CN103706403B - The application in triacetyl glycerine reaction prepared by one class polyacid intercalation hydrotalcite catalyst - Google Patents
The application in triacetyl glycerine reaction prepared by one class polyacid intercalation hydrotalcite catalyst Download PDFInfo
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Abstract
The invention discloses and belong to a class polyacid intercalation hydrotalcite catalyst of catalyst preparation technical field and the application of catalytic production Environment-friendlynon-toxic non-toxic triacetyl glycerine thereof.The present invention by ion-exchange by polyacid intercalation in hydrotalcite, and by its first Application to production triacetyl glycerine reaction in.Polyacid intercalation hydrotalcite catalyst prepared by the present invention has the laminar structured and nano-grade size of supermolecule, polyacid intercalation hydrotalcite catalyst is adopted to produce triacetyl glycerine, compare with phosphoric acid with the concentrated sulfuric acid, its advantage is that (1) can keep high-efficiency catalytic activity and catalytic selectivity when reaction temperature reduces; (2) little to equipment corrosion, do not produce the waste liquid of highly acidity; (3) easily recycle and reuse, good stability, catalyst uses 3 months continuously, does not occur catalyst poisoning phenomenon, and its activity does not occur obvious reduction yet.
Description
Technical field
The invention belongs to catalyst preparation technical field, particularly the application of class polyacid intercalation hydrotalcite catalyst in catalytic production Environment-friendlynon-toxic non-toxic triacetyl glycerine.
Background technology
Triacetyl glycerine, also known as glyceryl triacetate, English glyceryltriacetate by name; Triacetate is a kind of performance safety, to human body friendly innoxious solvent.Triacetyl glycerine dissolves in alcohol, ether, benzene, chloroform and castor oil, can dissolve nitrocellulose, cellulose acetate, acroleic acid resin, polyvinyl acetate etc.Its physicochemical properties are in table 1.1.
The physics of table 1.1 triacetyl glycerine, chemical property
Triacetyl glycerine, as important industrial chemicals, is widely used as plasticizer and binding agent in food, cosmetics, medicine and dye industry.
1) plasticizer industry
Disabled in a lot of fields due to the toxicity of adjacent benzene class plasticizer, various environment-friendly plasticizer arises at the historic moment.Triacetyl glycerine safety non-toxic, easily biological-degradable, and raw material all can derive from biochemical industry, is typical environment-friendly plasticizer kind, can be used for plasticizer and the binding agent of acetate fiber, cellulose nitrate etc.In process on the one hand in a lot of fields as binder, ink, biological plastics, triacetyl glycerine can replace or part replaces monomerics as directly application such as dibutyl phthalates (DBP); On the other hand, taking triacetyl glycerine as raw material, react, generate two acetic acid glyceryl monolaurates with the aliphatic acid (as laurate etc.) compared with Long carbon chain, is namely a kind of safety non-toxic, good environmental protection, the more comprehensive asepsis environment-protecting plasticizer of plasticising performance.Triacetyl glycerine can be applicable to manufacture microporous membrane, is widely used in petrochemical industry, the ultrafiltration system of alcohol industry, the micropore bandage, air detection acquisition system etc. of medical industry; Can be used as plasticizer and the adhesive of plastic package material and medical medicine articles for use, capsule pill and coated tablet, as the plastics containers for medical use etc. of PVC.
2) food and medicine
(1) because triacetyl glycerine has good solid water performance, the NMF of cake food is commonly used for; (2) in essence and flavoring agent industry, as solvent and the fixastive of essence and flavoring agent; (3) chewing gum.Chewing gum is also known as chewing gum.Its main component is except carbohydrate and sweetly hide except agent, also has rubber-like (natural gum, rubber polymer etc.), resin class (ester gum, hydrogenated rosin glyceride etc.), earthfill rockfill concrete riprap RCC (calcium carbonate, magnesium carbonate, talcum powder etc.), edible paraffin, spices and emulsifying agent etc.Emulsifying agent is made up of single, double ester fatty acid glyceride and triacetyl glycerine, and it can reduce the consistency and elasticity of rubber and resin, plays plasticising and emollescence; Make various material can be kneaded together equably simultaneously, play the effect improving mouthfeel.(4) triacetyl glycerine is due to its hypotoxic feature, also can be used as gentle bactericide, the NMF of veterinary antibiotics, animal glue and rubber polymer.
3) casting industry
Triacetyl glycerine is used as the curing agent of casting sand.Use the benefit of triacetyl glycerine, one is that molding sand does not need drying or blows carbon dioxide hardening, can produce from hard effect, can reach the hardness needed for casting in 24h; Two is the molding sand casting process using the organic esters such as triacetyl glycerine, does not produce toxic gas during casting; Because molding sand deformability is good, foundry goods flawless, any surface finish, dimensional accuracy is good, and allowance is little; During molding sand casting, collapsibility is good, and the reclamation rate of sand can reach 85% ~ 90%; Easy sand removal, at the bottom of labor strength, work situation is good.
4) electron trade
Triacetyl glycerine is also widely used as solvent, and as in the manufacture of laminated capacitor, triacetyl glycerine as primary solvent, can well solve the erosion occurred in original process for making.
Current production triacetyl glycerine main flow catalyst adopts the liquid such as the concentrated sulfuric acid, phosphoric acid acid as catalyst, although these liquid acid are cheap, catalytic activity is high, its catalytic reaction exists series of problems.As adopted phosphoric acid homogeneous catalysis, production is easily caused to occur safety problem; Adopt concentrated sulfuric acid homogeneous catalysis easily to cause environmental pollution, and the corrosivity of sulfuric acid by force and easily cause the side reactions such as oxidation, carbonization, dehydration, makes reactant liquor color and luster comparatively deeply, product post processing trouble etc.Suitable catalyst can reduce side reaction, can enhance productivity again, can reduce environmental pollution again simultaneously.Along with the development of catalytic science and the reinforcement of environmental consciousness, how high, the environmentally friendly catalyst of selective catalysis activity becomes another large research topic industrial of synthesizing triacetyl glycerine.
Hydrotalcite intercalation material (LDHs) is the novel nano inorganic functional material that a class has layer structure, and its similar is in shepardite, and composition general formula can be expressed as: [M
2+ 1-xm
3+ x(OH)
2]
x+(A
n-)
x/nmH
2o, wherein M
2+and M
3+be respectively the metal cation of divalence and trivalent in laminate, as: Mg
2+, Ni
2+, Co
2+, Zn
2+, Cu
2+and Al
3+, Cr
3+, Fe
3+deng; A
n-interlayer anion, as: CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6h
4(COO)
2 2-, heteropolyanion etc.; X is M
3+/ (M
2++ M
3+) molar ratio, its value is generally between 0.1 ~ 0.5; M is the number of intermediary water molecule.Metal cation on LDHs laminate is due to the impact by the minimum effect of lattice energy and lattice orientation effect thereof, and laminate is uniformly distributed in a certain way, and make on laminate in each small construction unit, its chemical composition and structure is constant.Simultaneously, being positioned at divalent metal on laminate can in certain proportion scope by the close trivalent metal cation same order elements of ionic radius, the Modulatory character of this chemical composition and the microscopic uniformity of structure, become the good precursor material of composite structure and the uniform composite metal oxide of composition.
Polyacid compound is the poly-metal deoxide that a class contains the metals such as V, Mo, W.What formed by oxyacid radical ion of the same race condensation is same polyanionic, and isopolyacid is in its acid.What formed by different types of oxyacid root anionic condensation is heteropolyanion, and heteropoly acid is in its acid.The atom that there will be a known nearly 70 kinds of elements at present can be used as the hetero atom in heteropoly acid, comprise whole First Series transition elements, second and third serial transition elements most, adds B, Al, Ga, Si, Ge, Sn, P, As, Sb, Bi, Se, Te, I etc.And often kind of hetero atom often can different valence state be present in heteropolyanion, so kind is quite various.Polyacid as catalyst have active with selective height, the advantage such as the little and reaction condition of corrosivity is gentle.It extensively makes the research for Chemistry of Polyacids to become history a very important research field in half a century with successfully applying in Industrial Catalysis field.But in actual application, often there is as catalyst powder reuniting and load polyacid cause separation in polyacid, reclaim and recycle on problem.
Summary of the invention
For solving produced problem in above-mentioned prior art, the invention provides the application of a class polyacid intercalation hydrotalcite catalyst and catalytic production Environment-friendlynon-toxic non-toxic triacetyl glycerine thereof.Compared with independent polyacid molecule, the present invention is by the confinement space that polyacid compound is inserted into hydrotalcite and provides, the intercalation assembling compound obtained not only is held concurrently the functional characteristic of anionic clay and polyoxoanion, and has practical significance for the immobilized problem of solution heteropoly acid in Industrial Catalysis process; Meanwhile, intercalation assembling compound has middle microcellular structure, and be suitable for very much shape selective catalysis reaction, this point is similar to the functional characteristic of molecular sieve.
The present invention be by ion-exchange by polyacid intercalation in hydrotalcite, and by its first Application in the reaction of production triacetyl glycerine, the greenization achieving triacetyl glycerine is produced, for the application of further Industrialized Production Practice is laid a good foundation.
The preparation method of polyacid intercalation hydrotalcite catalyst of the present invention:
1g hydrotalcite is joined the removal CO of 50-200mL
2deionized water in obtain hydrotacite suspension, regulate the pH value of hydrotacite suspension to be 6.0-6.5 with dilute nitric acid solution after the swelling 5-24h of hydrotalcite; Compound concentration is water-soluble many aqueous acids of 0.01-0.05M, is then added dropwise in hydrotacite suspension, and the mole of polyacid is 50-100 times of hydrotalcite mole; Keep 3-24h in 20-100 DEG C under an inert atmosphere, centrifuge washing 3-6 time, vacuum drying, obtains polyacid intercalation hydrotalcite catalyst.
Described hydrotalcite is the hydrotalcite directly preparing undried; Divalent metal in the laminate of hydrotalcite is Mg
2+, trivalent metal cation is Al
3+, interlayer anion is NO
3 -.
Described hydrotalcite is the magnalium hydrotalcite of nitrate anion intercalation, and the mol ratio of magnesium and aluminium is 3:1.
The chemical formula of the anion of described polyacid is [XM
11coO
39]
n-, wherein X=P or Si; M=W or Mo; N is valence number, n=5-6.
The chemical formula of described polyacid intercalation hydrotalcite catalyst is [Mg
6al
2(OH)
16] (XM
11coO
39)
2/nyH
2o; Wherein n=5-6, X=P or Si, M=W or Mo, y=3-6.
The polyacid intercalation hydrotalcite catalyst application of above-mentioned preparation is produced triacetyl glycerine in catalyzing glycerol and acetic acid generation esterification, and its concrete steps are as follows:
By even to 1.5g glycerine, 1-10g glacial acetic acid, 1-3g water entrainer and 0.03-0.15g polyacid intercalation hydrotalcite catalyst mix, magnetic agitation, under 120-145 DEG C of condition, heating is back to and separates without moisture, then the acetic acid that Rotary Evaporators decompression removing is unnecessary is used, add 0.1-0.5g aceticanhydride 100-150 DEG C again and carry out degree of depth esterification 2-8h, triacetyl glycerine steams by last high vacuum decompression distillation, obtains final products triacetyl glycerine after adding activated carbon decolorizing.
Described water entrainer is n-propyl acetate.
Polyacid intercalation hydrotalcite catalyst prepared by the present invention has the laminar structured and nano level size of supermolecule, the dispersiveness of the system that ensure that in course of reaction, and the material uniformity do not affected in tandem reaction sequence and catalytic performance; This catalyst is heterogeneous catalyst, adopt polyacid intercalation hydrotalcite catalyst to produce triacetyl glycerine, compare its advantage with the concentrated sulfuric acid with phosphoric acid and be that (1) can keep high-efficiency catalytic activity and catalytic selectivity when reaction temperature reduces; (2) little to equipment corrosion, do not produce the waste liquid of highly acidity; (3) easily recycle and reuse, good stability, catalyst uses 3 months continuously, does not occur catalyst poisoning phenomenon, and its activity does not occur obvious reduction yet.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the polyacid intercalation hydrotalcite catalyst that embodiment 1 prepares.
Detailed description of the invention
[embodiment 1]
A) 15.4g (0.06mol) Mg (NO is got
3)
26H
2o, 7.5g (0.02mol) Al (NO
3)
39H
2o, 4.53g (0.053mol) NaNO
3mixing, is dissolved in 80ml and removes CO
2deionized water in obtain mixing salt solution; Get 5.60g(0.133mol) NaOH be dissolved in 50ml remove CO
2deionized water in obtain aqueous slkali; At N
2under protection, aqueous slkali is slowly instilled in mixing salt solution, strong agitation, stop when pH is 6.0 dripping; Then pour in autoclave, in 100 DEG C of ageing 18h, then centrifuge washings, the divalent metal in the laminate of the hydrotalcite obtained is Mg
2+, trivalent metal cation is Al
3+, interlayer anion is NO
3 -, i.e. the magnalium hydrotalcite of nitrate anion intercalation, and the mol ratio of magnesium and aluminium is 3:1; The hydrotalcite of the 1g of the undried obtained is joined 65ml and remove CO
2deionized water in obtain hydrotacite suspension, the swelling 5h of hydrotalcite; Then the HNO of 0.3M is used
3adjust ph to 6.0;
B) 10gK is got
5[PW
11coO
39] 10H
2o, is dissolved in 50ml and removes CO
2deionized water in, heating makes it dissolve completely to obtain polyacid solution;
C) by step b) the polyacid solution prepared drops in the hydrotacite suspension that step a) obtains, and then keep 8h, last centrifuge washing at nitrogen protection 90 DEG C, vacuum drying obtains polyacid intercalation hydrotalcite catalyst, and its chemical formula is [Mg
6al
2(OH)
16] (PW
11coO
39)
2/54H
2o.
As shown in the X-ray powder diffraction pattern of Fig. 1, (003) crystal face diffraction of LDHs is moved to 6 ° from 10 °, and [PW is described
11coO
39]
5-successfully be inserted into hydrotalcite layers, obtain polyacid intercalation LDHs supermolecular structure nanometer catalyst.This nanocatalyst has laminar structured, can be used for shape selective catalytic reaction as a class micropore catalysis material.The particularly important is, this class intercalation configuration material has good reactivity and selective for esterification.This catalyst is used for the preparation of triacetyl glycerine, compared with homogeneous system, the clear superiority of heterogeneous system is that catalyst is easily separated from reactor product, can reuse after process and regeneration.
[embodiment 2]
A) 15.4g (0.06mol) Mg (NO is got
3)
26H
2o, 7.5g (0.02mol) Al (NO
3)
39H
2o, 4.53g (0.053mol) NaNO
3mixing, is dissolved in 80ml and removes CO
2deionized water in obtain mixing salt solution; Get 5.60g(0.133mol) NaOH be dissolved in 50ml remove CO
2deionized water in obtain aqueous slkali; At N
2under protection, aqueous slkali is slowly instilled in mixing salt solution, strong agitation, stop when pH is 6.0 dripping; Then pour in autoclave, in 100 DEG C of ageing 18h, then centrifuge washings; The hydrotalcite of the 1g obtained is joined 65ml and remove CO
2deionized water in obtain hydrotacite suspension, the swelling 5h of hydrotalcite; Then the HNO of 0.3M is used
3adjust ph to 6.0;
B) 10gK is got
6[SiW
11coO
39] 10H
2o, is dissolved in 50ml and removes CO
2deionized water in, heating makes it dissolve completely to obtain polyacid solution;
C) by step b) the polyacid solution prepared drops in the hydrotacite suspension that step a) obtains, and then keep 8h, last centrifuge washing at nitrogen protection 90 DEG C, vacuum drying obtains polyacid intercalation hydrotalcite catalyst, and its chemical formula is [Mg
6al
2(OH)
16] (SiW
11coO
39)
2/64H
2o.
[Application Example 1]
By even for the polyacid intercalation hydrotalcite catalyst mix in 1.5g glycerine, 3.2g acetic acid, 2g n-propyl acetate and 0.05g embodiment 1, magnetic agitation, under 130 DEG C of conditions, heating is back to and separates without moisture, then the acetic acid that Rotary Evaporators decompression removing is unnecessary is used, add 140 DEG C, 0.3g acid anhydrides again and carry out degree of depth esterification 2h, triacetyl glycerine steams by last high vacuum decompression distillation, obtains final products triacetyl glycerine after adding activated carbon decolorizing.
[Application Example 2]
By even for the polyacid intercalation hydrotalcite catalyst mix in 1.5g glycerine, 3.2g acetic acid, 2g n-propyl acetate and 0.05g embodiment 2, magnetic agitation, under 130 DEG C of conditions, heating is back to and separates without moisture, then the acetic acid that Rotary Evaporators decompression removing is unnecessary is used, add 130 DEG C, 0.3g acid anhydrides again and carry out degree of depth esterification 2h, triacetyl glycerine steams by last high vacuum decompression distillation, obtains final products triacetyl glycerine after adding activated carbon decolorizing.
[catalytic reaction effect]
Compare with phosphoric acid with the concentrated sulfuric acid, adopt polyacid intercalation hydrotalcite catalyst, reaction temperature can be made to be reduced to about 130 DEG C, reactivity is fine, and conversion ratio, about 93%, is selectively greater than 99%.Meanwhile, polyacid intercalation hydrotalcite catalyst is very little to the corrosivity of equipment, and is very easy to recycling, easy and simple to handle.In addition, in the Catalytic processes adopted at present, there is not catalyst poisoning phenomenon in the good stability of polyacid intercalation hydrotalcite catalyst.In pilot scale and amplification production process, catalyst uses 3 months continuously, its active not appearance significantly reduction.In addition, thermogravimetric analysis shows, the heat endurance of polyacid intercalation hydrotalcite catalyst is fine, just occurs degraded more than 300 DEG C.The triacetyl glycerine obtained is through verifying as the oily liquids of colorless and odorless, and density is 1.16%g/cm
3, index of refraction is 1.4310, and content is 99.8%.
Table 1
Claims (3)
1. polyacid intercalation hydrotalcite catalyst glycerine and acetic acid generation esterification produce an application for triacetyl glycerine, and it is characterized in that, its concrete steps are as follows:
By even to 1.5g glycerine, 1-10g acetic acid, 1-3g water entrainer and 0.03-0.15g polyacid intercalation hydrotalcite catalyst mix, magnetic agitation, under 120-145 DEG C of condition, heating is back to and separates without moisture, then the acetic acid that Rotary Evaporators decompression removing is unnecessary is used, add 0.1-0.5g aceticanhydride 100-150 DEG C again and carry out degree of depth esterification 2-8h, triacetyl glycerine steams by last high vacuum decompression distillation, obtains final products triacetyl glycerine after adding activated carbon decolorizing; Described water entrainer is n-propyl acetate;
The preparation method of described polyacid intercalation hydrotalcite catalyst is: removal CO 1g hydrotalcite being joined 50-200mL
2deionized water in obtain hydrotacite suspension, regulate the pH value of hydrotacite suspension to be 6.0-6.5 with dilute nitric acid solution after the swelling 5-24h of hydrotalcite; Compound concentration is water-soluble many aqueous acids of 0.01-0.05M, is then added dropwise in hydrotacite suspension, and the mole of polyacid is 50-100 times of hydrotalcite mole; Keep 3-24h in 20-100 DEG C under an inert atmosphere, centrifuge washing 3-6 time, vacuum drying, obtains polyacid intercalation hydrotalcite catalyst;
Described hydrotalcite is the hydrotalcite directly preparing undried; Divalent metal in the laminate of described hydrotalcite is Mg
2+, trivalent metal cation is Al
3+, interlayer anion is NO
3 -;
The chemical formula of the anion of described polyacid is [XM
11coO
39]
n-, wherein X=P or Si; M=W or Mo; N is valence number, n=5-6.
2. application according to claim 1, is characterized in that, described hydrotalcite is the magnalium hydrotalcite of nitrate anion intercalation, and the mol ratio of magnesium and aluminium is 3:1.
3. application according to claim 1, is characterized in that, the chemical formula of described polyacid intercalation hydrotalcite catalyst is [Mg
6al
2(OH)
16] (XM
11coO
39)
2/nyH
2o; Wherein n=5-6, X=P or Si, M=W or Mo, y=3-6.
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| CN103965045B (en) * | 2014-05-06 | 2015-05-13 | 江苏瑞晨化学有限公司 | Preparation process and device for glycerol triacetate |
| CN103922930B (en) * | 2014-05-06 | 2015-06-10 | 江苏瑞晨化学有限公司 | Method for preparing n-propyl acetate by using multi-acid intercalated hydrotalcite catalyst |
| CN104841487B (en) * | 2015-03-26 | 2017-04-05 | 北京化工大学 | Polyacid intercalation hydrotalcite catalysis material and preparation method thereof |
| CN105669443A (en) * | 2015-12-31 | 2016-06-15 | 江苏瑞佳化学有限公司 | Method of preparing tributyl citrate with nano-scale intercalated hydrotalcite catalyst |
| CN105622404A (en) * | 2015-12-31 | 2016-06-01 | 江苏瑞佳化学有限公司 | Method for preparing isooctyl acetate through nanoscale intercalated hydrotalcite catalyst |
| CN105399630A (en) * | 2015-12-31 | 2016-03-16 | 江苏瑞佳化学有限公司 | Method for preparing triethyl citrate through using nanometer intercalated hydrotalcite catalyst |
| CN106045852B (en) * | 2016-07-04 | 2019-01-22 | 宜兴市永加化工有限公司 | A kind of preparation method of triacetyl glycerine |
| CN106946698A (en) * | 2017-05-09 | 2017-07-14 | 江苏瑞晨化学有限公司 | A kind of method that utilization macromolecule loading mesoporous catalyst prepares triacetyl glycerine |
| CN107537529B (en) * | 2017-08-30 | 2020-09-04 | 江南大学 | Composite catalyst for esterification reaction and bisphenol F synthesis and preparation method thereof |
| CN107552093B (en) * | 2017-08-30 | 2020-09-04 | 江南大学 | Supported iridium catalyst for bisphenol F and esterification reaction and preparation method thereof |
| CN115084542B (en) * | 2022-06-21 | 2024-06-25 | 北京化工大学 | Multi-metal sulfur cluster electrocatalyst and preparation method and application thereof |
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| CN101898155B (en) * | 2010-07-21 | 2012-04-04 | 北京化工大学 | Preparation method and application of sandwich type polyacid intercalated hydrotalcite composite material |
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