CN105618137A - Porous acidic resin catalyst, preparation method and applications thereof - Google Patents
Porous acidic resin catalyst, preparation method and applications thereof Download PDFInfo
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Abstract
The present invention provides a porous acidic resin catalyst, wherein a nanometer material adopted as a pore forming hard template agent is directly doped into a macromolecule resin, reaction dissolving is performed in an acid solution to remove the nanometer material so as to form nanometer pore channels in the macromolecule resin, and then a sulfonation reaction is performed to achieve acid functionalization so as to prepare the nano-pore resin solid acid. The present invention further provides a preparation method and applications of the porous acidic resin catalyst. According to the present invention, the porous acidic resin catalyst has characteristics of large pore volume, large specific surface area, and strong acidity; and with the application of the porous acidic resin catalyst as the solid acid catalyst in the catalytic reaction for esterification synthesis of sec-butyl acetate from acetic acid and butene, the reaction activity is high, the reaction stability is good, and the butene conversion rate and the sec-butyl acetate yield of the esterification reaction can be significantly improved.
Description
Technical field
The invention belongs to the preparation field of catalyst, be specifically related to a kind of porous acid resin catalyst being combined to sec-Butyl Acetate for acetic acid and butene esters.
Background technology
Acetate is to be esterified, with acetic acid or other carboxylic acid catalysis direct addition, other acetate and other carboxylates such as producing corresponding isopropyl acetate, sec-Butyl Acetate, isobutyl acetate respectively by rudimentary rare hydrocarbon such as propylene, 1-butylene, 2-butylene, isobutene.. The product at present with the most extensive market prospect is isopropyl acetate and sec-Butyl Acetate.
Sec-Butyl Acetate, also referred to as the another butyl ester of acetic acid, acetic acid the second butyl ester, it is one of four kinds of isomers of butyl acetate, for colourless, inflammable, there is the liquid of fruit taste, in most of the cases all similar to the performance of other isomer, solubilized various kinds of resin and Organic substance. Positive butyl ester and isobutyl ester that its boiling point is more common are low, and evaporation rate is very fast. The solubility property of sec-butyl acetate (SBA) and n-butyl acetate, isobutyl acetate are similar, can the extensively positive butyl ester of substituted acetic acid and isobutyl acetate in formulation for coating material. Many materials are had a good dissolubility by sec-butyl acetate, industrial can be used as manufacturing nitrocellulose lacquer, acrylic paint, and the solvent of polyurethane paint etc., these paint classes can be used as aircraft wing coating, dermatine coating, car paint etc. Sec-butyl acetate can also be used for celluloid goods, rubber, safety glass, art paper, the manufacture process of the products such as coat of paint. It can also make the solvent flashing in printing-ink, in the application such as offset printing; Additionally can be used as the quick dry agent of sensitive material. Sec-butyl acetate can be used as the refining of penicillin; Owing to its volatility is moderate, there is good percutaneous permeability, it is possible to promote component as drug absorption. Sec-butyl acetate is chiral molecule, the same with other butyl acetate two kinds conventional, can be used as reaction medium, as being used for synthesizing trialkylamine oxides, and N, N-diallyl ethylenediamine etc. Sec-butyl acetate can be used as extractant, such as materials such as extract and separate ethanol-propanol, acrylic acid. Or it being used as azeotropic distillation solvent, part replaces toluene, dimethylbenzene and methylisobutylketone.
Sec-Butyl Acetate commercial production catalyst is in the past main based on sulphuric acid, utilizes the esterification under sulfuric acid catalyst exists of acetic acid and sec-butyl alcohol to produce. Acetic acid, sec-butyl alcohol and sulphuric acid heat in the reactor to 90 DEG C, remove the steam containing sec-Butyl Acetate, sec-butyl alcohol and water after reaction and condense, the tower of reboiler is arranged at feeding bottom, upper strata, unreacting alcohol flash distillation also circulates to reactor, and thick ester admixture isolates sec-Butyl Acetate through second time distillation from other by-products. But production process also exists sulphuric acid corrosive equipment, product and catalyst be not readily separated, easily cause environmental pollution and the shortcoming such as personal injury is serious so that the commercial Application of sec-butyl acetate and expanding production are greatly limited. So, butyl acetate industry now to substitute existing liquid strong acid, finds new catalysis material in the urgent need to the acidic catalyst of a kind of " close friend ", development of new catalyst is then the fundamental way solving the existing environment of butyl acetate and etching problem.
CN101544562A has invented a kind of method of Zeolite molecular sieve catalysis acetic acid and butylene catalytic Synthesis of sec-Butyl Acetate, with butylene and acetic acid for raw material, with modified beta zeolite molecular sieve for catalyst, and continuous synthesis sec-butyl acetate in fixed bed reactors; But zeolite molecular sieve catalyst is prone to knot carbon reaction temperature 90��130 DEG C, and reaction inactivation is very fast, so while it does not have severe corrosive and the toxic of sulphuric acid, but this catalyst also exists the problem of life-time service less stable, constrains its industrial applications.
Sulfonated phenylethylene hydrogen form cation acidic resins have homogeneous acid strength, stronger acidity and good stability, at present replace sulphuric acid to be widely used in the various acid catalyzed reactions such as various esterification, etherificate, alkylation of phenol, alkene hydration as solid acid resin catalyst, have that product postprocessing is simple, equipment corrosion degree is little, be easy to the advantages such as continuous prodution. Preparation and application about storng-acid cation exchange resin acidic catalyst have many disclosed patents. The preparation method that patent CN1389297A discloses highly acid macroporous cation exchange resin catalyst; Patent CN1555924A also discloses that a kind of high-capacity resin Catalysts and its preparation method. But the pore volume of common styrene-divinylbenzene cation exchange resin itself is with specific surface area is little, the sour amount of hole surface is less, cause its restricted problem of Reaction-diffusion terms as solid acid catalyst, so that its reactivity in heterogeneous catalysis is applied is relatively low with selectivity. Chinese patent CN101948385A proposes the synthetic method of a kind of sec-Butyl Acetate, and the catalyst used by reaction is macropore strong acid cation exchanger resin; Owing to common macropore strong acid cation exchanger resin specific surface area is less, catalysis is active relatively low with raw material conversion per pass, pressurized operation, raw material acetic acid and C must be passed through4Alkene continues through three fixed bed reactors all in liquid form in the same direction, and the circulation adopted is relatively larger, so energy and material consumption is higher, have impact on its economy.
The Nafion perfluorinated sulfonic resin of Dupont company exploitation is the solid super-strong acid being prepared from by perfluorinated sulfonic acid ether and tetrafluoroethene copolymerization, can be used for the direct alkylation catalytic reaction of iso-butane butylene. But due to the very low (0.02m of the surface area of Nafion resin2/ g), need to be carried on porous material just has higher catalysis activity. [the ShenW such as WeiShen, GuaY, XuHL.Alkylationofisobutane/1-buteneonmethyl-modifiedNafi on/SBA-15materials.AppliedCatalysisA:General, 2010,377:1-8.] Nafion is passed through dip loading on the SBA-15 that trimethylethoxysilane synthesizes, obtain surface hydrophobic, acid stronger Organic-inorganic composite solid-acid material. Result shows, under equal acid load capacity, its catalytic effect is better than carried heteropoly acid and molecular sieve catalyst. But the preparation cost of both Nafion resin and mesoporous material is all higher, and load preparation process easily blocks SBA-15 duct, there is the shortcoming that operation is wayward, prepare poor repeatability, limit the probability of its industrial applications. The preparation method that patent CN1167011A discloses high thermal stability sulfonic acid type cation exchange resin catalyst, patent CN1569334A also discloses that comparatively similar Thermostable strong acid cation resin Catalysts and its preparation method. By introducing the resistance to elevated temperatures of the electron withdraw group raising polystyrene highly acidic resin catalyst such as F, Cl, Br on phenyl ring, but resin catalyst specific surface area still relatively low (30-50m2/ g), cause that its reactivity is relatively low, and easily fouling and inactivate very fast.
From above-mentioned, existing acetic acid and butene esters being combined to technology and the analysis of cation acid resin catalyst preparation method, the replacement liquid acid of restriction resin solid acid at present realizes the problem of industrial applications and is mainly resin catalyst specific surface area still relatively low (30-50m2/ g), cause that its reactivity is low, reaction selectivity is poor, still can not meet the requirement carrying out esterification application as heterogeneous catalyst.
Summary of the invention
For overcoming deficiency of the prior art, the present invention provides a kind of porous acid resin catalyst, it has big specific surface area, acid strong, when being combined in the reaction of sec-Butyl Acetate for catalysis acetic acid and butene esters, it is possible to significantly improve alkylated reaction catalysis activity and the selectivity of resin solid acid.
For achieving the above object, the technical scheme is that, a kind of porous acid resin catalyst, it is that nano material is directly incorporated in macromolecule resin as pore hard mould agent, then removal nano material is dissolved in reaction in an acidic solution, thus forming nano pore in macromolecule resin, then carry out sulfonating reaction and realize acid functionalization, and the nano-pore resin solid acid prepared.
Wherein, described porous acid resin catalyst specific surface area is more than 350m2/ g, exchange capacity is more than 4.0mmol/g.
The preparation method that the present invention also provides for a kind of porous acid resin catalyst, nano material is directly incorporated in macromolecule resin as pore hard mould agent, then removal nano material is dissolved in reaction in an acidic solution, thus forming nano pore in macromolecule resin, carrying out sulfonating reaction again and realize acid functionalization, namely prepared nano-pore resin solid acid be porous acid resin catalyst;
The preparation method of described porous acid resin catalyst comprises the following steps that;
(1) the pre-modification of nano material: nano material that parts by weight 70��95 parts, size are 10��200nm and 5��30 parts of propenyls or propanoic acid are put in acetone solvent, reacts 1��4 hour at 50��60 DEG C; Then being evaporated removing acetone solvent at 80��100 DEG C, the surface esterification namely completing nano material modifiies, and obtains the modified porous nano material of hydrophobization;
(2) macromolecule resin polymerization synthesis: modified porous nano material, porogen and solvent that monomer A, crosslinking copolymerization monomer, initiator, step (1) obtain are made into oil-phase solution A;
Oil-phase solution A includes following components by weight percentage: modified porous nano material 2��20%; Monomer A30��70%; Crosslinking copolymerization monomer 2��18%; Initiator 0.1��3%; Porogen 5��20%; Surplus is solvent;
Being made into aqueous phase solution B with pure water, glue dispersant and inorganic dispersant, pure water, glue dispersant and inorganic dispersant weight ratio are 100: 1.6��2.0: 1.4��1.5;
Being mixed with weight ratio 1: 2.4��2.8 with aqueous phase solution B by oil-phase solution A, under stirring at 210��280 revs/min after even suspension dispersion, then be warming up to 80��84 DEG C of reaction 2h��6h, cooling, filtration washing obtain the polymer microballoon containing modified porous nano material; Then adopt steam distillation method to remove porogen and residual monomer at 95��102 DEG C described polymer microballoon again, obtain porous resin catalyst body Archon;
(3) molten except fill nano material: the bulk resin Archon that step (2) obtains with 2%��10% hydrochloric acid solution at 40��50 DEG C of stirring reaction 2��5h, wash and dried at 50��110 DEG C through drainage, obtain the bulk resin Archon containing nano-pore;
(4) acid functionalization of resin catalyst sulfonating reaction: the resin body Archon containing nano-pore obtained in step (3): oleum: dichloroethane solvent: the weight ratio of sulfonation catalyst be 100: 410��480: 240��300: 3��5 ratio be made into reaction raw materials, at 50��85 DEG C swelling 1��3 hour; Being warming up at 82��140 DEG C stirring reaction 3��6h again, washing filtering removes remaining sulphuric acid, then removes dichloroethane solvent at 60��120 DEG C with distillating method, namely obtains porous resin solid acid catalyst.
Wherein, described nano material is mesopore nano material.
Wherein, described nano material at least one in nano-calcium carbonate, nano aluminium oxide or CNT.
Wherein, described monomer A is at least one in styrene monomer, butene monomers, methyl methacrylate monomer, acrylonitrile monemer.
Wherein, described crosslinking copolymerization monomer at least one in diallyl benzene, divinylbenzene, divinyl phenylmethane.
Wherein, described initiator at least one in azodiisobutyronitrile or cumyl peroxide.
Wherein, described solvent at least one in petroleum ether, normal hexane, butanone or ethyl acetate.
Wherein, described porogen at least one in benzene, toluene, butanol or normal heptane.
Wherein, described glue dispersant is at least one in gelatin, arabic gum.
Wherein, described inorganic dispersant is at least one in silicon oxide, titanium oxide.
The present invention also provides for the application of a kind of porous acid resin catalyst, and described porous acid resin catalyst is combined in the reaction of sec-Butyl Acetate for acetic acid and butene esters.
Nano material is directly incorporated in macromolecule resin as pore hard mould agent by the present invention, then removal nano material is dissolved in reaction in an acidic solution, thus forming nano pore in macromolecule styrene resin, carry out sulfonating reaction again and realize acid functionalization, and prepare the acid of nanoporous resin solid, solve the pore volume of conventional resin solid acid and the problem that specific surface area is little, the sour amount of hole surface is less.
The pore volume of porous resin acidic catalyst prepared by the present invention is big with specific surface area, acid by force, porosity is high, Reaction-diffusion terms is good, it is applied to acetic acid as solid acid catalyst and is combined in the catalytic reaction of sec-Butyl Acetate with butene esters, reactivity is high, reaction stability is good, and butene conversion and the sec-Butyl Acetate yield of esterification can be significantly improved, there is very important using value, achieve good technique effect.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further. Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention. In addition, it is to be understood that after having read present disclosure, the present invention can be made various changes or modifications by those skilled in the art, these equivalent form of values fall within limited range of the present invention equally.
Embodiment 1
(1) nano-material modified: to be the Nano-meter CaCO3 of 10nm by parts by weight 70 parts, size3Material powder and 30 parts of propanoic acid react 3 hours in 50 parts of acetone solvents, at 50 DEG C; Then it is evaporated removing acetone solvent at 100 DEG C, namely completes mesopore Nano-meter CaCO33The surface esterification of material modifiies, and obtains the modified porous nano material of hydrophobization.
(2) polymer suspension polymerization synthesis: by 40wt% styrene monomer, 10wt% diallyl benzene crosslinking copolymerization monomer, 3wt% azodiisobutyronitrile initiator, 3wt% modified Nano CaCO3Material, 15% toluene porogen and 29wt% petroleum ether solvent are made into oil-phase solution A;
Pure water, arabic gum dispersant and titanium oxide dispersant are joined for aqueous phase solution B, pure water, arabic gum dispersant and titanium oxide dispersant weight ratio are 100: 1.6: 1.4, oil-phase solution A is mixed with weight ratio 1: 2.4 with aqueous phase solution B, being warming up to 80 DEG C of reaction 6h at 210 revs/min under stirring, cooling, filtration washing obtain the polymer microballoon containing modified porous nano material; Then polymer microballoon adopts steam distillation method remove monomer A and the diallyl benzene crosslinking copolymerization monomer of porogen and residual again at 95 DEG C, obtains porous resin catalyst body Archon;
(3) molten except nano material: the porous resin catalyst body Archon that step (2) obtains with 2% hydrochloric acid solution at 50 DEG C of stirring reaction 5h, wash and dried at 110 DEG C through drainage, obtain the bulk resin Archon containing nano-pore;
(4) sulfonating reaction: the nano-pore resin Archon obtained by step (3): oleum: dichloroethane solvent: Cu2SO4The weight ratio of sulfonation catalyst be 100: 420: 250: 5 ratio prepare reaction raw materials, swelling 3 hours at 50 DEG C; In being warming up at 140 DEG C stirring reaction 5h, washing filtering removes remaining sulphuric acid, then removes dichloroethane solvent at 60 DEG C with distillating method, obtains porous acid resin catalyst A#, is placed in vacuum desiccator standby; It is 4.3mmol/g that alkalimetric titration analysis records the exchange capacity of porous acid resin catalyst A#, and it is 256m that physical absorption BET analyzes the specific surface area measured2/g��
Embodiment 2
(1) porous nanometer material modifiies: be the Nano-meter CaCO3 of 200nm by parts by weight 95 parts, size3Material and 5 parts of propanoic acid react 1 hour in 40 parts of acetone solvents at 60 DEG C; Then it is evaporated removing acetone solvent at 80 DEG C, namely completes inorganic nano CaCO3The hydrophobic modification of material support.
(2) resin polymerization synthesis: by 60wt% butene monomers, 2wt% divinylbenzene crosslinking copolymerization monomer, 0.1wt% cumyl peroxide initiator, 20wt% modified Nano CaCO3Material, 5% butanol porogen and 12.9wt% normal hexane solvent are made into oil-phase solution A;
With pure water, arabic gum dispersant and titanium oxide dispersant for aqueous phase solution B, pure water, arabic gum dispersant and titanium oxide dispersant weight ratio are 100: 2.0: 1.5, oil-phase solution A is mixed with weight ratio 1: 2.5 with aqueous phase solution B, being warming up to 83 DEG C of reaction 3h at 240 revs/min under stirring, cooling, filtration washing obtain the polymer microballoon containing nano material; Then polymer microballoon adopts steam distillation method remove porogen and residual monomer again at 102 DEG C, obtains bulk resin Archon;
(3) molten except nano material: by the bulk resin Archon of step (2) gained with 10% hydrochloric acid solution at 40 DEG C of stirring reaction 2h, wash and dried at 50 DEG C through drainage, obtain the bulk resin Archon containing nano-pore;
(4) sulfonating reaction: the nano-pore bulk resin Archon obtained by step (3): oleum: dichloroethane solvent: Cu2SO4The weight ratio of sulfonation catalyst be 100: 480: 300: 4 ratio prepare reaction raw materials, be warming up to 85 DEG C swelling 1 hour; Stirring reaction 6h at 85 DEG C again, washing filtering removes remaining sulphuric acid, then removes dichloroethane solvent at 120 DEG C with distillating method, obtains nano-pore sulfate resin solid acid, i.e. porous acid resin catalyst B#, is placed in vacuum desiccator standby;
It is 402m that alkalimetric titration analysis records the specific surface area of resin solid acid B# exchange capacity 4.2mmol/g, physical absorption BET analysis mensuration2/g��
Embodiment 3
(1) nano-material modified: by nanometer Al that parts by weight 80 parts, size are 100nm2O3Material and 20 parts of propanoic acid react 2 hours in 45 parts of acetone solvents at 55 DEG C; Then it is evaporated removing acetone solvent at 90 DEG C, namely completes inorganic nano Al2O3The hydrophobic modification of material support.
(2) macromolecule resin suspension polymerisation: by 30wt% methyl methacrylate monomer, 15wt% divinyl phenyl first crosslinking copolymerization monomer, 1.0wt% cumyl peroxide initiator, 10wt% modified Nano Al2O3Material, 15% normal heptane porogen and 29wt% butanone solvent are made into oil-phase solution A;
With pure water, gelatin dispersant and titanium oxide dispersant for aqueous phase solution B, pure water, gelatin dispersant and titanium oxide dispersant weight ratio are 100: 2: 1.5, oil-phase solution is mixed with weight ratio 1: 2.8 with aqueous phase solution, being warming up to 81 DEG C of reaction 4h at 230 revs/min under stirring, cooling, filtration washing obtain the polymer microballoon containing nano material; Then polymer microballoon adopts steam distillation method remove porogen and residual monomer again at 102 DEG C, obtains bulk resin Archon;
(3) molten except nano material: the bulk resin Archon of step (2) gained with 6% hydrochloric acid solution at 48 DEG C of stirring reaction 3h, wash and dried at 110 DEG C through drainage, obtain the bulk resin Archon containing nano-pore;
(4) sulfonating reaction: the nano-pore resin Archon obtained in step (3): oleum: dichloroethane solvent: the weight ratio of sulfonation catalyst be 100: 460: 260: 4 ratio prepare reaction raw materials, swelling 1 hour at 85 DEG C; Stirring reaction 4h at 83 DEG C again, washing filtering removes remaining sulphuric acid, then removes dichloroethane solvent at 100 DEG C with distillating method, obtains porous acid resin catalyst C#, is placed in vacuum desiccator standby; It is 367m that alkalimetric titration analysis records the specific surface area of porous acid resin catalyst C# exchange capacity 4.4mmol/g, physical absorption BET analysis mensuration2/g��
Embodiment 4
1) nano-material modified: by nanometer Al that parts by weight 85 parts, size are 80nm2O3Material and 15 parts of propanoic acid react 3 hours in 47 parts of acetone solvents at 54 DEG C; Then it is evaporated removing acetone solvent at 95 DEG C, namely completes inorganic nano Al2O3The hydrophobic modification of material support.
(2) suspension polymerisation: by 48wt% acrylonitrile monemer, 12wt% divinyl phenylmethane crosslinking copolymerization monomer, 1.5wt% cumyl peroxide initiator, 15wt% modified Nano Al2O3Material, 10% normal heptane porogen and 13.5wt% ethyl acetate solvent are made into oil-phase solution A;
With pure water, arabic gum dispersant and silicon oxide dispersant for aqueous phase solution B, pure water, arabic gum dispersant and silicon oxide dispersant weight ratio are 100: 1.8: 1.4, oil-phase solution A is mixed with weight ratio 1: 2.4 with aqueous phase solution B, being warming up to 82 DEG C of reaction 4.5h at 220 revs/min under stirring, cooling, filtration washing obtain the polymer microballoon containing nano material; Then polymer microballoon adopts steam distillation method remove porogen and residual monomer again at 102 DEG C, obtains bulk resin Archon;
(3) molten except nano material: the bulk resin Archon of step (2) gained with 5% hydrochloric acid solution at 46 DEG C of stirring reaction 3.5h, wash and dried at 110 DEG C through drainage, obtain the bulk resin Archon containing nano-pore;
(4) sulfonating reaction: the nano-pore resin Archon obtained in step (3): oleum: dichloroethane solvent: the weight ratio of sulfonation catalyst be 100: 440: 260: 5 ratio prepare reaction raw materials, swelling 2 hours at 65 DEG C; Being warming up at 82 DEG C stirring reaction 4h, washing filtering removes remaining sulphuric acid, then removes dichloroethane solvent at 90 DEG C with distillating method, obtains porous acid resin catalyst D#, is placed in vacuum desiccator standby; It is 382m that alkalimetric titration analysis records the specific surface area of porous acid resin catalyst D# exchange capacity 4.3mmol/g, physical absorption BET analysis mensuration2/g��
Embodiment 5,
Take the porous acid resin catalyst A of preparation in above-described embodiment 1-4 one by one, B, C or D#20g, it is loaded on thermostatically controlled rustless steel tubular fixed-bed reactor can be combined to sec-Butyl Acetate for acetic acid and butene esters as catalyst, reaction temperature 85 DEG C, acetic acid/butene molar ratio 2, successive reaction 300h when air speed WHSV1.5h-1, average butene conversion reaches more than 99wt%, the reaction yield of synthesis sec-Butyl Acetate is calculated as more than 95wt% with butylene, and concrete outcome is shown in Table 1.
Table 1 catalyst effect table
| Catalyst | Butene conversion | Sec-Butyl Acetate yield |
| A | 99.2% | 96.7% |
| B | 99.5% | 97.1% |
| C | 99.3% | 96.8% |
| D | 99.6% | 96.4% |
As seen from Table 1, the porous acid resin catalyst of the present invention, namely nano-pore sulfate resin solid acid is combined in the fixed bed reaction technique of sec-Butyl Acetate as catalyst for acetic acid and butene esters, when relatively low reaction temperature and higher reaction velocity, average butene conversion reaches more than 99wt%, sec-Butyl Acetate yield is calculated as more than 96wt% with butylene.
Be currently used for compared with acetic acid is combined to sec-Butyl Acetate catalysts technology with butene esters, the pore volume of the porous resin acidic catalyst of the present invention is big with specific surface area, acid strong, porosity is high, Reaction-diffusion terms is good. Achieve reactivity height during catalyst reaction, sec-Butyl Acetate yield is high, reaction stability is good technique effect.
It is more than the description to the embodiment of the present invention, by the described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or use the present invention. The multiple amendment of these embodiments be will be apparent from for those skilled in the art, and generic principles defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments. Therefore, the present invention is not intended to be limited to the embodiments shown herein, and is to fit to the widest scope consistent with principles disclosed herein and features of novelty.
Claims (10)
1. a porous acid resin catalyst, it is characterized in that, described porous acid resin catalyst is to be directly incorporated in macromolecule resin using nano material as pore hard mould agent, then removal nano material is dissolved in reaction in an acidic solution, thus forming nano pore in macromolecule resin, carry out sulfonating reaction again and realize acid functionalization, and the nano-pore resin solid prepared is sour.
2. porous acid resin catalyst according to claim 1, it is characterised in that described porous acid resin catalyst specific surface area is more than 350m2/ g, exchange capacity is more than 4.0mmol/g.
3. the preparation method of a porous acid resin catalyst, it is characterized in that, nano material is directly incorporated in macromolecule resin as pore hard mould agent, then removal nano material is dissolved in reaction in an acidic solution, thus forming nano pore in macromolecule resin, carrying out sulfonating reaction again and realize acid functionalization, namely prepared nano-pore resin solid acid be porous acid resin catalyst;
The preparation method of described porous acid resin catalyst comprises the following steps that;
(1) the pre-modification of nano material: nano material that parts by weight 70��95 parts, size are 10��200nm and 5��30 parts of propenyls or propanoic acid are put in acetone solvent, reacts 1��4 hour at 50��60 DEG C; Then being evaporated removing acetone solvent at 80��100 DEG C, the surface esterification namely completing nano material modifiies, and obtains the modified porous nano material of hydrophobization;
(2) macromolecule resin polymerization synthesis: modified porous nano material, porogen and solvent that monomer A, crosslinking copolymerization monomer, initiator, step (1) obtain are made into oil-phase solution A;
Oil-phase solution A includes following components by weight percentage: modified porous nano material 2��20%; Monomer A30��70%; Crosslinking copolymerization monomer 2��18%; Initiator 0.1��3%; Porogen 5��20%; Surplus is solvent;
Being made into aqueous phase solution B with pure water, glue dispersant and inorganic dispersant, pure water, glue dispersant and inorganic dispersant weight ratio are 100: 1.6��2.0: 1.4��1.5;
Being mixed with weight ratio 1: 2.4��2.8 with aqueous phase solution B by oil-phase solution A, under stirring at 210��280 revs/min after even suspension dispersion, then be warming up to 80��84 DEG C of reaction 2h��6h, cooling, filtration washing obtain the polymer microballoon containing modified porous nano material; Then adopt steam distillation method to remove porogen and residual monomer at 95��102 DEG C described polymer microballoon again, obtain porous resin catalyst body Archon;
(3) molten except fill nano material: the porous resin catalyst body Archon that step (2) obtains with 2%��10% hydrochloric acid solution at 40��50 DEG C of stirring reaction 2��5h, wash and dried at 50��110 DEG C through drainage, obtain the bulk resin Archon containing nano-pore;
(4) acid functionalization of resin catalyst sulfonating reaction: the resin body Archon containing nano-pore obtained by step (3): oleum: dichloroethane solvent: Cu2SO4The weight ratio of sulfonation catalyst be 100: 410��480: 240��300: 3��5 ratio be made into reaction raw materials, at 50��85 DEG C swelling 1��3 hour; Being warming up at 82��140 DEG C stirring reaction 3��6h again, washing filtering removes remaining sulphuric acid, then removes dichloroethane solvent at 60��120 DEG C with distillating method, namely obtains porous resin solid acid catalyst;
Wherein, described nano material at least one in nano-calcium carbonate, nano aluminium oxide or CNT;
Wherein, described monomer A is at least one in styrene monomer, butene monomers, methyl methacrylate monomer, acrylonitrile monemer.
4. the preparation method of porous acid resin catalyst according to claim 3, it is characterised in that described crosslinking copolymerization monomer at least one in diallyl benzene, divinylbenzene, divinyl phenylmethane.
5. the preparation method of porous acid resin catalyst according to claim 3, it is characterised in that described initiator at least one in azodiisobutyronitrile or cumyl peroxide.
6. the preparation method of porous acid resin catalyst according to claim 3, it is characterised in that described solvent at least one in petroleum ether, normal hexane, butanone or ethyl acetate.
7. the preparation method of porous acid resin catalyst according to claim 3, it is characterised in that described porogen at least one in benzene, toluene, butanol or normal heptane.
8. the preparation method of porous acid resin catalyst according to claim 3, it is characterised in that described glue dispersant is at least one in gelatin, arabic gum.
9. the preparation method of porous acid resin catalyst according to claim 3, it is characterised in that described inorganic dispersant is at least one in silicon oxide, titanium oxide.
10. the application of a porous acid resin catalyst, it is characterised in that described porous acid resin catalyst is combined in the reaction of sec-Butyl Acetate for acetic acid and butene esters.
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| CN112495447A (en) * | 2020-12-25 | 2021-03-16 | 中国科学院兰州化学物理研究所 | Catalyst composition for synthesizing methyl methacrylate |
| CN113117750A (en) * | 2021-03-17 | 2021-07-16 | 南京福昌环保有限公司 | Preparation and application of continuous esterification composite catalyst for acrylic acid and ester waste oil recovery device |
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| CN106975517A (en) * | 2017-05-16 | 2017-07-25 | 同济大学 | A kind of green high-efficient synthesizes the heterogeneous catalyst of 2,4 DI-tert-butylphenol compounds |
| CN107876031A (en) * | 2017-11-28 | 2018-04-06 | 珠海健帆生物科技股份有限公司 | A kind of uremia blood-purifying adsorbing agent and preparation method thereof |
| CN107876031B (en) * | 2017-11-28 | 2020-11-13 | 健帆生物科技集团股份有限公司 | Blood purification adsorbent for uremia and preparation method thereof |
| CN111359661A (en) * | 2020-03-19 | 2020-07-03 | 辽宁科京新材料科技有限公司 | Preparation method of perfluorosulfonic acid resin super acidic catalyst with porous structure |
| CN112371093A (en) * | 2020-10-28 | 2021-02-19 | 江门市长优实业有限公司 | Nickel recovery agent and application thereof |
| CN114433242A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Embedded copper oxide nanotube catalyst |
| CN114433242B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | Embedded copper oxide nanotube catalyst |
| CN112495447A (en) * | 2020-12-25 | 2021-03-16 | 中国科学院兰州化学物理研究所 | Catalyst composition for synthesizing methyl methacrylate |
| CN113117750A (en) * | 2021-03-17 | 2021-07-16 | 南京福昌环保有限公司 | Preparation and application of continuous esterification composite catalyst for acrylic acid and ester waste oil recovery device |
| CN115784879A (en) * | 2022-11-24 | 2023-03-14 | 凯瑞环保科技股份有限公司 | Synthesis method of sec-butyl acetate |
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