CN103706403A - Application of polyacid intercalated hydrotalcite catalyst in preparing glyceryl triacetate - Google Patents
Application of polyacid intercalated hydrotalcite catalyst in preparing glyceryl triacetate Download PDFInfo
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- CN103706403A CN103706403A CN201310715031.0A CN201310715031A CN103706403A CN 103706403 A CN103706403 A CN 103706403A CN 201310715031 A CN201310715031 A CN 201310715031A CN 103706403 A CN103706403 A CN 103706403A
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Abstract
The invention discloses a polyacid intercalated hydrotalcite catalyst and application of the polyacid intercalated hydrotalcite catalyst to preparation of environment-friendly toxic-free glyceryl triacetate, which belong to the technical field of catalyst preparation. Polyacid is intercalated into hydrotalcite through an ion exchanging method and firstly used for producing the glyceryl triacetate. The prepared polyacid intercalated hydrotalcite catalyst has a supermolecular lamella structure and a nano-grade size; the glyceryl triacetate is prepared through the catalysis of the polyacid intercalated hydrotalcite catalyst. Compared with concentrate sulfuric acid and phosphoric acid, the polyacid intercalated hydrotalcite catalyst has the advantages that the high-efficient catalytic activity and catalytic selectivity can be maintained under the situation that the reaction temperature is lowered; the corrosion on equipment is small, and no waste liquid with high acidity is produced; easiness in recycling can be realized, the stability is good, and after the catalyst is continuously used for 3 months, the poisoning phenomenon of the catalyst does not occur and the activity of the catalyst is not obviously reduced.
Description
Technical field
The invention belongs to catalyst preparation technical field, the particularly application of a class polyacid intercalation hydrotalcite catalyst in catalytic production environment-protecting asepsis type triacetyl glycerine.
Background technology
Triacetyl glycerine, claims again glyceryl triacetate, English glyceryl triacetate by name; Triacetate, is a kind of performance safety, to the friendly type innoxious solvent of human body.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
Because the toxicity of adjacent benzene class plasticizer is and disabled in a lot of fields, various environment-friendly plasticizers arise 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 a lot of fields as in the process of binder, ink, biological plastics, triacetyl glycerine can replace or part replaces monomerics as directly application such as dibutyl phthalates (DBP) on the one hand; On the other hand, take triacetyl glycerine as raw material, react with the aliphatic acid of longer carbochain (as laurate etc.), generate two acetic acid glyceryl monolaurates, is 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 the ultrafiltration system of petrochemical industry, alcohol industry, the micropore bandage of medical industry, atmosphere detect acquisition system etc.; Can be used as plasticizer and the adhesive of plastic package material and medical medicine articles for use, capsule pill and tablet sugar-coat, as plastics containers for medical use of PVC etc.
2) food and medicine
(1) because triacetyl glycerine has good solid water performance, be commonly used for the NMF of cake food; (2) in essence and flavoring agent industry, as solvent and the fixastive of essence and flavoring agent; (3) chewing gum.Chewing gum claims again chewing gum.Its main component, except carbohydrate and sweet hiding 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 comprised 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 the various materials can be kneaded together equably simultaneously, play the effect that improves mouthfeel.(4) triacetyl glycerine, due to its hypotoxic feature, also can be used as gentle bactericide, the NMF of vegetables, fruit, animal glue and rubber polymer.
3) casting industry
Triacetyl glycerine is as the curing agent of casting sand.Use the benefit of triacetyl glycerine, the one, molding sand does not need drying or blows carbon dioxide hardening, in 24h, can produce from hard effect, can reach the required hardness of casting; The 2nd, the molding sand casting process of the organic esters such as use 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%; Easily 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 can be used as primary solvent, can well solve the erosion occurring in original process for making.
Produce at present triacetyl glycerine main flow catalyst and adopt the liquid acid as catalyst such as the concentrated sulfuric acid, phosphoric acid, although these liquid acid are cheap, catalytic activity is high, there is series of problems in its catalytic reaction.As adopt phosphoric acid homogeneous catalysis, easily cause production to occur safety problem; Adopt concentrated sulfuric acid homogeneous catalysis easily to cause environmental pollution, and the corrosivity of sulfuric acid is strong and easily cause the side reactions such as oxidation, carbonization, dehydration, makes reactant liquor color and luster darker, 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, high, the environmentally friendly catalyst of How to choose catalytic activity becomes industrial another large research topic of synthetic triacetyl glycerine.
Hydrotalcite intercalation material (LDHs) is the novel nano inorganic functional material that a class has layer structure, and its structure is similar to shepardite, and forming 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, it is worth generally between 0.1～0.5; M is the number of intermediary water molecule.Metal cation on LDHs laminate, owing to being subject to the impact of the minimum effect of lattice energy and lattice orientation effect thereof, is uniformly distributed in a certain way on laminate, makes on laminate in each small construction unit, and its chemical composition and structure is constant.Simultaneously, the divalent metal being positioned on laminate can be replaced by the close trivalent metal cation isomorphous of ionic radius in certain proportion scope, the Modulatory character of this chemical composition and the microscopic uniformity of structure, become composite structure and the good precursor material that forms uniform composite metal oxide.
Polyacid compound is the poly-metal deoxide that a class contains the metals such as V, Mo, W.What by oxyacid radical ion of the same race condensation, formed is same polyanionic, and isopolyacid is in its acid.What by the condensation of different types of oxyacid root anion, formed is heteropolyanion, and heteropoly acid is in its acid.At present known have the atom of nearly 70 kinds of elements to can be used as the hetero atom in heteropoly acid, comprise whole First Series transition elements, most second and third serial transition elements, adds B, Al, Ga, Si, Ge, Sn, P, As, Sb, Bi, Se, Te, I etc.And every kind of hetero atom often can different valence state be present in heteropolyanion, so kind is quite various.Polyacid has active and selective high, the advantage such as corrosivity is little and reaction condition is gentle as catalyst.It extensively makes research for the Chemistry of Polyacids very important research field in half a century that becomes history with successful application Industrial Catalysis field.But often there is separation that powder reuniting and load polyacid cause in polyacid, the problem on reclaiming and recycling in actual application as catalyst.
Summary of the invention
For solving the problem occurring in above-mentioned prior art, the invention provides the application of a class polyacid intercalation hydrotalcite catalyst and catalytic production environment-protecting asepsis type triacetyl glycerine thereof.Compare 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 the obtaining functional characteristic of anionic clay and polyoxoanion of not only holding concurrently, and there is practical significance for solving the immobilized problem of heteropoly acid in Industrial Catalysis process; Meanwhile, intercalation assembling compound has middle microcellular structure, is suitable for very much shape selective catalysis reaction, and 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 to producing in triacetyl glycerine reaction, realized the greenization of triacetyl glycerine and produced, for further Industrialized Production Practice application is laid a good foundation.
The preparation method of polyacid intercalation hydrotalcite catalyst of the present invention:
1g hydrotalcite is joined to the removal CO of 50-200mL
2deionized water in obtain hydrotalcite suspension, after hydrotalcite swelling 5-24h, with dilute nitric acid solution, regulating the pH value of hydrotalcite suspension is 6.0-6.5; Compound concentration is water-soluble many aqueous acids of 0.01-0.05M, is then added dropwise in hydrotalcite suspension, and the mole of polyacid is 50-100 times of hydrotalcite mole; Under inert atmosphere, keep 3-24h in 20-100 ℃, centrifuge washing 3-6 time, vacuum drying, obtains polyacid intercalation hydrotalcite catalyst.
Described hydrotalcite is for directly preparing the hydrotalcite of 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; N=5-6 wherein, X=P or Si, M=W or Mo, y=3-6.
The polyacid intercalation hydrotalcite catalyst of above-mentioned preparation is applied to catalyzing glycerol and acetic acid generation esterification production triacetyl glycerine, and its concrete steps are as follows:
1.5g glycerine, 1-10g glacial acetic acid, 1-3g band aqua and 0.03-0.15g polyacid intercalation hydrotalcite catalyst mix is even, magnetic agitation, under 120-145 ℃ of condition, heating is back to without moisture and separates, then use Rotary Evaporators decompression to remove unnecessary acetic acid, add again 100-150 ℃ of 0.1-0.5g aceticanhydride to carry out degree of depth esterification 2-8h, last high vacuum decompression distillation steams triacetyl glycerine, obtains final products triacetyl glycerine after adding activated carbon decolorizing.
Described band aqua is n-propyl acetate.
Polyacid intercalation hydrotalcite catalyst prepared by the present invention has the laminar structured and nano level size of supermolecule, has guaranteed the dispersiveness of system in course of reaction, and does not affect material uniformity and catalytic performance in tandem reaction sequence; This catalyst is heterogeneous catalyst, adopts polyacid intercalation hydrotalcite catalyst to produce triacetyl glycerine, compares its advantage be that (1) can keep high-efficiency catalytic activity and catalytic selectivity in the situation that reaction temperature reduces with the concentrated sulfuric acid with phosphoric acid; (2) little to equipment corrosion, do not produce the waste liquid of high acidity; (3) easily recycle and reuse, good stability, catalyst is used 3 months continuously, does not occur catalyst poisoning phenomenon, and significantly reducing does not appear in its activity yet.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the polyacid intercalation hydrotalcite catalyst for preparing of embodiment 1.
The specific embodiment
[embodiment 1]
A) get 15.4g (0.06mol) Mg (NO
3)
26H
2o, 7.5g (0.02mol) Al (NO
3)
39H
2o, 4.53g (0.053mol) NaNO
3mix, be dissolved in 80ml and remove CO
2deionized water in obtain mixing salt solution; Getting 5.60g(0.133mol) NaOH is dissolved in 50ml and removes CO
2deionized water in obtain aqueous slkali; At N
2under protection, aqueous slkali is slowly splashed in mixing salt solution, strong agitation, pH stops dripping for 6.0 o'clock; Then pour in autoclave, in 100 ℃ of ageing 18h, centrifuge washing then, the divalent metal in the laminate of the hydrotalcite obtaining is Mg
2+, trivalent metal cation is Al
3+, interlayer anion is NO
3 -, i.e. the mol ratio of the magnalium hydrotalcite of nitrate anion intercalation, and magnesium and aluminium is 3:1; The hydrotalcite of the 1g of the undried obtaining is joined to 65ml and remove CO
2deionized water in obtain hydrotalcite suspension, hydrotalcite swelling 5h; Then use the HNO of 0.3M
3regulate pH value to 6.0;
B) get 10gK
5[PW
11coO
39] 10H
2o, is dissolved in 50ml and removes CO
2deionized water in, heating dissolves it to obtain polyacid solution completely;
C) by step b) the polyacid solution of preparation drops in the hydrotalcite suspension that step a) obtains, and then at 90 ℃ of nitrogen protections, keeps 8h, last centrifuge washing, 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 has moved to 6 ° from 10 °, and [PW is described
11coO
39]
5-successfully be inserted into hydrotalcite layers, obtained polyacid intercalation LDHs supermolecular structure nanometer catalyst.This nanocatalyst has laminar structured, can be used as a class micropore catalysis material for shape selective catalytic reaction.The particularly important is, this class intercalation configuration material has good reactivity and selective for esterification.Preparation by this catalyst for triacetyl glycerine, compares with homogeneous system, and the clear superiority of heterogeneous system is that catalyst is easily separated from reactor product, after processing and regenerating, can reuse.
[embodiment 2]
A) get 15.4g (0.06mol) Mg (NO
3)
26H
2o, 7.5g (0.02mol) Al (NO
3)
39H
2o, 4.53g (0.053mol) NaNO
3mix, be dissolved in 80ml and remove CO
2deionized water in obtain mixing salt solution; Getting 5.60g(0.133mol) NaOH is dissolved in 50ml and removes CO
2deionized water in obtain aqueous slkali; At N
2under protection, aqueous slkali is slowly splashed in mixing salt solution, strong agitation, pH stops dripping for 6.0 o'clock; Then pour in autoclave, in 100 ℃ of ageing 18h, then centrifuge washings; The hydrotalcite of the 1g obtaining is joined to 65ml and remove CO
2deionized water in obtain hydrotalcite suspension, hydrotalcite swelling 5h; Then use the HNO of 0.3M
3regulate pH value to 6.0;
B) get 10gK
6[SiW
11coO
39] 10H
2o, is dissolved in 50ml and removes CO
2deionized water in, heating dissolves it to obtain polyacid solution completely;
C) by step b) the polyacid solution of preparation drops in the hydrotalcite suspension that step a) obtains, and then at 90 ℃ of nitrogen protections, keeps 8h, last centrifuge washing, 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]
Polyacid intercalation hydrotalcite catalyst mix in 1.5g glycerine, 3.2g acetic acid, 2g n-propyl acetate and 0.05g embodiment 1 is even, magnetic agitation, under 130 ℃ of conditions, heating is back to without moisture and separates, then use Rotary Evaporators decompression to remove unnecessary acetic acid, add again 140 ℃, 0.3g acid anhydrides to carry out degree of depth esterification 2h, last high vacuum decompression distillation steams triacetyl glycerine, obtains final products triacetyl glycerine after adding activated carbon decolorizing.
[Application Example 2]
Polyacid intercalation hydrotalcite catalyst mix in 1.5g glycerine, 3.2g acetic acid, 2g n-propyl acetate and 0.05g embodiment 2 is even, magnetic agitation, under 130 ℃ of conditions, heating is back to without moisture and separates, then use Rotary Evaporators decompression to remove unnecessary acetic acid, add again 130 ℃, 0.3g acid anhydrides to carry out degree of depth esterification 2h, last high vacuum decompression distillation steams triacetyl glycerine, 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, can make reaction temperature be reduced to 130 ℃ of left and right, reactivity is fine, and conversion ratio, in 93% left and right, is selectively greater than 99%.Meanwhile, polyacid intercalation hydrotalcite catalyst is very little to the corrosivity of equipment, and very easy recycling, easy and simple to handle.In addition,, in the Catalytic processes adopting 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 is used 3 months continuously, its significantly reduction of active not appearance.In addition, thermogravimetric analysis shows, the heat endurance of polyacid intercalation hydrotalcite catalyst is fine, at 300 ℃, just occurs above degraded.Resulting triacetyl glycerine 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, content is 99.8%.
Table 1
Claims (7)
1. a preparation method for polyacid intercalation hydrotalcite catalyst, is characterized in that, its concrete preparation process is: the removal CO that 1g hydrotalcite is joined to 50-200mL
2deionized water in obtain hydrotalcite suspension, after hydrotalcite swelling 5-24h, with dilute nitric acid solution, regulating the pH value of hydrotalcite suspension is 6.0-6.5; Compound concentration is water-soluble many aqueous acids of 0.01-0.05M, is then added dropwise in hydrotalcite suspension, and the mole of polyacid is 50-100 times of hydrotalcite mole; Under inert atmosphere, keep 3-24h in 20-100 ℃, centrifuge washing 3-6 time, vacuum drying, obtains polyacid intercalation hydrotalcite catalyst.
2. preparation method according to claim 1, is characterized in that, described hydrotalcite is for directly preparing the hydrotalcite of undried; Divalent metal in the laminate of described hydrotalcite is Mg
2+, trivalent metal cation is Al
3+, interlayer anion is NO
3 -.
3. preparation method according to claim 2, 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.
4. preparation method according to claim 1, is characterized in that, 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.
5. preparation method 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; N=5-6 wherein, X=P or Si, M=W or Mo, y=3-6.
6. the application that the polyacid intercalation hydrotalcite catalyst glycerine preparing according to the arbitrary described method of claim 1-5 and acetic acid generation esterification are produced triacetyl glycerine, is characterized in that, its concrete steps are as follows:
1.5g glycerine, 1-10g glacial acetic acid, 1-3g band aqua and 0.03-0.15g polyacid intercalation hydrotalcite catalyst mix is even, magnetic agitation, under 120-145 ℃ of condition, heating is back to without moisture and separates, then use Rotary Evaporators decompression to remove unnecessary acetic acid, add again 100-150 ℃ of 0.1-0.5g aceticanhydride to carry out degree of depth esterification 2-8h, last high vacuum decompression distillation steams triacetyl glycerine, obtains final products triacetyl glycerine after adding activated carbon decolorizing.
7. application according to claim 6, is characterized in that, described band aqua is n-propyl acetate.
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| CN103922930A (en) * | 2014-05-06 | 2014-07-16 | 江苏瑞晨化学有限公司 | Method for preparing n-propyl acetate by using multi-acid intercalated hydrotalcite catalyst |
| CN103965045A (en) * | 2014-05-06 | 2014-08-06 | 江苏瑞晨化学有限公司 | Preparation process and device for glycerol triacetate |
| CN104841487A (en) * | 2015-03-26 | 2015-08-19 | 北京化工大学 | Polyacid intercalation hydrotalcite catalytic material and preparation method therefor |
| 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 |
| 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 |
| 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 |
| CN106045852A (en) * | 2016-07-04 | 2016-10-26 | 宜兴市永加化工有限公司 | Preparation method of glycerol triacetate |
| 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 |
| CN107537529A (en) * | 2017-08-30 | 2018-01-05 | 江南大学 | A kind of composite catalyst synthesized for esterification and Bisphenol F and preparation method |
| CN107552093A (en) * | 2017-08-30 | 2018-01-09 | 江南大学 | A kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification |
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| CN103922930A (en) * | 2014-05-06 | 2014-07-16 | 江苏瑞晨化学有限公司 | Method for preparing n-propyl acetate by using multi-acid intercalated hydrotalcite catalyst |
| CN103965045A (en) * | 2014-05-06 | 2014-08-06 | 江苏瑞晨化学有限公司 | Preparation process and device for glycerol triacetate |
| 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 |
| CN104841487A (en) * | 2015-03-26 | 2015-08-19 | 北京化工大学 | Polyacid intercalation hydrotalcite catalytic material and preparation method therefor |
| 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 |
| CN106045852A (en) * | 2016-07-04 | 2016-10-26 | 宜兴市永加化工有限公司 | Preparation method of glycerol triacetate |
| 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 |
| CN107537529A (en) * | 2017-08-30 | 2018-01-05 | 江南大学 | A kind of composite catalyst synthesized for esterification and Bisphenol F and preparation method |
| CN107552093A (en) * | 2017-08-30 | 2018-01-09 | 江南大学 | A kind of supporting iridium catalyst and preparation method for Bisphenol F and esterification |
| 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 |
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