CN103691484A

CN103691484A - Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds

Info

Publication number: CN103691484A
Application number: CN201310693632.6A
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: 2014-04-02
Anticipated expiration: 2033-12-17
Also published as: CN103691484B

Abstract

The invention provides a solid acid catalyst which comprises an active component and a support, wherein the active component is heteropoly acid and/or heteropoly acid salt; the acid radical of the heteropoly acid comprises a first central atom and a first coordinating atom; the acid radical of the heteropoly acid salt comprises a second central atom and a second coordinating atom; the first central atom and second central atom are P or Si; and the first coordinating atom and second coordinating atom comprise one or more of W, Mo and V. The catalyst provided by the invention can catalyze condensation reaction between carbonyl compounds disclosed as Formula (I) and mono-olefin compounds disclosed as Formula (II) to prepare the diolefin compounds. The catalyst provided by the invention has higher product selectivity, reduces the possibility of side reactions in the condensation reaction process, and enhances the yield of the diolefin compounds. Besides, the catalyst provided by the invention has high catalytic activity and higher conversion rate.

Description

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

Technical field

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

Background technology

Double olefin compound is the unsaturated hydrocarbon that contains two carbon-carbon double bonds.Isoprene main application in double olefin compound is to produce isoprene rubber, butyl rubber, medical pesticide intermediate and synthetic lubricant fluid additive, vulcanizer etc.

In prior art, the preparation method of isoprene mainly contains dehydriding, synthetic method and extraction process, and wherein synthetic method comprises isobutene-formaldehyde method, acetylene-acetone method and propylene dimerization.According to the difference of reaction process, isobutene and formaldehyde method can also be divided into two-step method and one-step method.Wherein, two-step method is that isobutene and formaldehyde carry out condensation reaction at 70 ℃～100 ℃ under acidic catalyst exists, and generates 4,4-dimethyl-1,3-dioxane and byproduct, isolates 4,4-dimethyl-1,3-dioxane; Then, 4,4-dimethyl-1,3-dioxane cracking Isoprene, formaldehyde and water at 250 ℃～280 ℃.The technological process of this two-step method is loaded down with trivial details, and accessory substance is complicated.One-step method is that gas phase isobutene and formaldehyde are more than 200 ℃ under acidic catalyst exists, and Direct Dehydration condensation obtains isoprene and water.The technique of this one-step method has the advantages such as flow process is short, accessory substance is few.Therefore, the synthetic isoprene of olefine aldehydr gas-phase one-step method becomes the focus of research.

Catalyst is the key problem in technology of isobutene and the synthetic isoprene of formaldehyde gas-phase one-step method efficiently.Cross scholar (scholar in crossing, Xue Jinzhen, Xu Xianlun etc.The research of alkene, aldehyde one-step synthesis isoprene boric acid catalyst.Chemistry of fuel journal, March nineteen eighty-three, 11 3 phases of volume, 57～63.) etc. people has added again vanadium, potassium and aluminium three components in boron and phosphorus two-component catalyst, obtain five component catalysts, and the condensation reaction for catalyzing iso-butane alkene and formaldehyde by described five component catalysts, isoprene obtained.Result of study shows, the regenerability of boron, phosphorus, vanadium, aluminium and potassium five component catalysts is improved compared with boron and phosphorus two-component catalyst, but selectively still very low for isoprene in condensation reaction products of this boron, phosphorus, vanadium, aluminium and potassium five component catalysts, is difficult to suitability for industrialized production.

Summary of the invention

In view of this, the object of the present invention is to provide the preparation method of a kind of solid acid catalyst, its preparation method and double olefin compound.Solid acid catalyst provided by the invention is prepared in the process of double olefin compound at gas-phase one-step method, has higher selectivity of product, has improved the productive rate of double olefin compound.

The invention provides a kind of solid acid catalyst, comprise active component and carrier;

Described active component is heteropoly acid and/or heteropolyacid salt;

The acid group of described heteropoly acid comprises the first central atom and the first coordination atom;

The acid group of described heteropolyacid salt comprises the second central atom and the second coordination atom;

Described the first central atom and the second central atom are independently selected from P or Si;

Described the first coordination atom and the second coordination atom are independently selected from one or more in W, Mo and V.

Preferably, described heteropoly acid comprises one or more in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, molybdovanaphosphoric acid and silicon molybdenum vanadic acid;

Preferably, described heteropolyacid salt comprises one or more in heteropoly acid normal salt and heteropoly acid acid salt.

Preferably, described carrier comprise the compound of magnesium, the compound of the compound of aluminium, titanium, one or more in the compound of silicon and material with carbon element.

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

A) carry out load after heteropoly compound is mixed in solvent with carrier, obtain catalyst intermediate;

B) catalyst intermediate described step a) being obtained is carried out roasting after being dried, and obtains solid acid catalyst.

Preferably, described step a) in the temperature of load be 20 ℃～95 ℃;

A) time of middle load is 0.5h～8h to described step.

Preferably, the described catalyst intermediate that described step a) is obtained is carried out roasting after dry and is specially:

The catalyst intermediate that described step a) is obtained is carried out the first roasting and the second roasting after being dried;

The temperature of described the first roasting is lower than the temperature of described the second roasting.

Preferably, the temperature of described the first roasting is 300 ℃～350 ℃, and the time of the first roasting is 0.5h～8h;

The temperature of described the second roasting is 500 ℃～550 ℃, and the time of the second roasting is 1h～10h.

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

The compound containing carbonyl with structure shown in formula (I) is carried out to condensation reaction with the monoolefine compound with structure shown in formula (II) under the effect of catalyst, obtain double olefin compound;

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

Wherein, R ₁, R ₂, R ₃and R ₄independently selected from hydrogen, alkyl or aromatic radical.

Preferably, R ₁, R ₂, R ₃and R ₄the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that the branched alkyl that the straight chained alkyl that is 1～8 independently selected from hydrogen, carbon number, carbon number are 1～8, carbon number are 1～8 replaces or carbon number are 1～8 replaces.

The compound containing carbonyl preferably, with structure shown in formula (I) is 1:1～12 with the mol ratio with the monoolefine compound of structure shown in formula (II);

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

Preferably, the temperature of described condensation reaction is 220 ℃～350 ℃;

The time of condensation reaction is 20min～40min.

The invention provides a kind of solid acid catalyst, comprise active component and carrier; Described active component is heteropoly acid and/or heteropolyacid salt; The acid group of described heteropoly acid comprises the first central atom and the first coordination atom; The acid group of described heteropolyacid salt comprises the second central atom and the second coordination atom; Described the first central atom and the second central atom are independently selected from P or Si; Described the first coordination atom and the second coordination atom are independently selected from one or more in W, Mo and V.Solid acid catalyst provided by the invention can catalysis has the compound containing carbonyl of structure shown in formula (I) and has the condensation reaction of the monoolefine compound of structure shown in formula (II), prepares double olefin compound.Solid acid catalyst provided by the invention has higher selectivity of product, has reduced the generation of side reaction in condensation reaction, has improved the productive rate of double olefin compound.And solid acid catalyst catalytic activity provided by the invention is high, has higher conversion ratio.In addition, solid acid catalyst toxicity provided by the invention is little, the life-span is long, regenerability good, is easy to suitability for industrialized production.Experimental result shows, isobutene and formaldehyde are under the effect of solid acid catalyst, and selective (in the aldehyde) of product is up to 78.3%, and conversion ratio (in aldehyde) is up to 84.3%.

Accompanying drawing explanation

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

Fig. 2 is regeneration and the life assessment figure that the embodiment of the present invention 50 obtains solid acid catalyst.

The specific embodiment

The invention provides a kind of solid acid catalyst, comprise active component and carrier; Described active component is heteropoly acid and/or heteropolyacid salt; The acid group of described heteropoly acid comprises the first central atom and the first coordination atom; The acid group of described heteropolyacid salt comprises the second central atom and the second coordination atom; Described the first central atom and the second central atom are independently selected from P or Si; Described the first coordination atom and the second coordination atom are independently selected from one or more in W, Mo and V.

Solid acid catalyst provided by the invention can catalysis has the compound containing carbonyl of structure shown in formula (I) and has the condensation reaction of the monoolefine compound of structure shown in formula (II), prepares double olefin compound.Solid acid catalyst provided by the invention has higher selectivity of product, has reduced the generation of side reaction in condensation reaction, has improved the productive rate of double olefin compound.And solid acid catalyst catalytic activity provided by the invention is high, has higher conversion ratio.In addition, solid acid catalyst toxicity provided by the invention is little, the life-span is long, regenerability good, is suitable for suitability for industrialized production.

Solid acid catalyst provided by the invention comprises active component, and described active component is heteropoly acid and/or heteropolyacid salt; The acid group of described heteropoly acid comprises the first central atom and the first coordination atom; The acid group of described heteropolyacid salt comprises the second central atom and the second coordination atom; Described the first central atom and the second central atom are independently selected from P or Si; Described the first coordination atom and the second coordination atom are independently selected from one or more in W, Mo and V.In the present invention, described heteropoly acid preferably includes one or more in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, molybdovanaphosphoric acid and silicon molybdenum vanadic acid; More preferably comprise one or more in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid and silicomolybdic acid;

In the present invention, described heteropolyacid salt preferably includes one or more in heteropoly acid normal salt and heteropoly acid acid salt, more preferably comprises one or more in phosphotungstate, phosphomolybdate, silicotungstate, silicomolybdate, molybdovanaphosphoric acid salt and silicon molybdenum vanadate;

In the present invention, described heteropoly acid normal salt preferably includes one or more in phosphotungstic acid normal salt, phosphomolybdic acid normal salt, silico-tungstic acid normal salt, silicomolybdic acid normal salt, molybdovanaphosphoric acid normal salt and silicon molybdenum vanadic acid normal salt, more preferably comprises one or more in phosphotungstic acid normal salt, phosphomolybdic acid normal salt, silico-tungstic acid normal salt and silicomolybdic acid normal salt;

In the present invention, described heteropoly acid acid salt comprises acid group and cation, and described acid group comprises the second central atom, the second coordination atom and hydrogen ion; Described cation preferably includes one or more in ammonium ion, alkali metal ion, alkaline-earth metal ions and transition metal ions, more preferably comprises one or more in ammonium ion, sodium ion, potassium ion, magnesium ion, barium ions, chromium ion, manganese ion, iron ion, cobalt ions, nickel ion, platinum ion, palladium ion and copper ion.

In the present invention, concrete, described heteropoly acid acid salt preferably includes one or more in phosphotungstic acid acid salt, phosphomolybdic acid acid salt, silico-tungstic acid acid salt, silicomolybdic acid acid salt, molybdovanaphosphoric acid acid salt and silicon molybdenum vanadic acid acid salt, more preferably comprise one or more in phosphotungstic acid acid salt, phosphomolybdic acid acid salt, silico-tungstic acid acid salt and silicomolybdic acid acid salt, most preferably comprise one or more in phosphotungstic acid acid sodium, phosphomolybdic acid acid potassium and silicomolybdic acid acid iron.

In the present invention, the percentage composition that the quality of described active component accounts for solid acid catalyst quality is preferably greater than and equals 10% and be less than 100%, and more preferably 20%～90%, most preferably be 30%～80%.

Solid acid catalyst provided by the invention comprises carrier.In the present invention, described carrier preferably include the compound of magnesium, the compound of the compound of aluminium, titanium, one or more in the compound of silicon and material with carbon element; More preferably the salt compounds, the TiO that comprise magnesium ₂, Al ₂o ₃, SiO ₂with one or more in material with carbon element, most preferably comprise MgCl ₂, Al ₂o ₃, TiO ₂, SiO ₂, one or more in Graphene and CNT.The present invention does not have special restriction to the source of described carrier, adopts above-mentioned carrier well known to those skilled in the art, can adopt the commercial goods of above-mentioned carrier.

The present invention carries out load after heteropoly compound is mixed in solvent with carrier, obtains catalyst intermediate.The present invention is preferably dissolved in described heteropoly compound in solvent, after heteropoly compound dissolves completely, then adds wherein carrier, carries out load, obtains catalyst intermediate.The present invention does not have special restriction to the mode that adds of described heteropoly compound and carrier, preferably under the condition stirring, mixes.The container that the present invention uses during to described mix does not have special restriction, adopts container well known to those skilled in the art, and as being flask, in an embodiment of the present invention, described container can be specially round-bottomed flask.

In the present invention, described carrier is consistent with the kind of carrier described in technique scheme, does not repeat them here; The mass ratio of described carrier and heteropoly compound is preferably (5～10): 1, more preferably (6～9): 1.

In the present invention, described heteropoly compound comprises one or more in heteropoly acid and heteropolyacid salt; Described heteropoly acid is consistent with the kind of heteropoly acid described in technique scheme and heteropolyacid salt with heteropolyacid salt, does not repeat them here.

The present invention does not have special restriction to the source of described solvent and kind, adopts solvent well known to those skilled in the art.In the present invention, described solvent is preferably one or more in running water, distilled water and deionized water; Deionized water more preferably.In the present invention, the mass ratio of described heteropoly compound and solvent is preferably 1:10～15, and more preferably 1:11～14, most preferably are 1:12～13.

In the present invention, the temperature of described load is preferably 20 ℃～95 ℃, more preferably 25 ℃～90 ℃, most preferably is 30 ℃～50 ℃; The time of described load is preferably 0.1h～8h, and more preferably 0.2h～5h, most preferably is 0.5h～2.5h.

Obtain after catalyst intermediate, after the present invention is dry by described catalyst intermediate, carry out roasting, obtain solid acid catalyst.In the present invention, describedly carry out roasting after described catalyst intermediate is dry and be preferably specially:

After described catalyst intermediate is dry, carry out the first roasting and the second roasting;

The present invention does not have special restriction to described dry method, adopts dry technology scheme well known to those skilled in the art.The present invention is in order to distinguish being dried in following technical proposals, and the dry called after that catalyst intermediate is carried out first is dry, the described first dry evaporate to dryness that is preferably; In the present invention, described the first dry temperature is preferably 80 ℃～125 ℃, more preferably 90 ℃～120 ℃, most preferably is 95 ℃～105 ℃; The present invention does not have special restriction to described the first dry time, and described catalyst intermediate is dried to constant weight.

Complete after described catalyst intermediate dry, the present invention preferably carries out the first roasting by described dry catalyst intermediate, obtains the first product of roasting.The present invention does not have special restriction to the equipment of described the first roasting, adopts roasting apparatus well known to those skilled in the art, as can adopt Muffle furnace to as described in dry catalyst intermediate carry out the first roasting.In the present invention, the temperature of described the first roasting is preferably 300 ℃～350 ℃, more preferably 320 ℃～340 ℃; The time of described the first roasting is preferably 0.5h～8h, and more preferably 2h～6h, most preferably is 3h～4h.

Obtain after the first product of roasting, the present invention preferably carries out phosphoric acid solution processing by described the first product of roasting.The present invention, to the not restriction of the addition sequence of described the first product of roasting and phosphoric acid solution, preferably joins phosphoric acid solution in the first product of roasting.In the present invention, the mass concentration of described phosphoric acid solution is preferably 1%～20%, and more preferably 3%～15%, most preferably be 5%～9%.The present invention does not have special restriction to the consumption of described phosphoric acid solution, preferably the first product of roasting described in submergence.In the present invention, the temperature that described phosphoric acid solution is processed is preferably 80 ℃～100 ℃, more preferably 85 ℃～95 ℃; The time that described phosphoric acid solution is processed is preferably 0.5h～8h, more preferably 1.0h～1.5h.

After completing the phosphoric acid solution processing of described the first product of roasting, the first product of roasting after the present invention preferably processes described phosphoric acid solution carries out second and is dried, and will complete second dried the first product of roasting and process with ammonia spirit.The present invention does not have special restriction to described the second dry method, adopts dry technology scheme well known to those skilled in the art, the described second dry evaporate to dryness that is preferably.In the present invention, described the second dry temperature is preferably 95 ℃～120 ℃; More preferably 100 ℃～110 ℃; The present invention does not have special restriction to described the second dry time, and the first product of roasting after described phosphoric acid solution is processed is dried to constant weight.The present invention does not have special restriction to the consumption of described ammonia spirit, preferably second dried the first product of roasting described in submergence.In the present invention, the mass concentration of described ammonia spirit is preferably 1%～10%, and more preferably 2%～8%, most preferably be 4%～6%; In the present invention, the temperature that described ammonia spirit is processed is preferably 80 ℃～100 ℃, more preferably 85 ℃～95 ℃; The time that described ammonia spirit is processed is preferably 1h～3h, more preferably 1.5h～2.5h.

After completing the ammonia spirit of described the first product of roasting being processed, the first product of roasting after the present invention preferably processes the ammonia spirit obtaining filters, washes and be the 3rd dry, then carries out the second roasting, obtains solid acid catalyst.The present invention does not have special restriction to described filtration and washing, adopts filtration well known to those skilled in the art and water-washing technique scheme.The first product of roasting after the present invention preferably processes ammonia spirit filters after washing 2 times～3 times.The present invention does not have special restriction to described dry method, adopts dry technology scheme well known to those skilled in the art.In the present invention, the described the 3rd dry evaporate to dryness that is preferably; Described the 3rd dry temperature is preferably 100 ℃～140 ℃; More preferably 120 ℃～130 ℃; Described the 3rd dry time does not have special restriction, and the first product of roasting after described filtration and washing is dried to constant weight.

Complete dry to described the first product of roasting the 3rd after, the present invention preferably carries out the second roasting by the 3rd dried the first product of roasting, obtains solid acid catalyst.The present invention does not have special restriction to the equipment of described the second roasting, adopts roasting apparatus well known to those skilled in the art, as adopted Muffle furnace to carry out the second roasting.In the present invention, the temperature of described the second roasting is preferably 500 ℃～550 ℃, more preferably 510 ℃～530 ℃; The time of described the second roasting is preferably 1h～10h, and more preferably 1.5h～8h, most preferably is 2h～4h.

The monoolefine compound that solid acid catalyst provided by the invention can catalysis has the compound containing carbonyl of structure shown in formula (I) and has a structure shown in formula (II) carries out condensation reaction, obtains double olefin compound.Solid acid catalyst provided by the invention has two kinds of activated centre: Bronsted acid (being called for short B acid) activated centre and Lewis acid (being called for short L acid) activated centre.In olefine aldehyde condensation course of reaction, B acid activity center Main Function, solid acid catalyst provided by the invention has the B acid activity center of high level, the B acid activity center of high level makes solid acid catalyst provided by the invention have higher selectivity of product, reduce the generation of side reaction in condensation reaction, improved the productive rate of double olefin compound; The specific area of solid acid catalyst provided by the invention is large, has higher catalytic activity, thereby has improved conversion ratio.

The present invention measures ratio and the specific area at the total acid content of the solid acid catalyst obtaining, B acid activity center and L acid activity center.Measurement result shows, the total acid content of solid acid catalyst provided by the invention is up to 3.42mmol/g, and B acid activity center is with the ratio at L acid activity center for being up to 2.33, and specific area is 295m to the maximum ²/ g.

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

In the present invention, the compound containing carbonyl with structure shown in formula (I) carries out condensation reaction with the monoolefine compound with structure shown in formula (II), and the reaction equation of condensation reaction is suc as formula shown in (a).

formula (a)

Wherein, cat represents solid acid catalyst provided by the invention; R ₁, R ₂, R ₃and R ₄with the R described in technique scheme ₁, R ₂, R ₃and R ₄unanimously, at this to substituent R ₁, R ₂, R ₃and R ₄repeat no more; R ₄' compare R ₄few one-H.

The present invention carries out condensation reaction by the compound containing carbonyl with structure shown in formula (I) with the monoolefine compound with structure shown in formula (II) under the effect of catalyst, obtains double olefin compound.The present invention does not have special restriction to described kind and the source with the compound containing carbonyl of structure shown in formula (I), adopts the compound containing carbonyl with structure shown in formula (I) well known to those skilled in the art.In the present invention, the R in formula (I) ₁and R ₂independently selected from hydrogen, alkyl or aromatic radical; Preferably, R ₁and R ₂the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that the branched alkyl that the straight chained alkyl that is 1～8 independently selected from hydrogen, carbon number, carbon number are 1～8, carbon number are 1～8 replaces or carbon number are 1～8 replaces, more preferably, R ₁and R ₂independently selected from one or more in hydrogen, methyl and isopropyl.In formula of the present invention (I), work as R ₁and R ₂during phenyl that the branched alkyl that the phenyl that the straight chained alkyl that is 1～8 independently selected from carbon number replaces or carbon number are 1～8 replaces, the present invention does not have special restriction to the replacement site on described phenyl, can be ortho position, can be also a position, can also be contraposition.

Particularly, work as R ₁and R ₂during for hydrogen, described in what have structure shown in formula (I) is formaldehyde containing the compound of carbonyl; Work as R ₁for methyl, R ₂during for hydrogen, described in what have structure shown in formula (I) is acetaldehyde containing the compound of carbonyl; Work as R ₁for isopropyl, R ₂during for hydrogen, described in what have structure shown in formula (I) is isobutylaldehyde containing the compound of carbonyl.

The present invention does not have special restriction to described kind and the source with the monoolefine compound of structure shown in formula (II), adopts the monoolefine compound with structure shown in formula (II) well known to those skilled in the art.

In formula of the present invention (II), R ₃and R ₄independently selected from hydrogen, alkyl or aromatic radical; Preferably, R ₃and R ₄the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that the branched alkyl that the straight chained alkyl that is 1～8 independently selected from hydrogen, carbon number, carbon number are 1～8, carbon number are 1～8 replaces or carbon number are 1～8 replaces, more preferably, R ₃and R ₄independently selected from one or more in hydrogen, methyl, isopropyl and benzyl.Work as R ₃and R ₄during phenyl that the branched alkyl that the phenyl that the straight chained alkyl that is 1～8 independently selected from carbon number replaces or carbon number are 1～8 replaces, the present invention does not have special restriction to the replacement site on described phenyl, can be ortho position, can be also a position, can also be contraposition.

Particularly, work as R ₃and R ₄while being methyl simultaneously, described in there is structure shown in formula (II) monoolefine compound be isobutene; Work as R ₃for isopropyl, R ₄during for methyl, described in there is structure shown in formula (II) monoolefine compound be 2,3-dimethyl-1-butylene; Work as R ₃for methyl, R ₄during for phenyl, described in there is structure shown in formula (II) monoolefine compound be AMS.

In the present invention, described in there is structure shown in formula (II) monoolefine compound can be buied by market, also can prepare voluntarily according to preparation method well known to those skilled in the art.The preparation method in the present invention, with the monoolefine compound of the described structure of formula (II) preferably includes following steps:

The ether compound with structure shown in formula (III) is carried out to the reaction of ether solution, the monoolefine compound of the structure shown in (II) that obtains thering is formula;

Wherein, R ₅and R ₆independently selected from hydrogen, alkyl or aromatic radical.

In the present invention, the R in formula (III) ₅and R ₆independently selected from hydrogen, alkyl or aromatic radical; Preferably, R ₅and R ₆the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that the branched alkyl that the straight chained alkyl that is 1～8 independently selected from hydrogen, carbon number, carbon number are 1～8, carbon number are 1～8 replaces or carbon number are 1～8 replaces, more preferably, R ₅and R ₆independently selected from one or more in hydrogen, methyl, isopropyl and benzyl.Work as R ₅and R ₆during phenyl that the branched alkyl that the phenyl that the straight chained alkyl that is 1～8 independently selected from carbon number replaces or carbon number are 1～8 replaces, the present invention does not have special restriction to the replacement site on described phenyl, can be ortho position, can be also a position, can also be contraposition.Particularly, work as R ₅and R ₆while being methyl, the ether compound with 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 ℃～300 ℃, more preferably 180 ℃～280 ℃; The time of described ether solution reaction is preferably 1h～5h, more preferably 2h～4h; The catalyst that described ether solution reaction is used preferably includes Al ₂o ₃, sulfate, phosphate, the oxide of uranium is, one or more in the hydroxide of uranium and active carbon more preferably comprise Al ₂o ₃, U ₃o ₈and Ca ₃(PO ₄) ₂in one or more; The pressure of described ether solution reaction is preferably 0.3MPa～0.6MPa, more preferably 0.35MPa～0.55MPa.

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

In the present invention, the temperature of described condensation reaction is preferably 200 ℃～450 ℃, more preferably 250 ℃～400 ℃, most preferably is 280 ℃～350 ℃; The time of described condensation reaction is preferably 20min～40min, 25min～35min more preferably, and in described condensation reaction, gas-solid contact time is preferably 0.1s～1.2s, and more preferably 0.2s～1.0s, most preferably is 0.2s～0.8s.

The present invention does not have special restriction to the device of described condensation reaction, and preferably adopting reaction unit as shown in Figure 1, Fig. 1 is the structural representation of the fixed bed reactors of embodiment of the present invention employing.Wherein, 11 is the first material feeding pump; 12 is the second material feeding pump; 21 is the first valve, and 22 is the second valve, and 31 is the first material pipe, and 32 is the second material pipe, and 4 is mixed material pipeline, and 5 is reaction tube; 6 is condenser; 7 is gas-liquid separation and carbonyls retracting device; 8 is gas chromatograph.

In the present invention, described fixed bed reactors comprise the first material feeding pump 11 and the first material pipe 31, and the discharging opening of described the first material feeding pump 11 is connected with the charging aperture of described the first material pipe 31, by the first mass transport to the first material pipe 31; The present invention does not have special restriction to the diameter of described the first material pipe 31, material and length, meets practical operation condition required;

In the present invention, described fixed bed reactors comprise valve 21, and the present invention, in order to control the inlet amount of material, in an embodiment of the present invention, is provided with the first valve 21 on described the first material pipe 31, for controlling the conveying of described the first material.Whether the position that the present invention arranges on described the first material pipe 31 described the first valve 21 limits, and can be arranged at the optional position of described the first material pipe 31;

In the present invention, described fixed bed reactors comprise the second material feeding pump 12 and the second material pipe 32, and the discharging opening of described the second material feeding pump 12 is connected with the charging aperture of described the second material pipe 32, by the second mass transport to the second material pipe 32; The present invention does not have special restriction to the diameter of described the second material pipe 32, material and length, meets practical operation condition; The material variety not restriction of the present invention to described the first material pipe 31 and the second material pipe 32 conveyings, in an embodiment of the present invention, described the first material pipe 31 and the second material pipe 32 are delivered to the compound containing carbonyl with structure shown in formula (I) in mixed material pipeline 4 with the monoolefine compound with structure shown in formula (II) respectively;

In the present invention, described fixed bed reactors comprise valve 22, and the present invention, in order to control the inlet amount of material, in an embodiment of the present invention, is provided with the second valve 22 on described the second material pipe 32, for controlling the conveying of described the second material; The position that the present invention arranges on described the second material pipe 32 described the second valve 22 does not limit, and can be arranged at the optional position of described the second material pipe 32;

In the present invention, described fixed bed reactors comprise mixed material pipeline 4, the discharging opening of described mixed material pipeline 4 is connected with the entrance of reaction tube 5, and the present invention does not have special restriction to the diameter of described mixed material pipeline 4, material and length, meets practical operation condition required; In the present invention, described mixed material pipeline 4 by the first material being transported by described the first material pipe together with the second mixing of materials being transported by the second material pipe and be delivered to reaction tube 5;

In the present invention, described fixed bed reactors comprise reaction tube 5, and the outlet of described reaction tube 5 is connected with the entrance of described condenser 6, and reaction tube 5 is used for holding solid acid catalyst and the place of condensation reaction is provided.The present invention does not have special restriction to the size of described reaction tube, can be arbitrary dimension; In an embodiment of the present invention, the diameter of described reaction tube 5 is Φ 15mm～Φ 20mm;

In the present invention, described fixed bed reactors comprise condenser 6, the outlet of described condenser 6 is connected with the entrance of described gas-liquid separation and carbonyls retracting device 7, the product obtaining complete polymerisation in reaction tube 5 after is transported to condenser 6, and described condenser 6 is by wherein unreacted carbonyls and portion of product condensation are got off;

In the present invention, described fixed bed reactors comprise gas-liquid separation and carbonyls retracting device 7, the outlet of described gas-liquid separation and carbonyls retracting device 7 is connected with the entrance of described gas chromatograph 8, and gas-liquid separation and carbonyls retracting device 7 are used for the product through condenser 6 to carry out separation and reclaim unreacted carbonyls;

In the present invention, described fixed bed reactors comprise gas chromatograph 8, the gas-phase product that gas chromatograph 8 is used for measuring gas-liquid separation device separation form and product in the content of double olefin compound; In an embodiment of the present invention, described gas chromatograph is Thermo Scientific Trace GC ultra chromatograph.

Below in conjunction with the fixed bed reactors shown in Fig. 1, further the preparation method of double olefin compound provided by the invention is described in detail:

The present invention is delivered to the first material pipe 31 by the compound containing carbonyl with structure shown in formula (I) by the first material feeding pump 11, in the process of carrying, by the first valve 21, control the addition of the compound containing carbonyl with structure shown in formula (I); The monoolefine compound with structure shown in formula (II) is delivered to the second material pipe 32 by the second material feeding pump 12, in the process of carrying, by the second valve 22, control the addition with the monoolefine compound of structure shown in formula (II);

Described the first material pipe 31 is delivered to mixed material pipeline 4 by the carbonyl containing compound with structure shown in formula (I), and described the second material pipe 32 is delivered to mixed material pipeline 4 by the monoolefine compound with structure shown in formula (II); The described carbonyl containing compound with structure shown in formula (I) converges at mixed material pipeline 4 places with the monoolefine compound with structure shown in formula (II), and is delivered to reaction tube 5;

In reaction tube 5, be placed with in advance solid acid catalyst, the compound containing carbonyl with structure shown in formula (I) carries out condensation reaction with the monoolefine compound with structure shown in formula (II) under the effect of above-mentioned solid acid catalyst, obtain product, product is transported to condenser 6;

In condenser 6, portion of product obtains condensation, obtains liquid product and the uncooled gaseous substance of condensation, then the liquid product of described condensation and uncooled gaseous substance are delivered in gas-liquid separation and carbonyls retracting device 7;

Described gas-liquid separation and carbonyls retracting device 7 carry out gas-liquid separation and reclaim unreacted carbonyls, unreacted carbonyls is used dilute sulfuric acid titration after absorbing with sodium sulfite solution again, measure the content of unreacted carbonyls, and then calculate carbonyls conversion ratio; Finally gaseous substance is passed in gas chromatograph 8;

8 pairs of gaseous substances of gas chromatograph are measured, and measure the kind of the double olefin compound generating in gaseous substance and the content of double olefin compound.

The invention provides a kind of solid acid catalyst, comprise active component and carrier; Described active component is heteropoly acid and/or heteropolyacid salt; The acid group of described heteropoly acid comprises the first central atom and the first coordination atom; The acid group of described heteropolyacid salt comprises the second central atom and the second coordination atom; Described the first central atom and the second central atom are independently selected from P or Si; Described the first coordination atom and the second coordination atom are independently selected from one or more in W, Mo and V.Solid acid catalyst provided by the invention can catalysis has the compound containing carbonyl of structure shown in formula (I) and has the condensation reaction of the monoolefine compound of structure shown in formula (II), prepares double olefin compound.Solid acid catalyst provided by the invention has higher selectivity of product, has reduced the generation of side reaction in condensation reaction, has improved the productive rate of double olefin compound.And solid acid catalyst catalytic activity provided by the invention is high, has higher conversion ratio.In addition, solid acid catalyst toxicity provided by the invention is little, the life-span is long, regenerability good, is easy to suitability for industrialized production.

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

Embodiment 1

10g phosphotungstic acid and 130mL deionized water are placed in to the round-bottomed flask of 500mL, pour while stirring 80g silica dioxide granule after solid dissolves completely into, round-bottomed flask is connected in mixed sizing device, at 95 ℃, load 0.5h, obtains catalyst intermediate;

By temperature increase to 125 ℃, the moisture of evaporate to dryness catalyst intermediate, then catalyst intermediate is placed in to Muffle furnace, and at 350 ℃, carry out the first roasting 0.5h, then by temperature increase to 500 ℃, proceed the second roasting 10h, obtain solid acid catalyst.

The present invention tests ratio and the specific area at the total acid content of the solid acid catalyst obtaining, B acid activity center and L acid activity center.

The total acid content of the solid acid catalyst that the embodiment of the present invention obtains is 3.21mmol/g, and B acid activity center is 2.16 with the ratio at L acid activity center, and specific area is 295m ²/ g.

Embodiment 2

10g phosphotungstic acid and 130mL deionized water are placed in to the round-bottomed flask of 500mL, pour while stirring 80g silica dioxide granule after solid dissolves completely into, round-bottomed flask is connected in mixed sizing device, at 20 ℃, load 8h, obtains catalyst intermediate;

Temperature is increased to 80 ℃ of moisture in evaporate to dryness catalyst intermediate, again the catalyst intermediate after evaporate to dryness is placed in to Muffle furnace, at 300 ℃, carry out the first roasting 8h, obtain the first product of roasting, then to the phosphoric acid solution that adds 130mL mass fraction 6.5% in the first product of roasting, continuation is processed 2h at 90 ℃, temperature is increased to 100 ℃ again, evaporating water, then the ammonia spirit that is 5% by 130mL mass concentration is processed 2h at 90 ℃, then filter, by the solid washing obtaining 3 times, temperature being increased to 125 ℃ is again dried, finally be placed in Muffle furnace, at 550 ℃, carry out the second roasting 0.5h, obtain solid acid catalyst.

Test result shows, the total acid content of the solid acid catalyst that the embodiment of the present invention obtains is 3.42mmol/g, and B acid activity center is 2.33 with the ratio at L acid activity center, and specific area is 277m ²/ g.

Embodiment 3

10g phosphotungstic acid and 130mL deionized water are placed in to the round-bottomed flask of 500mL, after dissolving completely, pours while stirring solid 80g silica dioxide granule into, round-bottomed flask is connected in mixed sizing device, and load 2.5h at 90 ℃ of reaction temperatures, obtains catalyst intermediate;

Temperature is increased to 100 ℃, moisture in evaporate to dryness catalyst intermediate, again the catalyst intermediate after evaporate to dryness is placed in to Muffle furnace, the first roasting 4h at 330 ℃, obtain the first product of roasting, then to the phosphoric acid solution that adds 130mL mass fraction 6.5% in the first product of roasting, continuation is processed 2h at 90 ℃, temperature is increased to 120 ℃ again, evaporating water, then the ammonia spirit that is 5% by 130mL mass concentration is processed 2h at 90 ℃, then filter, by the solid washing obtaining 2 times, again temperature increase to 125 ℃ is dried, finally be placed in Muffle furnace, at 520 ℃, carry out the second roasting 4h, obtain solid acid catalyst.

Embodiment 4

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, the present embodiment be take 25g phosphomolybdic acid as active component.

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 30g Na _2.5h _0.5pW ₁₂o ₄₀for active component.

Embodiment 6

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, the present embodiment be take silicomolybdic acid as active component.

Embodiment 7

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, the present embodiment be take silicotungstic sodium as active component.

Embodiment 8

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, the present embodiment be take Calcium Phosphomolybdate as active component.

Embodiment 9

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, the present embodiment be take phosphomolybdic acid iron as active component.

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 1g Al ₂o ₃for carrier, described carrier is used after roasting 1h at 400 ℃.

Embodiment 11

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, the present embodiment be take Graphene as carrier, and described carrier is used after roasting 1h at 400 ℃.

Embodiment 12

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, the present embodiment be take CNT as carrier, and described carrier is used after roasting 1h at 400 ℃.

Embodiment 13

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, in the present embodiment, active component phosphotungstic acid is 5g, the H that mass concentration is 85% ₃pO ₄5mL.

Embodiment 14

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, in the present embodiment, active component phosphotungstic acid is 5g, the H that mass concentration is 85% ₃pO ₄10mL.

Embodiment 15

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and difference is, in the present embodiment, active component phosphotungstic acid is 20g, the H that mass concentration is 85% ₃pO ₄20mL.

Embodiment 16

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

Embodiment 17

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 1, and difference is, the SILVER REAGENT raw material that Kaolinite Preparation of Catalyst is used changes industrial raw material into, investigates the impact of impurity on catalyst performance.

Embodiment 18

The solid acid catalyst of 2g embodiment 1 gained is placed in to the fixed bed reactors shown in Fig. 1, isobutene is passed into reaction tube by the first material feeding pump, the first valve, the first material pipe and mixed material pipeline successively, formaldehyde is passed into reaction tube by the second material feeding pump, the second valve, the second material pipe and mixed material pipeline successively, the mol ratio that the present invention controls isobutene and formaldehyde is 5.5:1, in reaction tube, in reaction temperature, it is 290 ℃, gas-solid contact time is to react 30min under the condition of 0.8s, obtains product.

The present invention is to the product that obtains through gas chromatographic analysis, and result shows to contain in product isoprene.

The present invention selectively calculates isoprene, and result is referring to table 1, and table 1 is the experimental result of the embodiment of the present invention 18～49 alkene (ether) aldehyde reaction.

What as can be seen from Table 1, the embodiment of the present invention 18 be take formaldehyde isoprene is selectively 63.4%.

Embodiment 19

The solid acid catalyst of 2g embodiment 2 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 18, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 19 be take formaldehyde isoprene is selectively 62.3%.

Embodiment 20

The solid acid catalyst of 2g embodiment 3 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 18, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 20 be take formaldehyde isoprene is selectively 72.4%.

Embodiment 21

The solid acid catalyst of 2g embodiment 4 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 18, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 21 be take formaldehyde isoprene is selectively 69.6%.

Embodiment 22

The solid acid catalyst of 2g embodiment 5 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 22 be take formaldehyde isoprene is selectively 69.5%.

Embodiment 23

The solid acid catalyst of 2g embodiment 6 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 23 be take formaldehyde isoprene is selectively 55.7%.

Embodiment 24

The solid acid catalyst of 1g embodiment 7 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 24 be take formaldehyde isoprene is selectively 67.3%.

Embodiment 25

The solid acid catalyst of 3g embodiment 8 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 25 be take formaldehyde isoprene is selectively 66.0%.

Embodiment 26

The solid acid catalyst of 1.5g embodiment 9 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 26 be take formaldehyde isoprene is selectively 64.0%.

Embodiment 27

The solid acid catalyst of 2g embodiment 10 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 27 be take formaldehyde isoprene is selectively 69.1%.

Embodiment 28

The solid acid catalyst of 2g embodiment 11 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 28 be take formaldehyde isoprene is selectively 49.7%.

Embodiment 29

The solid acid catalyst of 2g embodiment 12 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 29 be take formaldehyde isoprene is selectively 52.8%.

Embodiment 30

The solid acid catalyst of 2g embodiment 13 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 30 be take formaldehyde isoprene is selectively 69.2%.

Embodiment 31

The solid acid catalyst of 2g embodiment 14 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 31 be take formaldehyde isoprene is selectively 65.4%.

Embodiment 32

The solid acid catalyst of 2g embodiment 15 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 32 be take formaldehyde isoprene is selectively 59.2%.

Embodiment 33

The solid acid catalyst of 2g embodiment 16 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 33 be take formaldehyde isoprene is selectively 63.8%.

Embodiment 34

The solid acid catalyst of 2g embodiment 17 gained is placed in to the fixed bed reactors shown in Fig. 1, the reaction condition that the present invention provides according to embodiment 19, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 34 be take formaldehyde isoprene is selectively 64.5%.

Embodiment 35

The solid acid catalyst that 2g embodiment 1 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 26, and isobutene and acetaldehyde carry out condensation reaction, obtain product.

The present invention is to the product that obtains through gas chromatographic analysis, and result shows to contain in product 2-methyl isophthalic acid, 3-pentadiene.

The present invention is to 2-methyl isophthalic acid, selectively the calculating of 3-pentadiene, and result is referring to table 1, and table 1 is the result of calculation of the embodiment of the present invention 18～49 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the embodiment of the present invention 35 is in acetaldehyde 2-methyl isophthalic acid, 3-pentadiene be selectively 66.2%.

Embodiment 36

The solid acid catalyst that 2g embodiment 1 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 18, and isobutene and isobutylaldehyde carry out condensation reaction, obtain product.

The present invention is to the product that obtains through gas chromatographic analysis, and result shows to contain in product 2,5-dimethyl-1,3-hexadiene.

The present invention is to 2,5-dimethyl-1, selectively the calculating of 3-hexadiene, and result is referring to table 1, and table 1 is the experimental result of the embodiment of the present invention 18～49 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the embodiment of the present invention 36 is in isobutylaldehyde 2,5-dimethyl-1,3-hexadiene be selectively 69.0%.

Embodiment 37

The solid acid catalyst that 2g embodiment 1 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 18, and AMS and formaldehyde carry out condensation reaction, obtain product.

The present invention is to the product that obtains through gas chromatographic analysis, and result shows to contain in product 2-phenyl-1,3-butadiene.

The present invention selectively calculates 2-phenyl-1,3-butadiene, and result is referring to table 1, and table 1 is the result of calculation of the embodiment of the present invention 18～49 alkene (ether) aldehyde reaction.

What as can be seen from Table 1, the embodiment of the present invention 37 be take formaldehyde 2-phenyl-1,3-butadiene is selectively 78.3%.

Embodiment 38

The solid acid catalyst that 2g embodiment 1 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 18, and 2,3-dimethyl-1-butylene and formaldehyde carry out condensation reaction, obtain product.

The present invention is to the product that obtains through gas chromatographic analysis, and result shows to contain in product 3,4-dimethyl-1,3-pentadiene.

The present invention selectively calculates 3,4-dimethyl-1,3-pentadiene, and result is referring to table 1, and table 1 is the result of calculation of the embodiment of the present invention 18～49 alkene (ether) aldehyde reaction.

As can be seen from Table 1, the embodiment of the present invention 38 is in formaldehyde 3,4-dimethyl-1,3-pentadiene be selectively 81.2%.

Embodiment 39

The solid acid catalyst that 2g embodiment 1 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 18, and methyl tertiary butyl ether(MTBE) and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 39 be take formaldehyde isoprene is selectively 58.1%.

Embodiment 40

The solid acid catalyst that 2g embodiment 1 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 18, difference is, fixed bed reactors are replaced by the fluidized-bed reactor that reaction tube is Φ 20mm, other conditions are with the experiment condition of fixed bed reactors, isobutene and formaldehyde carry out condensation reaction, obtain product.

The present invention selectively calculates isoprene, and result is referring to table 1, and table 1 is the result of calculation of the embodiment of the present invention 18～49 alkene (ether) aldehyde reaction.

What as can be seen from Table 1, the embodiment of the present invention 40 be take formaldehyde isoprene is selectively 57.4%.

Embodiment 41

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, difference is, the gas-solid contact time in condensation reaction is 0.2s, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 41 be take formaldehyde isoprene is selectively 77.3%.

Embodiment 42

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, difference is, the gas-solid contact time in condensation reaction is 0.4s, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 42 be take formaldehyde isoprene is selectively 65.7%.

Embodiment 43

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, difference is, the gas-solid contact time in condensation reaction is 1.0s, isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 43 be take formaldehyde isoprene is selectively 53.0%.

Embodiment 44

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, and difference is, and the reaction temperature of condensation reaction is 250 ℃, and isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 44 be take formaldehyde isoprene is selectively 77.3%.

Embodiment 45

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, and difference is, and the reaction temperature of condensation reaction is 270 ℃, and isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 45 be take formaldehyde isoprene is selectively 66.0%.

Embodiment 46

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, and difference is, and the reaction temperature of condensation reaction is 340 ℃, and isobutene and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 46 be take formaldehyde isoprene is selectively 49.5%.

Embodiment 47

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, and difference is, the isobutene that mol ratio is 2:1 and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 47 be take formaldehyde isoprene is selectively 71.0%.

Embodiment 48

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, and difference is, the isobutene that mol ratio is 4:1 and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 48 be take formaldehyde isoprene is selectively 65.9%.

Embodiment 49

The solid acid catalyst that 2g embodiment 2 is obtained is placed in the fixed bed reactors shown in Fig. 1, the reaction condition providing according to embodiment 19, and difference is, the isobutene that mol ratio is 10:1 and formaldehyde carry out condensation reaction, obtain product.

What as can be seen from Table 1, the embodiment of the present invention 49 be take formaldehyde isoprene is selectively 54.8%.

The experimental result of table 1 embodiment of the present invention 18～49 alkene (ether) aldehyde reaction

Embodiment 50

The present invention prepares solid acid catalyst according to the technical scheme described in embodiment 2, and isobutene and formaldehyde carry out condensation reaction, obtain product.Condensation reaction finishes directly by used solid acid catalyst roasting 50min at 500 ℃, to pass into air in roasting process afterwards, and Ventilation Rate is 20L/hr, obtains solid acid catalyst after regeneration.

By the solid acid catalyst after the regeneration obtaining, under the same reaction conditions providing with embodiment 1, isobutene and formaldehyde carry out condensation reaction, obtain product.

The experimental result of the present embodiment is shown in Fig. 2, and Fig. 2 is regeneration and the life assessment figure that the embodiment of the present invention 50 obtains solid acid catalyst, and wherein, curve 1 is conversion ratio, and curve 2 is selective, and curve 3 is yield.

As seen from Figure 2, the life-span of solid acid catalyst provided by the invention is long, and regenerability is good.

Embodiment 51

The catalyst that embodiment 1, embodiment 2 and embodiment 3 are obtained is fixed the amplification test of bed bioreactor and fluidized-bed reactor, and multiplication factor is 10 times.

The present invention measures product, and experimental result shows that amplification test result and little test result differ and is no more than 2%.

As seen from the above embodiment, the invention provides a kind of solid acid catalyst, comprise active component and carrier; Described active component is heteropoly acid and/or heteropolyacid salt; The acid group of described heteropoly acid comprises the first central atom and the first coordination atom; The acid group of described heteropolyacid salt comprises the second central atom and the second coordination atom; Described the first central atom and the second central atom are independently selected from P or Si; Described the first coordination atom and the second coordination atom are independently selected from one or more in W, Mo and V.Solid acid catalyst provided by the invention can catalysis has the compound containing carbonyl of structure shown in formula (I) and has the condensation reaction of the monoolefine compound of structure shown in formula (II), prepares double olefin compound.Solid acid catalyst provided by the invention has higher selectivity of product, has reduced the generation of side reaction in condensation reaction, has improved the productive rate of double olefin compound.And solid acid catalyst catalytic activity provided by the invention is high, has higher conversion ratio.In addition, solid acid catalyst toxicity provided by the invention is little, the life-span is long, regenerability good, is easy to suitability for industrialized production.

The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims

1. a solid acid catalyst, comprises active component and carrier;

Described active component is heteropoly acid and/or heteropolyacid salt;

2. solid acid catalyst according to claim 1, is characterized in that, described heteropoly acid comprises one or more in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, molybdovanaphosphoric acid and silicon molybdenum vanadic acid.

3. solid acid catalyst according to claim 1, is characterized in that, described heteropolyacid salt comprises one or more in heteropoly acid normal salt and heteropoly acid acid salt.

4. solid acid catalyst according to claim 1, is characterized in that, described carrier comprise the compound of magnesium, the compound of the compound of aluminium, titanium, one or more in the compound of silicon and material with carbon element.

5. a preparation method for solid acid catalyst, comprises the following steps:

6. preparation method according to claim 5, is characterized in that, the described step a) temperature of middle load is 20 ℃～95 ℃;

A) time of middle load is 0.5h～8h to described step.

7. preparation method according to claim 5, is characterized in that, carries out roasting and be specially after the described catalyst intermediate that described step a) is obtained is dry:

8. preparation method according to claim 7, is characterized in that, the temperature of described the first roasting is 300 ℃～350 ℃, and the time of the first roasting is 0.5h～8h;

The temperature of described the second roasting is 500 ℃～550 ℃, and the time of the second roasting is 1.0h～10h.

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

Described catalyst is the solid acid catalyst that preparation method obtains described in solid acid catalyst described in claim 1～4 any one or claim 5～8 any one;

10. preparation method according to claim 9, is characterized in that, R ₁, R ₂, R ₃and R ₄the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that the branched alkyl that the straight chained alkyl that is 1～8 independently selected from hydrogen, carbon number, carbon number are 1～8, carbon number are 1～8 replaces or carbon number are 1～8 replaces.

11. preparation methods according to claim 9, is characterized in that, described in what have structure shown in formula (I) is 1:1～12 containing the compound of carbonyl and the mol ratio with the monoolefine compound of structure shown in formula (II);

12. preparation methods according to claim 9, is characterized in that, the temperature of described condensation reaction is 220 ℃～350 ℃;

The time of condensation reaction is 20min～40min.