CN103638969B

CN103638969B - A kind of preparation method of solid acid catalyst, its preparation method and double olefin compound

Info

Publication number: CN103638969B
Application number: CN201310693710.2A
Authority: CN
Inventors: 张贺新; 张学全; 白晨曦; 张春雨; 张梦辉; 于琦周; 毕吉福; 代全权; 那丽华; 董博; 胡庆娟
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2013-12-17
Filing date: 2013-12-17
Publication date: 2016-08-24
Anticipated expiration: 2033-12-17
Also published as: CN103638969A

Abstract

The invention provides a kind of solid acid catalyst, including silicoaluminophosphamolecular molecular sieves and auxiliary agent；In described silicoaluminophosphamolecular molecular sieves, the mol ratio of silicon, aluminium and phosphorus is 0.005～2.5:1:0.1～5.The solid acid catalyst that the present invention provides can be catalyzed to be had the carbonyl-containing compound of structure shown in formula (I) and has the condensation reaction of the monoolefinic compound of structure shown in formula (II), prepares double olefin compound.The solid acid catalyst that the present invention provides has higher selectivity of product, decreases the generation of side reaction in condensation reaction, improves the productivity of double olefin compound.And, the solid acid catalyst catalysis activity that the present invention provides is high, has higher conversion ratio.It addition, the solid acid catalyst toxicity that the present invention provides is little, life-span length, regenerability are good, are suitable to industrialized production.

Description

A kind of preparation method of solid acid catalyst, its preparation method and double olefin compound

Technical field

The present invention relates to technical field of organic synthesis, particularly relate to a kind of solid acid catalyst, its preparation side Method and the preparation method of double olefin compound.

Background technology

Double olefin compound is the unsaturated hydrocarbon containing two carbon-carbon double bonds.Double olefin compound In isoprene be mainly used for producing isoprene rubber, butyl rubber, medicine pesticide intermediate and conjunction Become lube oil additive, vulcanizer etc..

In prior art, the preparation method of isoprene mainly has dehydriding, synthetic method and extraction process, its Middle synthetic method includes isobutene-formaldehyde method, acetylene-acetone method and propylene dimerization.According to reaction process not With, isobutene and formaldehyde method are further divided into two-step method and one-step method.Wherein, two-step method is to urge in acidity In the presence of agent, isobutene and formaldehyde carry out condensation reaction at 70 DEG C～100 DEG C, generate 4,4-dimethyl -1,3-dioxane and byproduct, isolate 4,4-dimethyl-1,3-dioxane；Then, 4,4-dimethyl -1,3-dioxane is cracked to form isoprene, formaldehyde and water at 250 DEG C～280 DEG C.This two-step method Technological process is loaded down with trivial details, and accessory substance is complicated.One-step method is in the presence of acidic, gas phase isobutene and Formaldehyde is more than 200 DEG C, and Direct Dehydration is condensed to yield isoprene and water.The technique of this one-step method has The advantages such as flow process is short, accessory substance is few.Therefore, olefine aldehydr gas-phase one-step method synthesis isoprene becomes research Focus.

Efficient catalyst is isobutene and the key problem in technology of formaldehyde gas-phase one-step method synthesis isoprene.Cross Middle scholar (scholar, Xue Jinzhen, Xu Xianlun etc. in Guoing.Alkene, aldehyde one-step synthesis isoprene boric acid catalyst Research.Chemistry of fuel journal, March nineteen eighty-three, volume 11 3 phase, 57～63.) et al. at boron and two groups of phosphorus Divided catalyst with the addition of again vanadium, potassium and aluminium three component, obtain five component catalysts, and by described five groups Divided catalyst is used for catalyzing iso-butane alkene and the condensation reaction of formaldehyde, obtains isoprene.Result of study shows, Regenerability relatively boron and the phosphorus two-component catalyst of boron, phosphorus, vanadium, aluminium and potassium five component catalyst obtain Improve, but this boron, phosphorus, vanadium, aluminium and potassium five component catalyst for isoamyl in condensation reaction products The selectivity of diene is the lowest, it is difficult to industrialized production.

Summary of the invention

In view of this, it is an object of the invention to provide a kind of solid acid catalyst, its preparation method and double The preparation method of olefin(e) compound.The solid acid catalyst that the present invention provides prepares diene at gas-phase one-step method During hydrocarbon compound, there is higher selectivity of product, improve the productivity of double olefin compound.

The invention provides a kind of solid acid catalyst, including silicoaluminophosphamolecular molecular sieves and auxiliary agent；

In described silicoaluminophosphamolecular molecular sieves, the mol ratio of silicon, aluminium and phosphorus is 0.005～2.5:1:0.1～5.

Preferably, described auxiliary agent is 0.1～20:100 with the mass ratio of silicoaluminophosphamolecular molecular sieves.

Preferably, described silicoaluminophosphamolecular molecular sieves is by including silicon source, aluminium source, phosphorus source and surfactant Raw material roasting obtains；

Described surfactant includes in cationic surfactant and hexadecyl trimethoxy silane Plant or two kinds.

The invention provides the preparation method of a kind of solid acid catalyst, comprise the following steps:

A) silicon source, aluminium source, phosphorus source and auxiliary agent raw material are mixed in a solvent, obtain catalyst precursor；

B) the catalyst precursor crystallization obtained by described step a), obtains catalyst intermediate；

C) the catalyst intermediate roasting obtained by described step b), obtains molecular sieve catalyst.

Preferably, described silicon source includes Ludox, Silica hydrogel, waterglass, silica and positive esters of silicon acis In one or more.

Preferably, source of aluminium includes aluminium salt, aluminate, aluminum oxide, alkoxy aluminum compound, vacation suddenly One or more in female stone and boehmite.

Preferably, during phosphorus source includes the oxide of phosphoric acid, phosphate, organic phosphoric acid compound and phosphorus One or more.

Preferably, in described step b), the temperature of crystallization is 50 DEG C～400 DEG C；

The time of crystallization is more than or equal to 5min.

Preferably, in described step c), the temperature of roasting is 200 DEG C～800 DEG C；

The time of roasting is more than or equal to 1h.

The invention provides the preparation method of a kind of double olefin compound, comprise the following steps:

To there is the carbonyl-containing compound of structure shown in formula (I) and there is the monoene hydrocarbonylation of structure shown in formula (II) Compound carries out condensation reaction under the effect of catalyst, obtains double olefin compound；

Prepare described in solid acid catalyst described in described catalyst technique scheme or technique scheme The solid acid catalyst that method obtains；

Wherein, R₁、R₂、R₃And R₄Independently selected from hydrogen, alkyl or aromatic radical.

Preferably, R₁、R₂、R₃And R₄Independently selected from the straight chained alkyl that hydrogen, carbon number are 1～8, Carbon number be 1～8 branched alkyl, carbon number be 1～8 the substituted phenyl of straight chained alkyl or carbon former Subnumber is the substituted phenyl of branched alkyl of 1～8.

Preferably, there is described in the carbonyl-containing compound of structure shown in formula (I) and there is structure shown in formula (II) The mol ratio of monoolefinic compound be 1:1～12；

The quality of described solid acid catalyst with there is the material of the carbonyl-containing compound of structure shown in formula (I) Amount than for (1～3) g:1mol.

Preferably, the temperature of described condensation reaction is 230 DEG C～370 DEG C；

The time of described condensation reaction is 30min～70min.

The invention provides a kind of solid acid catalyst, including silicoaluminophosphamolecular molecular sieves and auxiliary agent；Described phosphorus In acid Si-Al molecular sieve, the mol ratio of silicon, aluminium and phosphorus is 0.005～2.5:1:0.1～5.The solid that the present invention provides Acid catalyst can be catalyzed to be had the carbonyl-containing compound of structure shown in formula (I) and has structure shown in formula (II) The condensation reaction of monoolefinic compound, prepare double olefin compound.The solid acid that the present invention provides Catalyst has higher selectivity of product, decreases the generation of side reaction in condensation reaction, improves The productivity of double olefin compound.And, the solid acid catalyst catalysis activity that the present invention provides is high, tool There is higher conversion ratio.It addition, the present invention provide solid acid catalyst toxicity is little, life-span length, regeneration Performance is good, is suitable to industrialized production.Test result indicate that, isobutene and formaldehyde are at solid acid catalyst Under effect, the selectivity (in terms of aldehyde) of product up to 85.6%, conversion ratio (in terms of aldehyde) is the highest Reach 92.8%.

Accompanying drawing explanation

Fig. 1 is the structural representation of the fixed bed reactors that the embodiment of the present invention uses；

Fig. 2 is regeneration and the life assessment figure that the embodiment of the present invention 64 obtains solid acid catalyst.

Detailed description of the invention

The invention provides a kind of solid acid catalyst, including silicoaluminophosphamolecular molecular sieves and auxiliary agent；Described phosphorus In acid Si-Al molecular sieve, the mol ratio of silicon, aluminium and phosphorus is 0.005～2.5:1:0.1～5.

The solid acid catalyst that the present invention provides can be catalyzed has the chemical combination containing carbonyl of structure shown in formula (I) Thing and have the condensation reaction of the monoolefinic compound of structure shown in formula (II), prepares double olefin compound. The solid acid catalyst that the present invention provides has higher selectivity of product, decreases in condensation reaction The generation of side reaction, improves the productivity of double olefin compound.And, the solid acid that the present invention provides is urged Agent catalysis activity is high, has higher conversion ratio.It addition, the solid acid catalyst poison that the present invention provides Property little, life-span length, regenerability are good, are suitable to industrialize production continuously.

The solid acid catalyst that the present invention provides includes silicoaluminophosphamolecular molecular sieves.In the present invention, described phosphorus In acid Si-Al molecular sieve, the mol ratio of silicon, aluminium and phosphorus is 0.005～2.5:1:0.1～5, is preferably 0.01～2:1:0.2～4, more preferably 0.05～1:1:0.3～3.

In the present invention, described silicoaluminophosphamolecular molecular sieves is preferably by including silicon source, aluminium source and the raw material of phosphorus source Roasting obtains.In the present invention, described silicon source preferably includes Ludox, Silica hydrogel, waterglass, dioxy One or more in SiClx and positive esters of silicon acis, more preferably include Ludox, silica and positive esters of silicon acis In one or more, most preferably Ludox；Source of aluminium preferably includes aluminium salt, aluminate, oxidation One or more in aluminium, alkoxy aluminum compound, false boehmite and boehmite, more preferably include One or more in aluminum oxide, aluminium salt and boehmite, most preferably boehmite；Described phosphorus Source preferably includes one or more in the oxide of phosphoric acid, phosphate, organic phosphoric acid compound and phosphorus, More preferably include in phosphoric acid and organic phosphoric acid compound one or both, most preferably phosphoric acid.

In the present invention, the temperature of described roasting is preferably 200 DEG C～800 DEG C, more preferably 300 DEG C～700 DEG C, most preferably 500 DEG C～600 DEG C；The time of described roasting is preferably greater than equal to 1h, more preferably 1.5h～10h, most preferably 3h～5h.

In the present invention, prepare the raw material of described silicoaluminophosphamolecular molecular sieves the most also include surfactant and/ Or template.In the present invention, described surfactant preferably includes cationic surfactant and 16 One or both in alkyl trimethoxysilane；More preferably include tetradecyl trimethyl ammonium chloride, ten Six alkyl trimethyl ammonium bromides, dimethyl hexadecyl base [3-trimethyl silicane propyl group] ammonium chloride, dimethyl 18 One or more in alkyl [3-trimethyl silicane propyl group] ammonium chloride and hexadecyl trimethoxy silane；Optimum Choosing includes tetradecyl trimethyl ammonium chloride, dimethyl stearyl [3-trimethyl silicane propyl group] ammonium chloride and ten One or more in six alkyl trimethoxysilanes.In the present invention, described surfactant is with described The mol ratio of the aluminium in aluminium source is preferably 0.005～2.5:1；More preferably 0.01～2:1；Most preferably 0.1～1.5:1.

The present invention does not has special restriction to source and the kind of described template, uses people in the art Template known to Yuan.In the present invention, described template is preferably aminated compounds and alcohols The mixture of one or more in compound；More preferably triethylamine, diethylamine, n-propylamine, isopropylamine, Di-n-propylamine, diisopropylamine, tripropyl amine (TPA), n-butylamine, isobutyl amine, monoethanolamine, diethanol amine, three second Hydramine, tetramethyl oxyammonia, tetraethyl oxyammonia, tetrapropyl oxyammonia, tetrabutylammonium hydroxide One or more in amine, ethylene glycol, glycerine and polyethylene glycol；Most preferably triethylamine, isopropylamine, One or more in tetramethyl oxyammonia, diethanol amine and polyethylene glycol.In the present invention, described Template is preferably 0.15～10:1 with the mol ratio of the aluminium in source of aluminium；More preferably 1～8:1；Most preferably It is 3～5:1.

The solid acid catalyst that the present invention provides includes auxiliary agent.In the present invention, described auxiliary agent preferably includes The compound of Na, the compound of K, MgO, CaO, BaO, Al₂O₃、Bi₂O₃、Mn₂O₃、Sb₂O₃、 Ce₂O₃、ZnO、Zr₂O₃、Fe₂O₃、Ag、Si₂O₃、P₂O₅、C₆H₆SO₃H and B₂O₃In one Or it is multiple；More preferably include P₂O₅、Al₂O₃、Sb₂O₃、MoO₃、Ag、Fe₂O₃、CrO₃、CuO And Ni₂O₃In one or more.In the present invention, described auxiliary agent and described silicoaluminophosphamolecular molecular sieves Mass ratio is preferably 0.1～20:100；More preferably 2～5:100.

The solid acid catalyst that the present invention provides the most also includes carrier.In the present invention, described carrier is excellent Choosing includes one or more in the compound of magnesium, the compound of aluminium, the compound of silicon and material with carbon element；More Preferably include the salt compounds of magnesium, Al₂O₃、SiO₂With one or more in material with carbon element, most preferably wrap Include MgCl₂、Al₂O₃、SiO₂, one or more in Graphene and CNT.The present invention is to described The source of carrier does not has special restriction, uses above-mentioned carrier well known to those skilled in the art, can To use the commercial goods of above-mentioned carrier.In the present invention, described silicoaluminophosphamolecular molecular sieves and the matter of carrier Amount ratio preferably 0.01～1:1, more preferably 0.1～0.5:1.

C) the catalyst intermediate roasting obtained by described step b), obtains solid acid catalyst.

Silicon source, aluminium source, phosphorus source and auxiliary agent raw material are mixed by the present invention in a solvent, obtain body before catalyst Body.Aluminium source and phosphorus source preferably are charged first in solvent mix by the present invention, add silicon source and auxiliary agent Raw material, obtains catalyst precursor；More preferably it is charged first to aluminium source and phosphorus source in solvent mix, then to Wherein it is sequentially added into silicon source and auxiliary agent raw material, is eventually adding surfactant and/or template, is catalyzed Agent precursor；Most preferably aluminium source and phosphorus source are charged first in solvent mixing, carry out the first stirring, then add Enter silicon source and auxiliary agent raw material, carry out the second stirring, be eventually adding surfactant and/or template, carry out 3rd stirring, obtains catalyst precursor.

In the present invention, described silicon source, aluminium source and phosphorus source preferably with the silicon source described in technique scheme, Aluminium source is consistent with the kind of phosphorus source, does not repeats them here.The present invention is the most special to the source in described silicon source Restriction, use silicon source well known to those skilled in the art, as use above-mentioned silicon source commercial goods. In the present invention, the silicon in described silicon source is preferably 0.005～2.5:1 with the mol ratio of the aluminium in source of aluminium； More preferably 0.01～2:1；Most preferably 0.1～1.5:1.It is special that the source of phosphorus source is not had by the present invention Limit, use phosphorus source well known to those skilled in the art, as used the commercial goods of above-mentioned phosphorus source. In the present invention, the phosphorus in phosphorus source is preferably 0.1～5:1 with the mol ratio of the aluminium in source of aluminium；More It is preferably 0.5～4:1；Most preferably 1～3:1.

In the present invention, described auxiliary agent raw material preferably includes the compound of Na, the compound of K, Mg Compound, the compound of Ca, the compound of Co, the compound of Ba, the compound of Mo, the change of Al Compound, the compound of Bi, the compound of Mn, the compound of Sb, the compound of Ce, the compound of Cr, The compound of V, the compound of Zn, the compound of Zr, the compound of Fe, the compound of Ag, Re Compound, the compound of Si, the compound of P, the compound of Cu, the compound of Nd, the compound of S With one or more in the compound of B；More preferably include the compound of P, the compound of Al, Sb Compound, the compound of Mo, the compound of Ag, the compound of Fe, the compound of Cu and the change of Nd One or more in compound；Most preferably include P₂O₅、Al(OH)₃、Sb₂O₃、MoO₃、AgNO₃、 Fe₂O₃、CrO₃、CuSO₄And NdCl₃·6H₂One or more in O.In the present invention, described silicon source It is preferably 1～15:1, more preferably 2～10:1 with the mass ratio of auxiliary agent raw material.

In the present invention, described solvent is preferably water, more preferably includes running water, distilled water and deionization One or more in water；Most preferably deionized water.In the present invention, described solvent and source of aluminium In the mol ratio of aluminium be preferably 5～250:1；More preferably 10～200:1；Most preferably 30～100:1.

In the present invention, the temperature of described first stirring is preferably 15 DEG C～40 DEG C, more preferably 20 DEG C～30 ℃；The time of described first stirring is preferably 0.5h～1.5h, more preferably 1h.Described second stirring Temperature is preferably 15 DEG C～40 DEG C, more preferably 20 DEG C～30 DEG C；The time of described second stirring is preferably 0.5 H～1.5h, more preferably 1h；The temperature of described 3rd stirring is preferably 15 DEG C～40 DEG C, and more preferably 20 DEG C～30 DEG C；The time of described 3rd stirring is preferably 0.5h～1.5h, more preferably 1h.

After obtaining catalyst precursor, the present invention, by described catalyst precursor crystallization, obtains in catalyst Mesosome.Catalyst precursor is preferably placed in crystallization in synthesis reactor by the present invention, obtains catalyst intermediate. The present invention does not has special restriction to described synthesis reactor, uses synthesis reactor well known to those skilled in the art i.e. Can.In the present invention, described synthesis reactor is preferably stainless steel synthesis reactor, more preferably band polytetrafluoroethylene (PTFE) The stainless steel synthesis reactor of liner.

In the present invention, the temperature of described crystallization is preferably 50 DEG C～400 DEG C, more preferably 100 DEG C～350 DEG C, most preferably 150 DEG C～250 DEG C；The time of described crystallization is preferably greater than or equal to 5min；More preferably 1h～200h, most preferably 20h～40h.

After completing catalyst precursor crystallization, the present invention preferably the crystallization product obtained is carried out separation of solid and liquid, Wash, be dried, obtain catalyst intermediate.The present invention is the most special to the method for described separation and washing Restriction, use the technical scheme of separation well known to those skilled in the art and washing.The present invention is excellent The solid washing that choosing uses deionized water described separation of solid and liquid to be obtained is the most neutral.The present invention is dried described Method there is no special restriction, use dry technology scheme well known to those skilled in the art.This Crystallization product after washing is preferably dried by invention.The present invention does not has special limit to the described dry time System, is preferably dried the crystallization product after washing to constant weight；Described dry temperature is preferably 80 DEG C～110 DEG C, more preferably 95 DEG C～100 DEG C.

After obtaining catalyst intermediate, the present invention, by described catalyst intermediate roasting, obtains solid acid and urges Agent.The present invention does not has special restriction to the equipment of described roasting, preferably by described catalyst intermediate At Muffle kiln roasting.In the present invention, the temperature of described roasting is preferably 200 DEG C～800 DEG C, more preferably It is 300 DEG C～700 DEG C, most preferably 500 DEG C～600 DEG C；The time of described roasting is preferably greater than or equal to 1h, More preferably 1.5h～10h, most preferably 3h～5h.

The solid acid catalyst that the present invention provides can be catalyzed has the chemical combination containing carbonyl of structure shown in formula (I) Thing and there is the monoolefinic compound of structure shown in formula (II) carry out condensation reaction under the effect of catalyst, To double olefin compound.The solid acid catalyst that the present invention provides has two kinds of activated centre: Bronsted acid (letters Claim B acid) activated centre and Lewis acid (be called for short L acid) activated centre.In olefine aldehyde condensation course of reaction, B acid activity center Main Function, the solid acid catalyst that the present invention provides has the B acid of high level Activated centre, the solid acid catalyst that the B acid activity center of high level makes the present invention provide has relatively High selectivity of product, decreases the generation of side reaction in condensation reaction, improves diolefin chemical combination The productivity of thing；The specific surface area of the solid acid catalyst that the present invention provides is big, has higher catalysis activity, Thus improve conversion ratio.

The total acid content of the present invention solid acid catalyst to obtaining, B acid activity center and L acid activity center Ratio and specific surface area be determined.Measurement result shows, the solid acid catalysis that the present invention provides The total acid content of agent is up to the ratio at 3.54mmol/g, B acid activity center and L acid activity center for being up to 2.51, specific surface area is 342m to the maximum²/g。

Described catalyst is described in the solid acid catalyst described in technique scheme or technique scheme The solid acid catalyst that preparation method obtains；

In the present invention, there is the carbonyl-containing compound of structure shown in formula (I) and there is structure shown in formula (II) Monoolefinic compound carry out condensation reaction, shown in the reaction equation of condensation reaction such as formula (a).

Wherein, cat represents the solid acid catalyst that the present invention provides；R₁、R₂、R₃And R₄With above-mentioned skill R described in art scheme₁、R₂、R₃And R₄Unanimously, at this to substituent R₁、R₂、R₃And R₄The most superfluous State；R₄' and R₄Differ-a H.

The present invention will have the carbonyl-containing compound of structure shown in formula (I) and has the list of structure shown in formula (II) Olefin(e) compound carries out condensation reaction under the effect of catalyst, obtains double olefin compound.The present invention couple Described have the kind of the carbonyl-containing compound of structure shown in formula (I) and source there is no special restriction, adopt With well known to those skilled in the art, there is the carbonyl-containing compound of structure shown in formula (I).At this R in bright, in formula (I)₁And R₂Independently selected from hydrogen, alkyl or aromatic radical；Preferably, R₁And R₂Solely On the spot selected from hydrogen, carbon number be 1～8 straight chained alkyl, carbon number be 1～8 branched alkyl, carbon Atomicity is the substituted phenyl of straight chained alkyl of 1～8 or the substituted benzene of branched alkyl that carbon number is 1～8 Base, it is highly preferred that R₁And R₂Independently selected from one or more in hydrogen, methyl and isopropyl.At this In invention formula (I), work as R₁And R₂Independently selected from the substituted phenyl of the straight chained alkyl that carbon number is 1～8 or When carbon number is the substituted phenyl of branched alkyl of 1～8, the present invention is to the replacement site on described phenyl There is no special restriction, can be ortho position, it is also possible to for meta, it is also possible to for contraposition.

Specifically, R is worked as₁And R₂During for hydrogen, described in there is the carbonyl-containing compound of structure shown in formula (I) be Formaldehyde；Work as R₁For methyl, R₂During for hydrogen, described in there is the carbonyl-containing compound of structure shown in formula (I) be Acetaldehyde；Work as R₁For isopropyl, R₂During for hydrogen, described in there is the carbonyl-containing compound of structure shown in formula (I) For isobutylaldehyde.

The present invention to described have the kind of the monoolefinic compound of structure shown in formula (II) and source the most special Restriction, use and well known to those skilled in the art there is the monoolefinic compound of structure shown in formula (II).

In the present invention, in formula (II), R₃And R₄Independently selected from hydrogen, alkyl or aromatic radical；Preferably, R₃And R₄Independently selected from hydrogen, carbon number be 1～8 straight chained alkyl, carbon number be 1～8 side chain Alkyl, carbon number are the substituted phenyl of straight chained alkyl of 1～8 or branched alkyl that carbon number is 1～8 Substituted phenyl, it is highly preferred that R₃And R₄Independently selected from hydrogen, methyl, isopropyl and benzyl One or more.Work as R₃And R₄Independently selected from the substituted phenyl of the straight chained alkyl that carbon number is 1～8 or When carbon number is the substituted phenyl of branched alkyl of 1～8, the present invention is to the replacement site on described phenyl There is no special restriction, can be ortho position, it is also possible to for meta, it is also possible to for contraposition.

Specifically, R is worked as₃And R₄When being methyl simultaneously, described in there is the monoene hydrocarbonylation of structure shown in formula (II) Compound is isobutene；Work as R₃For isopropyl, R₄During for methyl, described in there is the monoene of structure shown in formula (II) Hydrocarbon compound is 2,3-dimethyl-1-butylene；Work as R₃For methyl, R₄During for phenyl, described in there is formula (II) The monoolefinic compound of shown structure is AMS.

In the present invention, described in there is the monoolefinic compound of structure shown in formula (II) can be buied by market, it is possible to Prepare voluntarily according to preparation method well known to those skilled in the art.In the present invention, there is described in formula (II) Shown in the preparation method of monoolefinic compound of structure preferably include following steps:

Carry out ether solution reaction by having the ether compound of structure shown in formula (III), obtain that there is formula (II) shown The monoolefinic compound of structure；

Wherein, R₅And R₆Independently selected from hydrogen, alkyl or aromatic radical.

In the present invention, the R in formula (III)₅And R₆Independently selected from hydrogen, alkyl or aromatic radical；Preferably, R₅And R₆Independently selected from hydrogen, carbon number be 1～8 straight chained alkyl, carbon number be 1～8 side chain Alkyl, carbon number are the substituted phenyl of straight chained alkyl of 1～8 or branched alkyl that carbon number is 1～8 Substituted phenyl, it is highly preferred that R₅And R₆Independently selected from hydrogen, methyl, isopropyl and benzyl One or more.Work as R₅And R₆Independently selected from the substituted phenyl of the straight chained alkyl that carbon number is 1～8 or When carbon number is the substituted phenyl of branched alkyl of 1～8, the present invention is to the replacement site on described phenyl There is no special restriction, can be ortho position, it is also possible to for meta, it is also possible to for contraposition.Specifically, when R₅And R₆When being methyl, having the ether compound of structure shown in formula (III) is methyl tertiary butyl ether(MTBE).

In the present invention, the temperature of described ether solution reaction is preferably 150 DEG C～300 DEG C, more preferably 180 DEG C ～280 DEG C；The time of described ether solution reaction is preferably 1h～5h, more preferably 2h～4h；Described ether solution is anti- The catalyst that should use preferably includes Al₂O₃, sulfate, phosphate, the oxide of uranium, the hydroxide of uranium One or more in thing and activated carbon, more preferably include Al₂O₃、U₃O₈And Ca₃(PO₄)₂In one Or it is multiple；The pressure of described ether solution reaction is preferably 0.3MPa～0.6MPa, and more preferably 0.35 MPa～0.55MPa.

In the present invention, there is described in the carbonyl-containing compound of structure shown in formula (I) and have shown in formula (II) The mol ratio of the monoolefinic compound of structure is preferably 1:1～12, more preferably 1:2～11, most preferably 1:3～10；The quality of described solid acid catalyst with there is the thing of the carbonyl-containing compound of structure shown in formula (I) The amount of matter, than being (1～3) g:1mol, is more preferably (1.5～2.5) g:1mol.

In the present invention, the temperature of described condensation reaction is preferably 230 DEG C～370 DEG C, more preferably 250 DEG C ～350 DEG C；The time of described condensation reaction is preferably 30min～70min, more preferably 40min～60min, In described condensation reaction, gas-solid contact time is preferably 0.1s～1.2s, more preferably 0.2s～1.0s, optimum Elect 0.3s～0.8s as.

The present invention does not has special restriction to the device of described condensation reaction, it is preferred to use as shown in Figure 1 Reaction unit, Fig. 1 is the structural representation of the fixed bed reactors that the embodiment of the present invention uses.Wherein, 11 is the first material feed pump；12 is the second material feed pump；21 is the first valve, and 22 is the second valve Door, 31 is the first material pipe, and 32 is the second material pipe, and 4 is mixed material pipeline, and 5 is reaction Pipe；6 is condenser；7 is gas-liquid separation and carbonyls retracting device；8 is gas chromatograph.

In the present invention, described fixed bed reactors include the first material feed pump 11 and the first material pipe 31, the discharging opening of described first material feed pump 11 is connected with the charging aperture of described first material pipe 31, First material is delivered to the first material pipe 31；The present invention to the diameter of described first material pipe 31, Material and length do not have special restriction, meet practical operation condition required；

In the present invention, described fixed bed reactors include valve 21, and the present invention is in order to control material Inlet amount, in an embodiment of the present invention, described first material pipe 31 is provided with the first valve 21, For controlling the conveying of described first material.The present invention to described first valve 21 at described first materail tube The position arranged on road 31, either with or without restriction, can be arranged at any position of described first material pipe 31 Put；

In the present invention, described fixed bed reactors include the second material feed pump 12 and the second material pipe 32, the discharging opening of described second material feed pump 12 is connected with the charging aperture of described second material pipe 32, Second material is delivered to the second material pipe 32；The present invention to the diameter of described second material pipe 32, Material and length do not have special restriction, meet practical operation condition；The present invention is to described first thing The material variety of pipe material 31 and the conveying of the second material pipe 32 does not limit, at embodiments of the invention In, described first material pipe 31 and the second material pipe 32 will have containing of structure shown in formula (I) respectively The compound of carbonyl and there is the monoolefinic compound of structure shown in formula (II) be delivered in mixed material pipeline 4 ?；

In the present invention, described fixed bed reactors include valve 22, and the present invention is in order to control material Inlet amount, in an embodiment of the present invention, described second material pipe 32 is provided with the second valve 22, For controlling the conveying of described second material；The present invention to described second valve 22 at described second materail tube The position arranged on road 32 does not limit, and can be arranged at the optional position of described second material pipe 32；

In the present invention, described fixed bed reactors include mixed material pipeline 4, described mixed material pipeline The discharging opening of 4 is connected with the entrance of reaction tube 5, and the present invention is to the diameter of described mixed material pipeline 4, material Matter and length do not have special restriction, meet practical operation condition required；In the present invention, described Mixed material pipeline 4 is by the first material come by described first material pipe conveying with by the second material pipe The second material that conveying comes mixes and is delivered to reaction tube 5；

In the present invention, described fixed bed reactors include reaction tube 5, the outlet of described reaction tube 5 and institute The entrance stating condenser 6 is connected, and reaction tube 5 is used for holding solid acid catalyst and providing condensation reaction Place.The present invention does not has special restriction to the size of described reaction tube, can be arbitrary dimension；At this In inventive embodiment, a diameter of Φ 15mm of described reaction tube 5～Φ 20mm；

In the present invention, described fixed bed reactors include condenser 6, the outlet of described condenser 6 and institute The entrance stating gas-liquid separation and carbonyls retracting device 7 is connected, and completes polymerization anti-in reaction tube 5 The product obtained after should be transported to condenser 6, and described condenser 6 is by the most unreacted carbonylation Compound and portion of product condense out；

In the present invention, described fixed bed reactors include gas-liquid separation and carbonyls retracting device 7, The outlet of described gas-liquid separation and carbonyls retracting device 7 and the entrance phase of described gas chromatograph 8 Even, gas-liquid separation and carbonyls retracting device 7 are used for separating the product through condenser 6 And reclaim unreacted carbonyls；

In the present invention, described fixed bed reactors include that gas chromatograph 8, gas chromatograph 8 are used for surveying The gas-phase product determining gas-liquid separation device separation forms and the content of double olefin compound in product；At this In bright embodiment, described gas chromatograph is Thermo Scientific Trace GC ultra chromatograph.

Below in conjunction with the fixed bed reactors shown in Fig. 1, the diolefin the chemical combination further present invention provided The preparation method of thing is described in detail:

The present invention is carried having the carbonyl containing compound of structure shown in formula (I) by the first material feed pump 11 To the first material pipe 31, during conveying, control to have knot shown in formula (I) by the first valve 21 The addition of the carbonyl containing compound of structure；To have the monoolefinic compound of structure shown in formula (II) by second Material feed pump 12 is delivered to the second material pipe 32, during conveying, by the second valve 22 Control that there is the addition of the monoolefinic compound of structure shown in formula (II)；

Described first material pipe 31 is delivered to mixture by having the carbonyl containing compound of structure shown in formula (I) Pipe material 4, described second material pipe 32 is delivered to having the monoolefinic compound of structure shown in formula (II) Mixed material pipeline 4；Described have the carbonyl containing compound of structure shown in formula (I) and have knot shown in formula (II) The monoolefinic compound of structure converges at mixed material pipeline 4, and is delivered to reaction tube 5；

In reaction tube 5, be pre-placed solid acid catalyst, have structure shown in formula (I) containing carbonyl Compound and there is the monoolefinic compound of structure shown in formula (II) enter under the effect of above-mentioned solid acid catalyst Row condensation reaction, obtains product, and product is transported to condenser 6；

In condenser 6, portion of product is condensed, and obtains the liquid product of condensation and uncooled gas phase Material, then liquid product and the uncooled gaseous substance of described condensation are delivered to gas-liquid separation and carbonylation In compound retracting device 7；

Described gas-liquid separation and carbonyls retracting device 7 carry out gas-liquid separation and reclaim unreacted carbonyl Based compound, unreacted carbonyls sodium sulfite solution titrates with dilute sulfuric acid after absorbing again, surveys Determine the content of unreacted carbonyls, and then calculate carbonyls conversion ratio；Finally by gaseous substance It is passed in gas chromatograph 8；

Gaseous substance is measured by gas chromatograph 8, measures the diolefin chemical combination generated in gaseous substance The kind of thing and the content of double olefin compound.

The invention provides a kind of solid acid catalyst, including silicoaluminophosphamolecular molecular sieves and auxiliary agent；Described phosphorus In acid Si-Al molecular sieve, the mol ratio of silicon, aluminium and phosphorus is 0.005～2.5:1:0.1～5.The solid that the present invention provides Acid catalyst can be catalyzed to be had the carbonyl-containing compound of structure shown in formula (I) and has structure shown in formula (II) The condensation reaction of monoolefinic compound, prepare double olefin compound.The solid acid that the present invention provides Catalyst has higher selectivity of product, decreases the generation of side reaction in condensation reaction, improves The productivity of double olefin compound.And, the solid acid catalyst catalysis activity that the present invention provides is high, tool There is higher conversion ratio.It addition, the present invention provide solid acid catalyst toxicity is little, life-span length, regeneration Performance is good, is suitable to industrialize production continuously.

In order to further illustrate the present invention, a kind of solid acid provided the present invention below in conjunction with embodiment is urged The preparation method of agent, its preparation method and double olefin compound is described in detail, but can not be by it Be interpreted as limiting the scope of the present invention.

Embodiment 1

By 40mL deionized water, boehmite and the 23g H of 17g alumina content 60wt%₃PO₄ Mixing and stirring, then it is added thereto to 6g Ludox, described Ludox contains the SiO of 40wt%₂、 Average grain diameter is 20 microns, Na⁺Content less than 0.1wt%, and more than 0, be eventually adding auxiliary agent, institute State auxiliary agent for containing 0.005molCa₃(PO₄)₂10mL deionized water solution, after being stirred at room temperature 1h Add 30g triethylamine, and continue to stir 1h, obtain catalyst precursor；

Obtained catalyst precursor is placed in the band teflon-lined stainless steel synthesis of 200mL In still, by airtight for stainless steel synthesis reactor heating, crystallization 24h at 60 DEG C, by gained crystallization product Remove mother liquor, be washed with deionized, after drying at 100 DEG C, obtain catalyst intermediate；

Dried catalyst intermediate being placed in Muffle furnace, at 800 DEG C, roasting 1h, obtains solid Acid catalyst.

The total acid content of the present invention solid acid catalyst to obtaining, B acid activity center and L acid activity center Ratio and specific surface area be tested.

The total acid content of the solid acid catalyst that the embodiment of the present invention obtains is in 3.49mmol/g, B acid activity The ratio at the heart and L acid activity center is 2.36, and specific surface area is 320m²/g。

Embodiment 2

By 40mL deionized water, boehmite and the 1g H of 17g alumina content 60wt%₃PO₄ Mixing and stirring, then it is added thereto to 37.5g Ludox, described Ludox contains the SiO of 40wt%₂、 Average grain diameter is 20 microns, Na⁺Content less than 0.1wt%, and more than 0, be eventually adding auxiliary agent, institute State auxiliary agent for containing 0.005mol CrO₃10mL deionized water solution, be stirred at room temperature after 1h and add 30g triethylamine, and continue to stir 1h, obtain catalyst precursor；

Gained catalyst precursor is placed in the band teflon-lined stainless steel synthesis reactor of 200mL In, by airtight for stainless steel synthesis reactor heating, crystallization 0.1h at 400 DEG C, by gained crystallization product Remove mother liquor, be washed with deionized, after drying at 100 DEG C, obtain catalyst intermediate；

The catalyst intermediate obtained being placed in Muffle furnace, at 200 DEG C, roasting 5h, obtains solid acid Catalyst.

The total acid content of the solid acid catalyst that the embodiment of the present invention obtains is 3.54mmol/g, B acid/L acid ratio Being 2.51, specific surface area is 342m²/g。

Embodiment 3

By 40mL deionized water, boehmite and the 50g H of 17g alumina content 60wt%₃PO₄ Mixing and stirring, then it is added thereto to 0.075g Ludox, described Ludox contains the SiO of 40wt%₂、 Average grain diameter is 20 microns, Na⁺Content less than 0.1wt%, and more than 0, be eventually adding auxiliary agent, institute Stating auxiliary agent is 0.05mol P₂O₅, add 30g triethylamine after being stirred at room temperature 1h, and continue to stir 1 H, obtains catalyst precursor；

Gained catalyst precursor is placed in the band teflon-lined stainless steel synthesis reactor of 200mL In, by airtight for stainless steel synthesis reactor heating, crystallization 1.5h at 300 DEG C, by gained crystallization product Remove mother liquor, be washed with deionized, after drying at 100 DEG C, obtain catalyst intermediate；

Embodiment 4

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, The present embodiment is with Al (OH)₃For auxiliary agent raw material.

Embodiment 5

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, The present embodiment is with Sb₂O₃For auxiliary agent raw material.

Embodiment 6

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, The present embodiment is with MoO₃For auxiliary agent raw material.

Embodiment 7

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, The present embodiment is with AgNO₃For auxiliary agent raw material.

Embodiment 8

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, The present embodiment is with Fe₂O₃For auxiliary agent raw material.

Embodiment 9

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, The present embodiment is with CuSO₄For auxiliary agent raw material.

Embodiment 10

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, The present embodiment is with NdCl₃·6H₂O is auxiliary agent raw material, described NdCl₃·6H₂O is previously dissolved in mass fraction The HCl solution of 10% pre-processes.

Embodiment 11

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment is with isopropylamine as template.

Embodiment 12

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment is with tetrabutylammonium hydroxide amine as template.

Embodiment 13

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment is with diethanol amine as template.

Embodiment 14

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment is with polyethylene glycol as template.

Embodiment 15

The solid acid catalyst that the present invention prepares according to the technical scheme described in embodiment 1, distinguishes In, in the present embodiment boehmite be 8.5g, 7mL mass fraction be the H of 85%₃PO₄。

Embodiment 16

The solid acid catalyst that the present invention prepares according to the technical scheme described in embodiment 1, distinguishes In, in the present embodiment boehmite be 17g, 7mL mass fraction be the H of 85%₃PO₄。

Embodiment 17

The solid acid catalyst that the present invention prepares according to the technical scheme described in embodiment 1, distinguishes In, in the present embodiment boehmite be 34g, 14mL mass fraction be the H of 85%₃PO₄。

Embodiment 18

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, Catalyst preparation process equal proportion is amplified 10 times by the present embodiment.

Embodiment 19

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, Change prepare the reagent grade materials used by catalyst as industrial raw material into, investigate impurity to catalyst performance Impact.

Embodiment 20

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment is with Al₂O₃For carrier, described carrier uses after roasting 1h at 400 DEG C.

Embodiment 21

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment is with CNT as carrier, and described carrier uses after roasting 1h at 400 DEG C.

Embodiment 22

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment adds surfactant tetradecyl trimethyl ammonium chloride.

Embodiment 23

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment adds surfactant dimethyl hexadecyl base [3-trimethyl silicane propyl group] ammonium chloride.

Embodiment 24

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, The present embodiment adds surfactant hexadecyl trimethoxy silane.

Embodiment 25

The solid acid catalyst of 2g embodiment 1 gained is placed in the fixed bed reactors shown in Fig. 1, then Being passed through isobutene and formaldehyde that mol ratio is 7:1, be 320 DEG C in reaction temperature, gas-solid contact time is 0.4 React 60min under conditions of s, obtain product.

The present invention product to obtaining carries out Structural Identification, and result shows in product containing isoprene.

The selectivity of isoprene is calculated by the present invention, and result sees table 1, and table 1 is implemented for the present invention The experimental result of example 25～63 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the embodiment of the present invention 25 selectivity of isoprene in terms of formaldehyde is 69.0%.

Embodiment 26

The solid acid catalyst of 2g embodiment 2 gained is placed in the fixed bed reactors shown in Fig. 1, different It is logical that butylene passes sequentially through the first material feed pump, the first valve, the first material pipe and mixed material pipeline Enter to reaction tube, formaldehyde is passed sequentially through the second material feed pump, the second valve, the second material pipe Being passed through to reaction tube with mixed material pipeline, it is 7:1 that the present invention controls the mol ratio of isobutene and formaldehyde, In reaction tube, being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, Obtain product.

As can be seen from Table 1, the embodiment of the present invention 26 selectivity of isoprene in terms of formaldehyde is 66.7%.

Embodiment 27

The solid acid catalyst of 2g embodiment 3 gained is placed in the fixed bed reactors shown in Fig. 1, this Implementing the reaction condition provided according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 27 selectivity of isoprene in terms of formaldehyde is 66.7%.

Embodiment 28

The solid acid catalyst of 2g embodiment 4 gained is placed in the fixed bed reactors shown in Fig. 1, this Implementing the reaction condition provided according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 28 selectivity of isoprene in terms of formaldehyde is 69.6%.

Embodiment 29

The solid acid catalyst of 2g embodiment 5 gained is placed in the fixed bed reactors shown in Fig. 1, this Implementing the reaction condition provided according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, obtain product. The present invention product to obtaining carries out Structural Identification, and result shows in product containing isoprene.

As can be seen from Table 1, the embodiment of the present invention 29 selectivity of isoprene in terms of formaldehyde is 69.5%.

Embodiment 30

The solid acid catalyst of 2g embodiment 6 gained is placed in the fixed bed reactors shown in Fig. 1, this Implementing the reaction condition provided according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, obtain product. The present invention product to obtaining carries out Structural Identification, and result shows in product containing isoprene.

As can be seen from Table 1, the embodiment of the present invention 30 selectivity of isoprene in terms of formaldehyde is 55.7%.

Embodiment 31

The solid acid catalyst of 2g embodiment 7 gained is placed in the fixed bed reactors shown in Fig. 1, this Implementing the reaction condition provided according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, obtain product. The present invention product to obtaining carries out Structural Identification, and result shows in product containing isoprene.

As can be seen from Table 1, the embodiment of the present invention 31 selectivity of isoprene in terms of formaldehyde is 69.1%.

Embodiment 32

The solid acid catalyst of 2g embodiment 8 gained is placed in the fixed bed reactors shown in Fig. 1, this Implementing the reaction condition provided according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, obtain product. The present invention product to obtaining carries out Structural Identification, and result shows in product containing isoprene.

As can be seen from Table 1, the embodiment of the present invention 32 selectivity of isoprene in terms of formaldehyde is 49.7%.

Embodiment 33

The solid acid catalyst of 2g embodiment 9 gained is placed in the fixed bed reactors shown in Fig. 1, then Being passed through isobutene and formaldehyde that mol ratio is 7:1, be 320 DEG C in reaction temperature, gas-solid contact time is 0.4 React 60min under conditions of s, obtain product.

As can be seen from Table 1, the embodiment of the present invention 33 selectivity of isoprene in terms of formaldehyde is 70.8%.

Embodiment 34

The solid acid catalyst of 2g embodiment 10 gained is placed in the fixed bed reactors shown in Fig. 1, The reaction condition that this enforcement provides according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, are produced Thing.

As can be seen from Table 1, the embodiment of the present invention 34 selectivity of isoprene in terms of formaldehyde is 69.0%.

Embodiment 35

The solid acid catalyst of 2g embodiment 11 gained is placed in the fixed bed reactors shown in Fig. 1, The reaction condition that this enforcement provides according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, are produced Thing.

As can be seen from Table 1, the embodiment of the present invention 35 selectivity of isoprene in terms of formaldehyde is 68.5%.

Embodiment 36

The solid acid catalyst of 2g embodiment 12 gained is placed in the fixed bed reactors shown in Fig. 1, The reaction condition that this enforcement provides according to embodiment 26, isobutene and formaldehyde carry out condensation reaction, are produced Thing.

As can be seen from Table 1, the embodiment of the present invention 36 selectivity of isoprene in terms of formaldehyde is 63.5%.

Embodiment 37

The solid acid catalyst of 1g embodiment 13 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 30min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 37 selectivity of isoprene in terms of formaldehyde is 75.1%.

Embodiment 38

The solid acid catalyst of 3g embodiment 14 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 40min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 38 selectivity of isoprene in terms of formaldehyde is 64.7%.

Embodiment 39

The solid acid catalyst of 2g embodiment 15 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 39 selectivity of isoprene in terms of formaldehyde is 76.6%.

Embodiment 40

The solid acid catalyst of 2g embodiment 16 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 50min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 40 selectivity of isoprene in terms of formaldehyde is 72.5%.

Embodiment 41

The solid acid catalyst of 2g embodiment 17 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 41 selectivity of isoprene in terms of formaldehyde is 65.6%.

Embodiment 42

The solid acid catalyst of 2g embodiment 18 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 42 selectivity of isoprene in terms of formaldehyde is 70.7%.

Embodiment 43

The solid acid catalyst of 2g embodiment 19 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 43 selectivity of isoprene in terms of formaldehyde is 71.4%.

Embodiment 44

The solid acid catalyst of 2g embodiment 20 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 44 selectivity of isoprene in terms of formaldehyde is 70.1%.

Embodiment 45

The solid acid catalyst of 2g embodiment 21 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 45 selectivity of isoprene in terms of formaldehyde is 71.8%.

Embodiment 46

The solid acid catalyst of 2g embodiment 22 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 46 selectivity of isoprene in terms of formaldehyde is 65.0%.

Embodiment 47

The solid acid catalyst of 2g embodiment 23 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 47 selectivity of isoprene in terms of formaldehyde is 62.4%.

Embodiment 48

The solid acid catalyst of 2g embodiment 24 gained is placed in the fixed bed reactors shown in Fig. 1, This enforcement is passed through, according to the materials-handling technology scheme of embodiment 26, the isobutene and formaldehyde that mol ratio is 7:1, Being 320 DEG C in reaction temperature, gas-solid contact time is reaction 60min under conditions of 0.4s, obtains product.

As can be seen from Table 1, the embodiment of the present invention 48 selectivity of isoprene in terms of formaldehyde is 65.1%.

Embodiment 49

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, isobutene and acetaldehyde carry out condensation reaction, obtain product.

The present invention product to obtaining carries out Structural Identification, and result shows in product containing 2-methyl isophthalic acid, 3-penta Diene.

2-methyl isophthalic acid, the selectivity of 3-pentadiene are calculated by the present invention, and result sees table 1, and table 1 is this The result of calculation of inventive embodiments 25～63 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the embodiment of the present invention 49 2-methyl isophthalic acid in terms of acetaldehyde, the selectivity of 3-pentadiene It is 71.8%.

Embodiment 50

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, isobutene and isobutylaldehyde carry out condensation reaction, obtain product.

The present invention product to obtaining carries out Structural Identification, and result shows containing 2 in product, 5-dimethyl-1,3- Hexadiene.

The present invention is to 2, and 5-dimethyl-1, the selectivity of 3-hexadiene calculates, and result sees table 1, table 1 Experimental result for the embodiment of the present invention 25～63 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the embodiment of the present invention 50 in terms of isobutylaldehyde 2,5-dimethyl-1,3-hexadiene Selectivity is 61.5%.

Embodiment 51

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, AMS and formaldehyde carry out condensation reaction, obtain product.

The present invention product to obtaining carries out Structural Identification, and result shows in product containing 2-phenyl-1,3-fourth Diene.

The selectivity of 2-phenyl-1,3-butadiene is calculated by the present invention, and result sees table 1, and table 1 is this The result of calculation of inventive embodiments 25～63 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the selectivity of the embodiment of the present invention 51 2-in terms of formaldehyde phenyl-1,3-butadiene It is 70.1%.

Embodiment 52

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, 2,3-dimethyl-1-butylene and formaldehyde carry out condensation reaction, are produced Thing.

The present invention product to obtaining carries out Structural Identification, and result shows containing 3 in product, 4-dimethyl-1,3- Pentadiene.

The present invention is to 3, and the selectivity of 4-dimethyl-1,3-pentadiene calculates, and result sees table 1, table 1 Result of calculation for the embodiment of the present invention 25～63 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the embodiment of the present invention 52 in terms of formaldehyde 3, the choosing of 4-dimethyl-1,3-pentadiene Selecting property is 68.4%.

Embodiment 53

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, methyl tertiary butyl ether(MTBE) and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 53 selectivity of isoprene in terms of formaldehyde is 58.1%.

Embodiment 54

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 26 provides, difference is, it is Φ 20mm that fixed bed reactors are replaced by reaction tube Fluidized-bed reactor, other conditions are carried out with the experiment condition of fixed bed reactors, isobutene and formaldehyde Condensation reaction, obtains product.

The selectivity of isoprene is calculated by the present invention, and result sees table 1, and table 1 is implemented for the present invention The result of calculation of example 25～63 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the embodiment of the present invention 54 selectivity of isoprene in terms of formaldehyde is 65.8%.

Embodiment 55

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, difference is, the gas-solid contact time in condensation reaction is 0.2 S, isobutene and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 55 selectivity of isoprene in terms of formaldehyde is 71.8%.

Embodiment 56

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, difference is, the gas-solid contact time in condensation reaction is 0.8 S, isobutene and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 56 selectivity of isoprene in terms of formaldehyde is 68.2%.

Embodiment 57

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, difference is, the gas-solid contact time in condensation reaction is 1.0 S, isobutene and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 57 selectivity of isoprene in terms of formaldehyde is 57.9%.

Embodiment 58

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, difference is, the reaction temperature of condensation reaction is 250 DEG C, isobutyl Alkene and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 58 selectivity of isoprene in terms of formaldehyde is 85.6%.

Embodiment 59

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, difference is, the reaction temperature of condensation reaction is 280 DEG C, isobutyl Alkene and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 59 selectivity of isoprene in terms of formaldehyde is 73.1%.

Embodiment 60

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to The reaction condition that embodiment 25 provides, difference is, the reaction temperature of condensation reaction is 350 DEG C, isobutyl Alkene and formaldehyde carry out condensation reaction, obtain product.

As can be seen from Table 1, the embodiment of the present invention 60 selectivity of isoprene in terms of formaldehyde is 54.9%.

Embodiment 61

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to Embodiment 25 provide reaction condition, difference is, the present embodiment isobutene with mol ratio as 3:1 and Formaldehyde carries out condensation reaction, obtains product.

As can be seen from Table 1, the embodiment of the present invention 61 selectivity of isoprene in terms of formaldehyde is 78.7%.

Embodiment 62

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to Embodiment 25 provide reaction condition, difference is, the present embodiment isobutene with mol ratio as 5:1 and Formaldehyde carries out condensation reaction, obtains product.

As can be seen from Table 1, the embodiment of the present invention 62 selectivity of isoprene in terms of formaldehyde is 73.0%.

Embodiment 63

The solid acid catalyst that embodiment 1 obtains is placed in the fixed bed reactors shown in Fig. 1, according to Embodiment 25 provide reaction condition, difference is, the present embodiment isobutene with mol ratio as 10:1 and Formaldehyde carries out condensation reaction, obtains product.

As can be seen from Table 1, the embodiment of the present invention 63 selectivity of isoprene in terms of formaldehyde is 60.7%.

The experimental result of table 1 embodiment of the present invention 25～63 alkene (ether) aldehyde reaction

Embodiment 64

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, isobutene and Formaldehyde carries out condensation reaction, obtains product.The solid acid catalysis that condensation reaction directly will be used after terminating Agent is roasting 50min at 500 DEG C, is passed through air in roasting process, and Ventilation Rate is 20L/hr, regeneration After obtain solid acid catalyst.

Solid acid catalyst after the regeneration that will obtain, under the same reaction conditions provided with embodiment 1, Isobutene and formaldehyde carry out condensation reaction, obtain product.

The experimental result of the present embodiment is shown in that Fig. 2, Fig. 2 are that the embodiment of the present invention 64 obtains solid acid catalyst Regeneration and life assessment figure, wherein, 1 is conversion ratio, 2 be selectivity, 3 is yield.

By Fig. 2 it will be seen that the life-span of the solid acid catalyst of present invention offer is long, regenerability is good.

Embodiment 65

The catalyst that embodiment 1 and embodiment 2 obtain is fixed a reactor and fluidized-bed reactor Amplification test, multiplication factor is 10 times.

Product is measured by the present invention, shows that amplification test result differs with pilot run less than 2%.

As seen from the above embodiment, the invention provides a kind of solid acid catalyst, divide including SAPO Son sieve and auxiliary agent；In described silicoaluminophosphamolecular molecular sieves, the mol ratio of silicon, aluminium and phosphorus is 0.005～2.5:1:0.1～5. The present invention provide solid acid catalyst can be catalyzed have the carbonyl-containing compound of structure shown in formula (I) and There is the condensation reaction of the monoolefinic compound of structure shown in formula (II), prepare double olefin compound.This The solid acid catalyst that invention provides has higher selectivity of product, decreases in condensation reaction secondary The generation of reaction, improves the productivity of double olefin compound.And, the solid acid catalysis that the present invention provides Agent catalysis activity is high, has higher conversion ratio.It addition, the solid acid catalyst toxicity that the present invention provides Little, life-span length, regenerability are good, are suitable to industrialized production.

The above is only the preferred embodiment of the present invention, it is noted that general for the art For logical technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvement and profit Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.

Claims

1. for preparing a solid acid catalyst for double olefin compound, including Silicoaluminophosphate molecular Sieve and auxiliary agent；

In described silicoaluminophosphamolecular molecular sieves, the mol ratio of silicon, aluminium and phosphorus is 0.005～2.5:1:0.1～5；

Described auxiliary agent is 0.1～20:100 with the mass ratio of silicoaluminophosphamolecular molecular sieves；

Described auxiliary agent is CaO, CrO₃、P₂O₅、Al₂O₃、Sb₂O₃、MoO₃、Ag、Fe₂O₃ With one or more in CuO.

Solid acid catalyst the most according to claim 1, it is characterised in that described silicon phosphate Aluminum molecular screen is obtained by the raw material roasting including silicon source, aluminium source, phosphorus source and surfactant；

Described surfactant includes in cationic surfactant and hexadecyl trimethoxy silane One or both.

3. a preparation method for solid acid catalyst as claimed in claim 1, including following step Rapid:

A) silicon source, aluminium source, phosphorus source and auxiliary agent raw material are mixed in a solvent, obtain body before catalyst Body；

Preparation method the most according to claim 3, it is characterised in that described silicon source includes silicon One or more in colloidal sol, Silica hydrogel, waterglass, silica and positive esters of silicon acis.

Preparation method the most according to claim 3, it is characterised in that source of aluminium includes aluminium In salt, aluminate, aluminum oxide, alkoxy aluminum compound, false boehmite and boehmite one Plant or multiple.

Preparation method the most according to claim 3, it is characterised in that phosphorus source includes phosphorus One or more in the oxide of acid, phosphate, organic phosphoric acid compound and phosphorus.

Preparation method the most according to claim 3, it is characterised in that brilliant in described step b) The temperature changed is 50 DEG C～400 DEG C；

The time of crystallization is more than or equal to 5min.

Preparation method the most according to claim 3, it is characterised in that roasting in described step c) The temperature burnt is 200 DEG C～800 DEG C；

The time of roasting is more than or equal to 1h.

9. a preparation method for double olefin compound, comprises the following steps:

To there is the carbonyl-containing compound of structure shown in formula (I) and there is the list of structure shown in formula (II) Olefin(e) compound carries out condensation reaction under the effect of catalyst, obtains double olefin compound；

Described catalyst is that the solid acid catalyst described in claim 1～2 any one or right are wanted Seek the solid acid catalyst that preparation method described in 3～8 any one obtains；

Preparation method the most according to claim 9, it is characterised in that R₁、R₂、R₃With R₄Independently selected from hydrogen, carbon number be 1～8 straight chained alkyl, carbon number be 1～8 side chain Alkyl, carbon number are the substituted phenyl of straight chained alkyl of 1～8 or side chain that carbon number is 1～8 The substituted phenyl of alkyl.

11. preparation methods according to claim 9, it is characterised in that described in there is formula (I) Shown in the carbonyl-containing compound of structure and there is rubbing of the monoolefinic compound of structure shown in formula (II) That ratio is 1:1～12；

The quality of described solid acid catalyst with there is the carbonyl-containing compound of structure shown in formula (I) The amount of material than for (1～3) g:1mol.

12. preparation methods according to claim 9, it is characterised in that described condensation reaction Temperature be 230 DEG C～370 DEG C；

The time of described condensation reaction is 30min～70min.