is homogeneous reaction, sulfuric acid can etching apparatus, seriously polluted, and product post processing inconvenience, product color are poor, make it develop and are restricted.
Peroxide phosphotungstic acid (salt) is the important heteropllyacids oxidation catalyst of a class, is widely used in, in the reactions such as alkene epoxidation, alcohol oxidation and sulfide oxidation, also to carry out alkene epoxidation efficiently.Compared with heteropoly acid, owing to introducing [O in peroxide heteropoly acid
2]
2-, its catalytic activity is higher, and advantages such as having reaction condition gentleness, catalyst amount is few, corrosivity is little, pollution-free, catalytic life is lasting is a kind of green catalyst.But, because peroxide phosphotungstic acid (salt) is soluble in water and in the reaction system of other polar organic matter existence, cause and reclaim difficulty, cause cost higher.Therefore by immobilized for the peroxide phosphotungstate catalyst carrier having high specific surface area, not only can solve the separation problem of catalyst in homogeneous catalytic reaction, and the catalytic efficiency of catalyst in heterogeneous catalytic reaction can be improved.Conventional catalyst carrier mainly contains Al
2o
3, MgO, silica gel, active carbon, TiO
2, ion exchange resin, molecular sieve, diatomite and other natural silicate material etc.
Attapulgite clay (abbreviation attapulgite) is the rich alumina magnesia silicate of a kind of porous chain layered hydrous, Main Ingredients and Appearance is silica, magnesia and alundum (Al2O3), there is unique pore passage structure, larger specific area, considerable micropore and heat endurance.Mg contained in attapulgite crystal structure unit
2+, Al
3+ion is easy to by other metal ion exchanged, and the structural hydroxyl group in Rotating fields can form Bronst acid site, and the Al exposed
3+ion then forms Lewis acid site, and being therefore the potential catalyst of many heterogeneous catalytic reactions, is also the excellent carrier of many catalyst.
Summary of the invention
The object of the invention is: a kind of preparation method for the epoxidised attapulgite based solid acid catalyst of vegetable fat is provided, solid acid catalyst prepared by the present invention is used for vegetable fat epoxidation reaction, has the features such as reaction condition gentleness, corrosivity is little, pollution-free, catalytic life lasting, catalyst is easily separated with product, product postprocessing is easy, catalyst can reuse, regenerative process is easy.
Technical solution of the present invention is: first synthesis is a kind of is used for grease epoxidation catalyst-peroxide phosphotungstic acid; Then attapulgite is purified, sour modification, organically-modified; Last with organically-modified attapulgite for carrier, load is carried out to peroxide phosphotungstic acid, obtains the solid acid catalyst of support type.
Wherein, the preparation method of peroxide phosphotungstic acid comprises the following steps:
(1) hydrogen peroxide being 30-85% by 5 ~ 10 parts of wolframic acids and 15 ~ 30 parts of mass percent concentrations adds in there-necked flask, stirs 30 ~ 240min in 60 ~ 90 DEG C, filter, and it is stand-by that solution is cooled to room temperature;
(2) phosphoric acid of 1 ~ 4 part of mass concentration 85% and 50 ~ 80 parts of water are joined in above-mentioned reactant liquor, stirring reaction 30 ~ 120min;
(3) 4 ~ 10 parts of n-octyltrimethylammonium ammonium chlorides and 50 ~ 100 parts of carrene are mixed, then be added drop-wise in solution that step (2) finally obtains, continue stirring reaction 15 ~ 60min;
(4) by step (3) solution separatory funnel standing separation, organic phase anhydrous magnesium sulfate drying spends the night, and 40 DEG C of decompressions steam carrene, obtain yellow syrup liquid, i.e. peroxide phosphotungstic acid catalyst.
Wherein, attapulgite modified preparation method is:
(1) by 10 ~ 20 parts of attapulgites, 100 ~ 200 parts of water and 0.1 ~ 1 part of calgon fully stir, and soak 24h; Suspension after soaking fully is stirred 60 ~ 120min at 30 ~ 80 DEG C, leaves standstill 0.5h, draw supernatant liquor 10cm with siphonage; Add water same position again, repeats above sedimentation, leaves standstill, draws supernatant liquor operation; The supernatant liquor of extraction is put into baking oven dry, pulverize, sieve, obtain purification attapulgite;
(2) by 5 ~ 10 parts of purification attapulgites, 1 ~ 5 part of acid and 15 ~ 50 parts of water mixings, stir 30 ~ 180min in 30 ~ 90 DEG C of constant temperature, then filter, dry, grind, sieve, obtained acid is attapulgite modified;
(3) utilize organic modifiers configuration quality concentration be 1.5 ~ 8.0% organic modifiers-toluene solution, join in the organically-modified agent solution of 100 parts by attapulgite modified for the acid described in 3 parts, backflow 24h, filters, dries, grinds, sieves, obtained organically-modified attapulgite; The order number of described purification attapulgite, the attapulgite modified and organically-modified attapulgite of acid is 200 orders; Described organic modifiers be hexadecyltrimethylammonium chloride,
γ-aminopropyl triethoxysilane, N-(
β-aminoethyl)-
γone in-aminopropyl trimethoxysilane.
Wherein, the carrying method of solid acid catalyst is: in 60 ~ 80 DEG C of vacuum drying 3 ~ 6h after pulverizing and sieving to the attapulgite carrier after organically-modified, by liquid-solid ratio 5:1 ~ 0.5:1(v/g) add peroxide phosphotungstic acid, with methanol dilution to 100ml, stir 6 ~ 24h, suction filtration, washing, vacuum drying makes residual solvent thoroughly remove, and crosses 200 mesh sieves, obtains attapulgite based solid acid catalyst.
Wherein, the vegetable fat epoxida tion catalyst reaction of described solid acid catalyst for taking hydrogen peroxide as oxygen source; Described vegetable fat comprises one or more in soybean oil, rapeseed oil, castor oil.
Tool of the present invention has the following advantages:
(1) carrier of the present invention using organically-modified attapulgite as peroxide phosphotungstic acid, catalyst can be uniformly dispersed on the larger organically-modified attapulgite of specific area, improves heat endurance and the catalytic activity of peroxide phosphotungstic acid.
(2) the attapulgite based solid acid catalyst prepared by the present invention can repeatedly repeat, catalyst regeneration is easy, after repeatedly using, its catalytic efficiency there is no obvious reduction, overcomes homogeneous catalyst simultaneously and is soluble in the problem that solvent causes recovery difficulty, little to equipment corrosion.
(3) production technology of attapulgite based solid acid catalyst of the present invention is simple, reliable, low in raw material price, peroxide phosphotungstic acid is loaded to the catalytic performance, utilization rate and the range of application that organically-modified attapulgite improve phosphotungstic acid, and improve the added value of attapulgite, what expand attapulgite utilizes scope, has important economic worth and realistic meaning.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited in this.
Embodiment 1:
(1) 10g attapulgite, 200g water, 1g calgon are fully stirred, soak 24h; Suspension after soaking fully is stirred 120min at 80 DEG C, leaves standstill 0.5h, draw supernatant liquor 10cm with siphonage; Add water same position again, repeats above sedimentation, leaves standstill, draws supernatant liquor operation; The supernatant liquor of extraction is put into baking oven dry, pulverize, cross 200 mesh sieves, obtain purification attapulgite; By above-mentioned for 5g purification attapulgite, 1g acid and the mixing of 15ml water, stir 180min in 30 DEG C of constant temperature, filtration, oven dry, grinding, cross 200 mesh sieves, obtained sour attapulgite modified; Take 3g acid attapulgite modified, 200 DEG C are incubated two hours, then add 1.5gN-(
β-aminoethyl)-
γ-aminopropyl trimethoxysilane, 98.5g toluene, refluxes 24 hours, filters, and grinding is crossed 200 mesh sieves, in 80 DEG C of vacuum drying 3h, obtained organically-modified attapulgite;
(2) hydrogen peroxide being 30% by 5g wolframic acid and 15g mass percent concentration adds in there-necked flask, stirs 240min in 60 DEG C, filter, and it is stand-by that solution is cooled to room temperature; Then add phosphoric acid and the 50g water of 1.0g mass concentration 85%, continue stirring reaction 30min; After having reacted, drip the mixture of 4g n-octyltrimethylammonium ammonium chloride and 50ml carrene, after being added dropwise to complete, continue stirring reaction 15min; Finally, solution is used separatory funnel standing separation, organic phase anhydrous magnesium sulfate drying spends the night, and 40 DEG C of decompressions steam carrene, obtain yellow syrup liquid, i.e. peroxide phosphotungstic acid catalyst;
(3) take the recessed native 2g after organically-modified, add the peroxide phosphotungstic acid methanol solution 2g of mass concentration 50%, be diluted to 100ml with absolute methanol, after magnetic agitation 24h, filter, dry, pulverize, cross 200 eye mesh screens, the solid obtained, at 60 DEG C of vacuum drying 48h, obtains solid acid catalyst.This solid acid is used for the epoxidation run of soybean oil, the epoxide number >6% of the epoxidized soybean oil obtained, iodine number <5.
Embodiment 2:
(1) 15g attapulgite, 200g water, 1g calgon are fully stirred, soak 24h; Suspension after soaking fully is stirred 60min at 80 DEG C, leaves standstill 0.5h, draw supernatant liquor 10cm with siphonage; Add water same position again, repeats above sedimentation, leaves standstill, draws supernatant liquor operation; The supernatant liquor of extraction is put into baking oven dry, pulverize, cross 200 mesh sieves, obtain purification attapulgite; By above-mentioned for 10g purification attapulgite, 5g acid and the mixing of 50ml water, stir 30min, then filter, dry, grind, cross 200 mesh sieves in 60 DEG C of constant temperature, obtained acid is attapulgite modified; Take 3g acid attapulgite modified, 200 DEG C are incubated two hours, then add 8g gamma-aminopropyl-triethoxy-silane, 92g toluene, reflux 24 hours, filter, and grinding is crossed 200 mesh sieves, in 80 DEG C of vacuum drying 6h, obtained organically-modified attapulgite;
(2) hydrogen peroxide being 35% by 10g wolframic acid and 30g mass percent concentration adds in there-necked flask, stirs 240min in 60 DEG C, filter, and it is stand-by that solution is cooled to room temperature; Then add phosphoric acid and the 80g water of 4.0g mass concentration 85%, continue stirring reaction 30min; After having reacted, drip the mixture of 10g n-octyltrimethylammonium ammonium chloride and 100ml carrene, after being added dropwise to complete, continue stirring reaction 60min; Finally, solution is used separatory funnel standing separation, organic phase anhydrous magnesium sulfate drying spends the night, and 40 DEG C of decompressions steam carrene, obtain yellow syrup liquid, i.e. peroxide phosphotungstic acid catalyst;
(3) the recessed native 2g after organically-modified is taken, add the peroxide phosphotungstic acid methanol solution 20g of mass concentration 50%, 100ml is diluted to absolute methanol, magnetic agitation 24h is after having reacted, dry, pulverize, cross 200 eye mesh screens, the solid obtained, at 60 vacuum drying 48h, obtains solid acid catalyst.This solid acid is used for the epoxidation run of castor oil, the epoxide number >3% of the epoxy castor oil obtained, iodine number <5.
Embodiment 3:
(1) 20g attapulgite, 100g water, 0.1g calgon are fully stirred, soak 24h; Suspension after soaking is stirred 90min at 60 DEG C of sonic oscillations simultaneously, leaves standstill 0.5h, draw supernatant liquor 10cm with siphonage; Add water same position again, repeats above sedimentation, leaves standstill, draws supernatant liquor operation; The supernatant liquor of extraction is put into baking oven dry, pulverize, cross 200 mesh sieves, obtain purification attapulgite; By above-mentioned for 10g purification attapulgite, 2g acid and the mixing of 50ml water, stir 180min in 90 DEG C of constant temperature, filtration, oven dry, grinding, cross 200 mesh sieves, obtained sour attapulgite modified; Take 3g acid attapulgite modified, 200 DEG C are incubated two hours, add 4g hexadecyltrimethylammonium chloride, 96g toluene, reflux 24 hours, filter, and grinding is crossed 200 mesh sieves, in 80 DEG C of vacuum drying 3h, obtained organically-modified attapulgite;
(2) hydrogen peroxide being 85% by 5g wolframic acid and 30g mass percent concentration adds in there-necked flask, stirs 30min in 90 DEG C, filter, and it is stand-by that solution is cooled to room temperature; Then add phosphoric acid and the 80g water of 4g mass concentration 85%, continue stirring reaction 120min; After having reacted, drip the mixture of 4.5g n-octyltrimethylammonium ammonium chloride and 100ml carrene, after being added dropwise to complete, continue stirring reaction 60min; Finally, solution is used separatory funnel standing separation, organic phase anhydrous magnesium sulfate drying spends the night, and 40 DEG C of decompressions steam carrene, obtain yellow syrup liquid, i.e. peroxide phosphotungstic acid catalyst;
(3) take the recessed native 2g after organically-modified, add the peroxide phosphotungstic acid methanol solution 5g of mass concentration 50%, be diluted to 100ml with absolute methanol, magnetic agitation 24h, after having reacted, dry, pulverize, cross 200 eye mesh screens, the solid obtained, at 60 vacuum drying 48h, obtains solid acid catalyst.This solid acid is used for the epoxidation run of rapeseed oil, the epoxide number >3.5% of the epoxy rapeseed oil obtained, iodine number <5.
Claims (1)
1., for the preparation method of the epoxidised attapulgite based solid acid catalyst of vegetable fat, first synthesis is a kind of is used for grease epoxidation catalyst-peroxide phosphotungstic acid; Then attapulgite is purified, sour modification, organically-modified; Last with organically-modified attapulgite for carrier, load is carried out to peroxide phosphotungstic acid, obtains the solid acid catalyst of support type; It is characterized in that: the preparation method of peroxide phosphotungstic acid comprises the following steps:
(1) hydrogen peroxide being 30-85% by 5 ~ 10 parts of wolframic acids and 15 ~ 30 parts of mass percent concentrations adds in there-necked flask, stirs 30 ~ 240min in 60 ~ 90 DEG C, filter, and it is stand-by that solution is cooled to room temperature;
(2) phosphoric acid of 1 ~ 4 part of mass concentration 85% and 50 ~ 80 parts of water are joined in above-mentioned reactant liquor, stirring reaction 30 ~ 120min;
(3) 4 ~ 10 parts of n-octyltrimethylammonium ammonium chlorides and 50 ~ 100 parts of carrene are mixed, then be added drop-wise in solution that step (2) finally obtains, continue stirring reaction 15 ~ 60min;
(4) by step (3) solution separatory funnel standing separation, organic phase anhydrous magnesium sulfate drying spends the night, and 40 DEG C of decompressions steam carrene, obtain yellow syrup liquid, i.e. peroxide phosphotungstic acid catalyst; Attapulgite modified preparation method is:
(1) by 10 ~ 20 parts of attapulgites, 100 ~ 200 parts of water and 0.1 ~ 1 part of calgon fully stir, and soak 24h; Suspension after soaking fully is stirred 60 ~ 120min at 30 ~ 80 DEG C, leaves standstill 0.5h, draw supernatant liquor 10cm with siphonage; Add water same position again, repeats above sedimentation, leaves standstill, draws supernatant liquor operation; The supernatant liquor of extraction is put into baking oven dry, pulverize, sieve, obtain purification attapulgite;
(2) by 5 ~ 10 parts of purification attapulgites, 1 ~ 5 part of acid and 15 ~ 50 parts of water mixings, stir 30 ~ 180min in 30 ~ 90 DEG C of constant temperature, then filter, dry, grind, sieve, obtained acid is attapulgite modified;
(3) utilize organic modifiers configuration quality concentration be 1.5 ~ 8.0% organic modifiers-toluene solution, join in the organically-modified agent solution of 100 parts by attapulgite modified for the acid described in 3 parts, backflow 24h, filters, dries, grinds, sieves, obtained organically-modified attapulgite; The order number of described purification attapulgite, the attapulgite modified and organically-modified attapulgite of acid is 200 orders; Described organic modifiers be hexadecyltrimethylammonium chloride,
γ-aminopropyl triethoxysilane, N-(
β-aminoethyl)-
γone in-aminopropyl trimethoxysilane; The carrying method of solid acid catalyst is: in 60 ~ 80 DEG C of vacuum drying 3 ~ 6h after pulverizing and sieving to the attapulgite carrier after organically-modified, peroxide phosphotungstic acid is added by liquid-solid ratio 5:1 ~ 0.5:1v/g, with methanol dilution to 100mL, stir 6 ~ 24h, suction filtration, washing, vacuum drying makes residual solvent thoroughly remove, cross 200 mesh sieves, obtain attapulgite based solid acid catalyst; The vegetable fat epoxida tion catalyst reaction of described solid acid catalyst for taking hydrogen peroxide as oxygen source; Described vegetable fat comprises one or more in soybean oil, rapeseed oil, castor oil.
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| CN111111667A (en) * | 2020-02-26 | 2020-05-08 | 江苏森茂能源发展有限公司 | Preparation method of attapulgite-based oil sludge cracking catalyst |
| CN112871191B (en) * | 2021-01-28 | 2023-02-17 | 盱眙凹土能源环保材料研发中心 | Preparation method of magnetic phosphotungstic acid/attapulgite solid acid catalyst and application method thereof in lignocellulose liquefaction |
| CN114672371B (en) * | 2022-03-17 | 2023-09-19 | 广西科技大学 | Preparation method of epoxidized oil |
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