CN103691484B - A kind of preparation method of solid acid catalyst, its preparation method and double olefin compound - Google Patents

Abstract

The invention provides a kind of solid acid catalyst, including active component and carrier；Described active component is heteropoly acid and/or heteropolyacid salt；The acid group of described heteropoly acid includes the first central atom and the first coordination atom；The acid group of described heteropolyacid salt includes the second central atom and the second coordination atom；Described first central atom and the second central atom are P or Si；Described first coordination atom and the second coordination atom include one or more in W, Mo and V.The 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.This catalyst has higher selectivity of product, decreases the generation of side reaction in condensation reaction, improves the productivity of double olefin compound.And, this catalyst activity is high, has higher conversion ratio.

Description

A kind of solid acid catalyst, its preparation method and the preparation method of diene compound

technical field

The invention relates to the technical field of organic synthesis, in particular to a solid acid catalyst, a preparation method thereof and a preparation method of a diolefin compound.

Background technique

Diolefin compounds are unsaturated hydrocarbons containing two carbon-carbon double bonds. The main use of isoprene in diene compounds is to produce isoprene rubber, butyl rubber, pharmaceutical and pesticide intermediates, synthetic lubricating oil additives, rubber vulcanizing agents, etc.

In the prior art, the preparation methods of isoprene mainly include dehydrogenation method, synthesis method and extraction method, wherein the synthesis method includes isobutylene-formaldehyde method, acetylene-acetone method and propylene dimerization method. According to the different reaction processes, the isobutylene and formaldehyde method can also be divided into two-step method and one-step method. Among them, the two-step method is that in the presence of an acidic catalyst, isobutene and formaldehyde undergo a condensation reaction at 70°C to 100°C to generate 4,4-dimethyl-1,3-dioxane and by-products, and separate 4, 4-Dimethyl-1,3-dioxane; then, 4,4-dimethyl-1,3-dioxane is cracked at 250℃～280℃ to produce isoprene, formaldehyde and water . The technological process of this two-step method is loaded down with trivial details, and by-product is complicated. The one-step method is that in the presence of an acidic catalyst, gas-phase isobutene and formaldehyde are directly dehydrated and condensed at a temperature above 200°C to obtain isoprene and water. This one-step process has the advantages of short process and less by-products. Therefore, the gas-phase one-step synthesis of isoprene from alkenal has become a research hotspot.

High-efficiency catalysts are the key technology for the one-step gas-phase synthesis of isoprene from isobutene and formaldehyde. Guo Zhongru (Guo Zhongru, Xue Jinzhen, Xu Xianlun, etc. Research on catalysts for the one-step synthesis of isoprene boronic acid from alkenes and aldehydes. Journal of Fuel Chemistry, March 1983, Volume 11, Issue 3, 57-63.) et al. Three components of vanadium, potassium and aluminum are added to the two-component catalyst of phosphorus and phosphorus to obtain a five-component catalyst, and the five-component catalyst is used to catalyze the condensation reaction of isobutylene and formaldehyde to obtain isoprene. The research results show that the regeneration performance of the boron, phosphorus, vanadium, aluminum and potassium five-component catalyst is improved compared with the boron and phosphorus two-component catalyst, but the boron, phosphorus, vanadium, aluminum and potassium five-component catalyst is not effective for condensation The selectivity of isoprene in the reaction product is still very low, and it is difficult to produce industrially.

Contents of the invention

In view of this, the object of the present invention is to provide a kind of solid acid catalyst, its preparation method and the preparation method of diene compound. The solid acid catalyst provided by the invention has higher product selectivity and improves the yield of the diolefin compound in the process of preparing the diolefin compound in the gas phase one-step method.

The invention provides a solid acid catalyst, comprising an active component and a carrier;

The active component is heteropolyacid and/or heteropolyacid salt;

The acid group of the heteropolyacid includes a first central atom and a first coordination atom;

The acid group of the heteropolyacid salt includes a second central atom and a second coordination atom;

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

The first coordinating atom and the second coordinating atom are independently selected from one or more of W, Mo and V.

Preferably, the heteropolyacid includes one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomomolybdic acid, phosphomolybdovanadate and silicomomolybdovanadate;

Preferably, the heteropoly acid salt includes one or more of heteropoly acid normal salt and heteropoly acid acid salt.

Preferably, the support includes one or more of magnesium compounds, aluminum compounds, titanium compounds, silicon compounds and carbon materials.

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

a) loading the heteropoly compound and the carrier in a solvent to obtain a catalyst intermediate;

b) drying the catalyst intermediate obtained in step a) and then roasting to obtain a solid acid catalyst.

Preferably, the temperature of the load in step a) is 20°C to 95°C;

The loading time in the step a) is 0.5h-8h.

Preferably, the drying of the catalyst intermediate obtained in the step a) after drying is specifically as follows:

Carrying out the first roasting and the second roasting after the catalyst intermediate obtained in the step a) is dried;

The temperature of the first calcination is lower than the temperature of the second calcination.

Preferably, the temperature of the first calcination is 300°C-350°C, and the time of the first calcination is 0.5h-8h;

The temperature of the second calcination is 500°C-550°C, and the time of the second calcination is 1h-10h.

The invention provides a kind of preparation method of diolefin compound, comprises the following steps:

Carrying out a condensation reaction of a carbonyl-containing compound having a structure represented by formula (I) and a monoolefin compound having a structure represented by formula (II) under the action of a catalyst to obtain a diolefin compound;

The catalyst is the solid acid catalyst described in the above technical scheme or the solid acid catalyst obtained by the preparation method described in the above technical scheme;

Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently selected from hydrogen, alkyl or aryl.

Preferably, R ₁ , R ₂ , R ₃ and R ₄ are independently selected from hydrogen, straight chain alkyl groups with 1 to 8 carbon atoms, branched chain alkyl groups with 1 to 8 carbon atoms, and A phenyl group substituted with a straight-chain alkyl group of 1-8 or a phenyl group substituted with a branched-chain alkyl group having 1-8 carbon atoms.

Preferably, the molar ratio of the carbonyl-containing compound having the structure represented by formula (I) to the monoolefin compound having the structure represented by formula (II) is 1:1-12;

The mass ratio of the solid acid catalyst to the carbonyl-containing compound having the structure represented by formula (I) is (1-3) g:1 mol.

Preferably, the temperature of the condensation reaction is 220°C to 350°C;

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

The invention provides a solid acid catalyst, including an active component and a carrier; the active component is a heteropolyacid and/or a heteropolyacid salt; the acid radical of the heteropolyacid includes a first central atom and a first ligand position atom; the acid radical of the heteropolyacid salt includes a second central atom and a second coordination atom; the first central atom and the second central atom are independently selected from P or Si; the first coordination atom and The second coordinating atom is independently selected from one or more of W, Mo and V. The solid acid catalyst provided by the invention can catalyze the condensation reaction of a carbonyl-containing compound having a structure represented by formula (I) and a monoolefin compound having a structure represented by formula (II) to prepare a diolefin compound. The solid acid catalyst provided by the invention has higher product selectivity, reduces the occurrence of side reactions in the condensation reaction process, and improves the yield of diolefin compounds. Moreover, the solid acid catalyst provided by the invention has high catalytic activity and high conversion rate. In addition, the solid acid catalyst provided by the invention has the advantages of low toxicity, long service life, good regeneration performance and easy industrial production. The experimental results show that the selectivity of isobutene and formaldehyde (calculated as aldehyde) reaches up to 78.3% and the conversion rate (calculated as aldehyde) reaches up to 84.3% under the action of solid acid catalyst.

Description of drawings

Fig. 1 is the structural representation of the fixed-bed reactor that the embodiment of the present invention adopts;

Fig. 2 is a regeneration and life evaluation diagram of the solid acid catalyst obtained in Example 50 of the present invention.

detailed description

The invention provides a solid acid catalyst, including an active component and a carrier; the active component is a heteropolyacid and/or a heteropolyacid salt; the acid radical of the heteropolyacid includes a first central atom and a first ligand position atom; the acid radical of the heteropolyacid salt includes a second central atom and a second coordination atom; the first central atom and the second central atom are independently selected from P or Si; the first coordination atom and The second coordinating atom is independently selected from one or more of W, Mo and V.

The solid acid catalyst provided by the invention can catalyze the condensation reaction of a carbonyl-containing compound having a structure represented by formula (I) and a monoolefin compound having a structure represented by formula (II) to prepare a diolefin compound. The solid acid catalyst provided by the invention has higher product selectivity, reduces the occurrence of side reactions in the condensation reaction process, and improves the yield of diolefin compounds. Moreover, the solid acid catalyst provided by the invention has high catalytic activity and high conversion rate. In addition, the solid acid catalyst provided by the invention has low toxicity, long service life and good regeneration performance, and is suitable for industrial production.

The solid acid catalyst provided by the invention includes an active component, which is a heteropolyacid and/or a heteropolyacid salt; the acid group of the heteropolyacid includes a first central atom and a first coordination atom; the The acid radical of the heteropolyacid salt includes a second central atom and a second coordination atom; the first central atom and the second central atom are independently selected from P or Si; the first coordination atom and the second coordination atom One or more independently selected from W, Mo and V. In the present invention, the heteropoly acid preferably includes one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomomolybdic acid, phosphomolybdovanadic acid and silicomomolybdovanadate; more preferably includes phosphotungstic acid One or more of acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid;

In the present invention, the heteropoly acid salt preferably includes one or more of heteropoly acid normal salt and heteropoly acid acid salt, more preferably includes phosphotungstate, phosphomolybdate, silicotungstate , one or more of silicomomolybdate, phosphomolybdovanadate and silicomomolybdovanadate;

In the present invention, the heteropolyacid normal salt preferably includes phosphotungstic acid normal salt, phosphomolybdic acid normal salt, silicotungstic acid normal salt, silicomomolybdic acid normal salt, phosphomolybdovanadate normal salt and silicon molybdovanadate normal salt One or more of salts, more preferably including one or more of phosphotungstic acid normal salt, phosphomolybdic acid normal salt, silicotungstic acid normal salt and silicomolybdic acid normal salt;

In the present invention, the heteropolyacid acid salt includes an acid radical and a cation, and the acid radical includes a second central atom, a second coordination atom and a hydrogen ion; the cation preferably includes an ammonium ion, an alkali metal ion, an alkaline earth metal One or more of ions and transition metal ions, more preferably including ammonium ions, sodium ions, potassium ions, magnesium ions, barium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, platinum ions, palladium ions One or more of ions and copper ions.

In the present invention, specifically, the heteropoly acid acid salt preferably includes phosphotungstic acid salt, phosphomolybdic acid salt, silicotungstic acid salt, silicomomolybdic acid salt, phosphomolybdovanadic acid One or more of acid salt and silicomomolybdovanadic acid salt, more preferably included in phosphotungstic acid salt, phosphomolybdic acid salt, silicomolybdic acid salt and silicomomolybdic acid salt One or more of, most preferably including one or more of sodium phosphotungstic acid, potassium phosphomolybdic acid and iron silicomolybdic acid.

In the present invention, the mass percentage of the active component to the mass of the solid acid catalyst is preferably greater than or equal to 10% and less than 100%, more preferably 20%-90%, most preferably 30%-80%.

The solid acid catalyst provided by the invention includes a carrier. In the present invention, the support preferably includes one or more of magnesium compounds, aluminum compounds, titanium compounds, silicon compounds, and carbon materials; more preferably includes magnesium salt compounds, TiO ₂ , Al ₂ One or more of O ₃ , SiO ₂ and carbon materials, most preferably one or more of MgCl ₂ , Al ₂ O ₃ , TiO ₂ , SiO ₂ , graphene and carbon nanotubes. In the present invention, the source of the carrier is not particularly limited, and the above-mentioned carriers well-known to those skilled in the art can be used, and commercially available products of the above-mentioned carriers can be used.

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

a) loading the heteropoly compound and the carrier in a solvent to obtain a catalyst intermediate;

b) drying the catalyst intermediate obtained in step a) and then roasting to obtain a solid acid catalyst.

In the invention, the heteropoly compound and the carrier are mixed in a solvent and then supported to obtain a catalyst intermediate. In the present invention, the heteropoly compound is preferably dissolved in a solvent. After the heteropoly compound is completely dissolved, a carrier is added therein for loading to obtain a catalyst intermediate. In the present invention, there is no special limitation on the adding method of the heteropoly compound and the carrier, and the mixing is preferably carried out under the condition of stirring. The present invention has no special limitation on the container used for the mixing, and the container well-known to those skilled in the art can be used, such as a flask. In an embodiment of the present invention, the container can be specifically a round-bottomed flask.

In the present invention, the carrier is consistent with the type of the carrier described in the above technical scheme, and will not be described in detail here; the mass ratio of the carrier to the heteropoly compound is preferably (5～10):1, more preferably (6 ~9): 1.

In the present invention, the heteropoly compound includes one or more of heteropoly acid and heteropoly acid salt; The types of salt are the same, and will not be repeated here.

In the present invention, there is no special limitation on the source and type of the solvent, and a solvent well known to those skilled in the art can be used. In the present invention, the solvent is preferably one or more of tap water, distilled water and deionized water; more preferably deionized water. In the present invention, the mass ratio of the heteropoly compound to the solvent is preferably 1:10-15, more preferably 1:11-14, and most preferably 1:12-13.

In the present invention, the loading temperature is preferably 20°C to 95°C, more preferably 25°C to 90°C, most preferably 30°C to 50°C; the loading time is preferably 0.1h to 8h, more preferably It is 0.2h to 5h, most preferably 0.5h to 2.5h.

After the catalyst intermediate is obtained, the present invention drys and roasts the catalyst intermediate to obtain a solid acid catalyst. In the present invention, the drying of the catalyst intermediate is preferably carried out as follows:

performing the first calcining and the second calcining after the catalyst intermediate is dried;

The temperature of the first calcination is lower than the temperature of the second calcination.

The present invention has no special limitation on the drying method, and the drying technical solution well known to those skilled in the art can be adopted. In order to distinguish the drying in the following technical solutions, the present invention names the drying of the catalyst intermediate as the first drying, and the first drying is preferably evaporated to dryness; in the present invention, the temperature of the first drying is preferably 80°C to 125°C, more preferably 90°C to 120°C, most preferably 95°C to 105°C; the present invention has no special limitation on the first drying time, and the catalyst intermediate is dried to a constant weight. Can.

After the drying of the catalyst intermediate is completed, in the present invention, the dried catalyst intermediate is preferably subjected to a first calcination to obtain a first calcination product. The present invention has no special limitation on the equipment for the first calcination, and the calcination equipment well-known to those skilled in the art can be used. For example, a muffle furnace can be used to perform the first calcination on the dried catalyst intermediate. In the present invention, the temperature of the first calcination is preferably 300°C to 350°C, more preferably 320°C to 340°C; the time of the first calcination is preferably 0.5h to 8h, more preferably 2h to 6h, Most preferably 3h-4h.

After the first roasted product is obtained, the present invention preferably treats the first roasted product with a phosphoric acid solution. In the present invention, the order of adding the first roasted product and the phosphoric acid solution is not limited, and the phosphoric acid solution is preferably added to the first roasted product. In the present invention, the mass concentration of the phosphoric acid solution is preferably 1%-20%, more preferably 3%-15%, and most preferably 5%-9%. In the present invention, there is no special limitation on the amount of the phosphoric acid solution, and it is preferred to immerse the first calcined product. In the present invention, the temperature for the phosphoric acid solution to be treated is preferably 80°C to 100°C, more preferably 85°C to 95°C; the time for the phosphoric acid solution to be treated is preferably 0.5h to 8h, more preferably 1.0h ~1.5h.

After the phosphoric acid solution treatment of the first roasted product is completed, the present invention preferably performs second drying on the first roasted product after the phosphoric acid solution treatment, and treats the first roasted product after the second drying with ammonia solution . The method of the second drying is not particularly limited in the present invention, and a drying technical solution well known to those skilled in the art can be adopted, and the second drying is preferably evaporated to dryness. In the present invention, the temperature of the second drying is preferably 95°C to 120°C; more preferably 100°C to 110°C; the present invention has no special limitation on the time of the second drying, and the phosphoric acid solution is treated The final first calcined product can be dried to constant weight. In the present invention, there is no special limitation on the amount of the ammonia solution, and it is preferred to submerge the second dried first calcined product. In the present invention, the mass concentration of the ammonia solution is preferably 1% to 10%, more preferably 2% to 8%, most preferably 4% to 6%; in the present invention, the temperature of the ammonia solution treatment Preferably it is 80°C-100°C, more preferably 85°C-95°C; the time for the ammonia solution treatment is preferably 1h-3h, more preferably 1.5h-2.5h.

After the ammonia solution treatment of the first calcined product is completed, the present invention preferably filters, washes and thirdly dries the obtained first calcined product after the ammonia solution treatment, and then performs the second calcining to obtain a solid acid catalyst. The present invention has no special limitations on the filtration and water washing, and the technical solution of filtration and water washing well known to those skilled in the art can be adopted. In the present invention, the first calcined product treated with the ammonia solution is preferably filtered and then washed with water for 2 to 3 times. The present invention has no special limitation on the drying method, and the drying technical solution well known to those skilled in the art can be adopted. In the present invention, the third drying is preferably evaporated to dryness; the temperature of the third drying is preferably 100°C to 140°C; more preferably 120°C to 130°C; the time of the third drying is not particularly limited , drying the first calcined product after filtering and washing with water to a constant weight.

After the third drying of the first calcined product is completed, in the present invention, the third dried first calcined product is preferably subjected to a second calcining to obtain a solid acid catalyst. The present invention has no special limitation on the equipment for the second calcination, and the calcination equipment well-known to those skilled in the art can be used, for example, a muffle furnace can be used for the second calcination. In the present invention, the temperature of the second calcination is preferably 500°C-550°C, more preferably 510°C-530°C; the time of the second calcination is preferably 1h-10h, more preferably 1.5h-8h, Most preferably, it is 2h to 4h.

The solid acid catalyst provided by the invention can catalyze the condensation reaction of a carbonyl-containing compound having a structure represented by formula (I) and a monoolefin compound having a structure represented by formula (II) to obtain a diolefin compound. The solid acid catalyst provided by the invention has two kinds of active centers: Bronsted acid (abbreviated as B acid) active center and Lewis acid (abbreviated as L acid) active center. In the alkenal condensation reaction process, the B acid active center plays a major role, and the solid acid catalyst provided by the invention has a higher content of the B acid active center, and the higher content of the B acid active center makes the solid acid catalyst provided by the invention have High product selectivity reduces the occurrence of side reactions in the condensation reaction process and improves the yield of diolefin compounds; the solid acid catalyst provided by the invention has a large specific surface area and high catalytic activity, thereby improving conversion Rate.

The present invention measures the total acid content, the ratio of the B acid active center to the L acid active center and the specific surface area of the obtained solid acid catalyst. The measurement results show that the total acid content of the solid acid catalyst provided by the invention is up to 3.42mmol/g, the ratio of B acid active center to L acid active center is up to 2.33, and the specific surface area is up to 295m ² /g.

The invention provides a kind of preparation method of diolefin compound, comprises the following steps:

Carrying out a condensation reaction of a carbonyl-containing compound having a structure represented by formula (I) and a monoolefin compound having a structure represented by formula (II) under the action of a catalyst to obtain a diolefin compound;

The catalyst is the solid acid catalyst described in the above technical scheme or the solid acid catalyst obtained by the preparation method described in the above technical scheme;

Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently selected from hydrogen, alkyl or aryl.

In the present invention, the carbonyl-containing compound having the structure shown in formula (I) and the monoolefin compound having the structure shown in formula (II) undergo condensation reaction, and the reaction formula of the condensation reaction is shown in formula (a).

Formula (a)

Wherein, cat represents the solid acid catalyst provided by the present invention; R ₁ , R ₂ , R ₃ and R ₄ are consistent with R ₁ , R ₂ , R ₃ and R ₄ described in the above technical scheme, and the substituent R ₁ , R ₂ , R ₃ and R ₄ will not be repeated; R ₄ ' has one -H less than R ₄ .

In the present invention, a carbonyl-containing compound having a structure represented by formula (I) and a monoolefin compound having a structure represented by formula (II) are condensed under the action of a catalyst to obtain a diolefin compound. The present invention has no special limitation on the type and source of the carbonyl-containing compound having the structure represented by formula (I), and the carbonyl-containing compound having the structure represented by formula (I) well known to those skilled in the art can be used. In the present invention, R ₁ and R ₂ in formula (I) are independently selected from hydrogen, alkyl or aryl; preferably, R ₁ and R ₂ are independently selected from hydrogen, carbon atoms with 1 to 8 Straight-chain alkyl, branched-chain alkyl with 1-8 carbon atoms, phenyl substituted with straight-chain alkyl with 1-8 carbon atoms or benzene substituted with branched-chain alkyl with 1-8 carbon atoms More preferably, R1 and R2 are independently selected from _one or more of _hydrogen , methyl and isopropyl. In formula (I) of the present invention, when R ₁ and R ₂ are independently selected from phenyl groups substituted by straight-chain alkyl groups with 1 to 8 carbon atoms or phenyl groups substituted with branched chain alkyl groups with 1 to 8 carbon atoms In the case of a phenyl group, the present invention has no special limitation on the substitution position on the phenyl group, which may be an ortho position, a meta position, or a para position.

Specifically, when R ₁ and R ₂ are hydrogen, the carbonyl-containing compound having the structure shown in formula (I) is formaldehyde; when R ₁ is methyl and R ₂ is hydrogen, the compound having the formula (I) The carbonyl-containing compound of the structure shown in ) is acetaldehyde; when R ₁ is isopropyl and R ₂ is hydrogen, the carbonyl-containing compound with the structure shown in formula (I) is isobutyraldehyde.

The present invention has no special limitation on the type and source of the monoolefin compound having the structure represented by formula (II), and the monoolefin compound having the structure represented by formula (II) well known to those skilled in the art can be used.

In formula (II) of the present invention, R ₃ and R ₄ are independently selected from hydrogen, alkyl or aryl; preferably, R ₃ and R ₄ are independently selected from hydrogen, straight chains with 1 to 8 carbon atoms Alkyl, branched chain alkyl with 1 to 8 carbon atoms, phenyl substituted with straight chain alkyl with 1 to 8 carbon atoms or phenyl substituted with branched chain alkyl with 1 to 8 carbon atoms, More preferably, _R3 and _R4 are independently selected from one or more of hydrogen, methyl, isopropyl and benzyl. When R ₃ and R ₄ are independently selected from a phenyl group substituted by a straight-chain alkyl group with 1 to 8 carbon atoms or a phenyl group substituted with a branched chain alkyl group with 1 to 8 carbon atoms, the present invention relates to the The substitution position on the phenyl group is not particularly limited, and it can be the ortho position, the meta position, or the para position.

Specifically, when R ₃ and R ₄ are methyl at the same time, the monoolefin compound having the structure shown in formula (II) is isobutylene; when R ₃ is isopropyl and R ₄ is methyl, the monoolefin compound having The monoalkene compound of structure shown in formula (II) is 2,3-dimethyl-1-butene; When R ₃ is methyl, R ₄ When being phenyl, described having the structure shown in formula (II) The monoolefin compound is α-methylstyrene.

In the present invention, the monoolefin compound having the structure represented by formula (II) can be purchased from the market, or can be prepared by itself according to the preparation methods well known to those skilled in the art. In the present invention, the preparation method of the monoolefin compound having the structure described in formula (II) preferably comprises the following steps:

Etherolysis of the ether compound having the structure shown in formula (III) to obtain a monoolefin compound having the structure shown in formula (II);

Wherein, R ₅ and R ₆ are independently selected from hydrogen, alkyl or aryl.

In the present invention, R ₅ and R ₆ in formula (III) are independently selected from hydrogen, alkyl or aryl; preferably, R ₅ and R ₆ are independently selected from hydrogen, carbon atoms with 1 to 8 Straight-chain alkyl, branched-chain alkyl with 1-8 carbon atoms, phenyl substituted with straight-chain alkyl with 1-8 carbon atoms or benzene substituted with branched-chain alkyl with 1-8 carbon atoms More preferably, _R5 and _R6 are independently selected from one or more of hydrogen, methyl, isopropyl and benzyl. When R ₅ and R ₆ are independently selected from a phenyl group substituted by a straight-chain alkyl group with 1 to 8 carbon atoms or a phenyl group substituted with a branched chain alkyl group with 1 to 8 carbon atoms, the present invention relates to the The substitution position on the phenyl group is not particularly limited, and it can be the ortho position, the meta position, or the para position. Specifically, when R ₅ and R ₆ are both methyl groups, the ether compound having the structure shown in formula (III) is methyl tert-butyl ether.

In the present invention, the temperature of the etherolysis reaction is preferably 150°C to 300°C, more preferably 180°C to 280°C; the time of the etherolysis reaction is preferably 1h to 5h, more preferably 2h to 4h; The catalyst used in the etherolysis reaction preferably includes one or more of Al ₂ O ₃ , sulfate, phosphate, uranium oxide, uranium hydroxide and activated carbon, more preferably Al ₂ O ₃ , U ₃ One or more of O ₈ and Ca ₃ (PO ₄ ) ₂ ; the pressure of the etherolysis reaction is preferably 0.3MPa-0.6MPa, more preferably 0.35MPa-0.55MPa.

In the present invention, the molar ratio of the carbonyl-containing compound having the structure represented by formula (I) to the monoolefin compound having the structure represented by formula (II) is preferably 1:1-12, more preferably 1:2 ～11, most preferably 1:3～10; The quality of described solid acid catalyst and the substance amount ratio of the carbonyl-containing compound having the structure shown in formula (I) are (1～3)g:1mol; More preferably It is (1.5～2.5)g:1mol.

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

The present invention has no special limitation on the device for the condensation reaction, preferably the reaction device shown in Figure 1, which is a schematic structural view of the fixed-bed reactor used in the embodiment of the present invention. Among them, 11 is the first material feed pump; 12 is the second material feed pump; 21 is the first valve, 22 is the second valve, 31 is the first material pipeline, 32 is the second material pipeline, 4 is the mixed material Pipeline, 5 is a reaction tube; 6 is a condenser; 7 is a gas-liquid separation and carbonyl compound recovery device; 8 is a gas chromatograph.

In the present invention, the fixed bed reactor includes a first material feed pump 11 and a first material pipeline 31, and the outlet of the first material feed pump 11 is connected to the feed of the first material pipeline 31. The mouth is connected, and the first material is transported to the first material pipeline 31; the present invention has no special restrictions on the diameter, material and length of the first material pipeline 31, as long as it meets the actual operating conditions;

In the present invention, the fixed bed reactor includes a valve 21. In order to be able to control the feeding amount of the material in the present invention, in an embodiment of the present invention, the first material pipeline 31 is provided with a first valve 21, which is used to for controlling the delivery of the first material. In the present invention, there is no limitation on the position of the first valve 21 on the first material pipeline 31, and it can be set at any position of the first material pipeline 31;

In the present invention, the fixed bed reactor includes a second material feed pump 12 and a second material pipeline 32, and the outlet of the second material feed pump 12 is connected to the feed of the second material pipeline 32. The second material is transported to the second material pipeline 32; the present invention has no special restrictions on the diameter, material and length of the second material pipeline 32, as long as it meets the actual operating conditions; There is no limit to the kind of material conveyed by the material pipeline 31 and the second material pipeline 32. In an embodiment of the invention, the first material pipeline 31 and the second material pipeline 32 will have carbonyl-containing carbonyl compounds of the structure shown in formula (I) respectively. The compound and the monoolefin compound with the structure shown in formula (II) are delivered to the mixed material pipeline 4 and get final product;

In the present invention, the fixed bed reactor includes a valve 22. In order to be able to control the feeding amount of the material in the present invention, in an embodiment of the present invention, the second material pipeline 32 is provided with a second valve 22, which is used to It is used to control the delivery of the second material; the present invention does not limit the position of the second valve 22 on the second material pipeline 32, and can be set at any position of the second material pipeline 32;

In the present invention, the fixed-bed reactor includes a mixed material pipeline 4, and the outlet of the mixed material pipeline 4 is connected to the inlet of the reaction tube 5. The diameter, material and length of the mixed material pipeline 4 in the present invention There are no special restrictions, as long as the actual operating conditions are met; in the present invention, the mixed material pipeline 4 will be the first material transported by the first material pipeline and the second material transported by the second material pipeline. mixed together and delivered to reaction tube 5;

In the present invention, the fixed-bed reactor includes a reaction tube 5, the outlet of the reaction tube 5 is connected to the inlet of the condenser 6, and the reaction tube 5 is used to contain the solid acid catalyst and provide a place for condensation reaction. The present invention has no special limitation on the size of the reaction tube, which can be any size; in the embodiment of the present invention, the diameter of the reaction tube 5 is Φ15mm-Φ20mm;

In the present invention, the fixed bed reactor includes a condenser 6, the outlet of the condenser 6 is connected to the inlet of the gas-liquid separation and carbonyl compound recovery device 7, and the obtained after the polymerization reaction is completed in the reaction tube 5 The reaction product is sent to the condenser 6, and the unreacted carbonyl compound and part of the product are condensed by the condenser 6;

In the present invention, the fixed bed reactor includes a gas-liquid separation and carbonyl compound recovery device 7, the outlet of the gas-liquid separation and carbonyl compound recovery device 7 is connected to the inlet of the gas chromatograph 8, and the gas-liquid separation and carbonyl compound recovery device 7 are connected to each other. The carbonyl compound recovery unit 7 is used to separate the product passing through the condenser 6 and recover unreacted carbonyl compounds;

In the present invention, the fixed bed reactor includes a gas chromatograph 8, and the gas chromatograph 8 is used to measure the composition of the gas phase product separated by the gas-liquid separation device and the content of diolefin compounds in the product; in an embodiment of the present invention, The gas chromatograph is a Thermo Scientific Trace GC ultra chromatograph.

Below in conjunction with the fixed-bed reactor shown in Fig. 1, further the preparation method of the diolefin compound provided by the present invention is described in detail:

In the present invention, the carbonyl-containing compound having the structure shown in formula (I) is transported to the first material pipeline 31 through the first material feed pump 11, and in the process of transporting, the compound having the formula (I) is controlled by the first valve 21. The addition of the carbonyl-containing compound shown in the structure; the monoolefin compound with the structure shown in the formula (II) is transported to the second material pipeline 32 by the second material feed pump 12, and in the process of transport, through the second valve 22. Control the addition of the monoolefin compound with structure shown in formula (II);

The first material pipeline 31 transports the carbonyl-containing compound having the structure shown in formula (I) to the mixed material pipeline 4, and the second material pipeline 32 transports the monoolefin compound having the structure shown in formula (II) to the mixture Feed pipeline 4; The carbonyl-containing compound having the structure shown in formula (I) and the monoolefin compound having the structure shown in formula (II) converge at the mixed feed pipeline 4 and are delivered to the reaction tube 5;

In the reaction tube 5, a solid acid catalyst is placed in advance, and the carbonyl-containing compound with the structure shown in formula (I) and the monoolefin compound with the structure shown in formula (II) carry out condensation reaction under the effect of the above-mentioned solid acid catalyst, Obtain product, product is delivered to condenser 6;

Part of the product is condensed in the condenser 6 to obtain condensed liquid-phase products and uncondensed gas-phase substances, and then the condensed liquid-phase products and uncondensed gas-phase substances are sent to the gas-liquid separation and carbonyl compound recovery device 7 ;

The gas-liquid separation and carbonyl compound recovery device 7 performs gas-liquid separation and recovers unreacted carbonyl compounds. The unreacted carbonyl compounds are absorbed with sodium sulfite solution and then titrated with dilute sulfuric acid to measure the content of unreacted carbonyl compounds, and then calculate the carbonyl compounds. Compound conversion rate; Finally, the gas phase substance is passed into the gas chromatograph 8;

The gas chromatograph 8 measures the gas phase substance, and measures the type and content of the diolefin compound produced in the gas phase substance.

The invention provides a solid acid catalyst, including an active component and a carrier; the active component is a heteropolyacid and/or a heteropolyacid salt; the acid radical of the heteropolyacid includes a first central atom and a first ligand position atom; the acid radical of the heteropolyacid salt includes a second central atom and a second coordination atom; the first central atom and the second central atom are independently selected from P or Si; the first coordination atom and The second coordinating atom is independently selected from one or more of W, Mo and V. The solid acid catalyst provided by the invention can catalyze the condensation reaction of a carbonyl-containing compound having a structure represented by formula (I) and a monoolefin compound having a structure represented by formula (II) to prepare a diolefin compound. The solid acid catalyst provided by the invention has higher product selectivity, reduces the occurrence of side reactions in the condensation reaction process, and improves the yield of diolefin compounds. Moreover, the solid acid catalyst provided by the invention has high catalytic activity and high conversion rate. In addition, the solid acid catalyst provided by the invention has the advantages of low toxicity, long service life, good regeneration performance and easy industrial production.

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

Example 1

Put 10g of phosphotungstic acid and 130mL of deionized water into a 500mL round-bottomed flask. When the solid is completely dissolved, pour 80g of silica particles into it while stirring. Connect the round-bottomed flask to a slurry mixing device and load it at 95°C 0.5h, obtain catalyst intermediate;

Raise the temperature to 125°C, evaporate the moisture of the catalyst intermediate, then place the catalyst intermediate in a muffle furnace, perform the first calcination at 350°C for 0.5h, then raise the temperature to 500°C, and proceed to the second Calcined for 10 hours to obtain a solid acid catalyst.

The present invention tests the total acid content, the ratio of the B acid active center to the L acid active center and the specific surface area of the obtained solid acid catalyst.

The solid acid catalyst obtained in the embodiment of the present invention has a total acid content of 3.21 mmol/g, a ratio of B acid active centers to L acid active centers of 2.16, and a specific surface area of 295 m ² /g.

Example 2

Put 10g of phosphotungstic acid and 130mL of deionized water into a 500mL round-bottomed flask, pour 80g of silica particles into it while stirring when the solid is completely dissolved, connect the round-bottomed flask to a slurry mixing device, and load it at 20°C 8h, obtain catalyst intermediate;

The temperature was raised to 80°C to evaporate the moisture in the catalyst intermediate, and then the evaporated catalyst intermediate was placed in a muffle furnace, and the first roasting was carried out at 300°C for 8 hours to obtain the first roasted product, and then to Add 130mL of phosphoric acid solution with a mass fraction of 6.5% to the first roasted product, continue to treat at 90°C for 2h, then raise the temperature to 100°C, evaporate the water, and then use 130mL of ammonia solution with a mass concentration of 5% at 90°C Down treatment for 2 hours, then filtering, washing the obtained solid three times with water, then raising the temperature to 125°C for drying, and finally placing it in a muffle furnace for a second calcination at 550°C for 0.5h to obtain a solid acid catalyst.

The present invention tests the total acid content, the ratio of the B acid active center to the L acid active center and the specific surface area of the obtained solid acid catalyst.

The test results show that the total acid content of the solid acid catalyst obtained in the embodiment of the present invention is 3.42mmol/g, the ratio of the B acid active center to the L acid active center is 2.33, and the specific surface area is 277m ² /g.

Example 3

Put 10g of phosphotungstic acid and 130mL of deionized water into a 500mL round-bottomed flask, pour 80g of silica particles into it while stirring when the solid is completely dissolved, connect the round-bottomed flask to the slurry mixing device, and the reaction temperature is 90°C Loading 2.5h, obtains catalyst intermediate;

The temperature was raised to 100°C, and the moisture in the catalyst intermediate was evaporated to dryness, then the evaporated catalyst intermediate was placed in a muffle furnace, and the first calcined product was obtained at 330°C for 4 hours to obtain the first calcined product, and then to Add 130mL of phosphoric acid solution with a mass fraction of 6.5% to the first roasted product, continue to treat at 90°C for 2h, then raise the temperature to 120°C, evaporate the water, and then use 130mL of ammonia solution with a mass concentration of 5% at 90°C Down treatment for 2 hours, then filtering, washing the obtained solid twice with water, then raising the temperature to 125°C for drying, and finally placing it in a muffle furnace for a second calcination at 520°C for 4 hours to obtain a solid acid catalyst.

Example 4

The present invention prepares the solid acid catalyst according to the technical scheme described in Example 2, the difference is that in this example, 25 g of phosphomolybdic acid is used as the active component.

Example 5

The present invention prepares a solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, 30g of Na _2.5 H _0.5 PW ₁₂ O ₄₀ is used as the active component.

Example 6

The present invention prepares the solid acid catalyst according to the technical solution described in Example 2, the difference is that this example uses silicomomolybdic acid as the active component.

Example 7

The present invention prepares a solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, sodium silicotungstate is used as an active component.

Example 8

The present invention prepares the solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, calcium phosphomolybdate is used as the active component.

Example 9

The present invention prepares the solid acid catalyst according to the technical scheme described in Example 2, the difference is that in this example, iron phosphomolybdate is used as the active component.

Example 10

The present invention prepares a solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, 1 g of Al ₂ O ₃ is used as a carrier, and the carrier is used after being calcined at 400° C. for 1 h.

Example 11

The present invention prepares a solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, graphene is used as a carrier, and the carrier is used after being calcined at 400° C. for 1 hour.

Example 12

The present invention prepares a solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, carbon nanotubes are used as a carrier, and the carrier is used after being calcined at 400° C. for 1 hour.

Example 13

The present invention prepares a solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, the active component phosphotungstic acid is 5g, and the mass concentration is 85% H ₃ PO ₄ 5mL.

Example 14

The present invention prepares a solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, the active component phosphotungstic acid is 5 g, and H ₃ PO ₄ with a mass concentration of 85% is 10 mL.

Example 15

The present invention prepares a solid acid catalyst according to the technical solution described in Example 2, the difference is that in this example, the active component phosphotungstic acid is 20g, and H ₃ PO ₄ with a mass concentration of 85% is 20mL.

Example 16

The present invention prepares a solid acid catalyst according to the technical solution described in Example 1, the difference is that this example amplifies the catalyst preparation process by 10 times.

Example 17

The present invention prepares a solid acid catalyst according to the technical scheme described in Example 1, the difference is that the reagent-grade raw materials used in the preparation of the catalyst are changed to industrial-grade raw materials, and the influence of impurities on the performance of the catalyst is investigated.

Example 18

2g of the solid acid catalyst obtained in Example 1 is placed in the fixed-bed reactor shown in Figure 1, and isobutylene is passed into the reactor through the first material feed pump, the first valve, the first material pipeline and the mixed material pipeline successively. In the tube, the formaldehyde is passed into the reaction tube through the second material feed pump, the second valve, the second material pipeline and the mixed material pipeline successively. The present invention controls the molar ratio of isobutylene and formaldehyde to be 5.5:1. In , the reaction temperature was 290°C and the gas-solid contact time was 0.8s for 30min to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 18 of the present invention, the selectivity of isoprene in terms of formaldehyde is 63.4%.

Example 19

2g of the solid acid catalyst obtained in Example 2 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 18 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 19 of the present invention, the selectivity of isoprene in terms of formaldehyde is 62.3%.

Example 20

2g of the solid acid catalyst obtained in Example 3 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 18 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 20 of the present invention, the selectivity of isoprene in terms of formaldehyde is 72.4%.

Example 21

2g of the solid acid catalyst obtained in Example 4 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 18 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 21 of the present invention, the selectivity of isoprene in terms of formaldehyde is 69.6%.

Example 22

2g of the solid acid catalyst obtained in Example 5 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 22 of the present invention, the selectivity of isoprene in terms of formaldehyde is 69.5%.

Example 23

2g of the solid acid catalyst obtained in Example 6 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 23 of the present invention, the selectivity of isoprene in terms of formaldehyde is 55.7%.

Example 24

1 g of the solid acid catalyst obtained in Example 7 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 24 of the present invention, the selectivity of isoprene in terms of formaldehyde is 67.3%.

Example 25

3g of the solid acid catalyst obtained in Example 8 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of isoprene in terms of formaldehyde in Example 25 of the present invention is 66.0%.

Example 26

1.5 g of the solid acid catalyst obtained in Example 9 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 26 of the present invention, the selectivity of isoprene in terms of formaldehyde is 64.0%.

Example 27

2g of the solid acid catalyst obtained in Example 10 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of isoprene in terms of formaldehyde in Example 27 of the present invention is 69.1%.

Example 28

2g of the solid acid catalyst obtained in Example 11 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 28 of the present invention, the selectivity of isoprene in terms of formaldehyde is 49.7%.

Example 29

2g of the solid acid catalyst obtained in Example 12 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 29 of the present invention, the selectivity of isoprene in terms of formaldehyde is 52.8%.

Example 30

2g of the solid acid catalyst obtained in Example 13 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 30 of the present invention, the selectivity of isoprene in terms of formaldehyde is 69.2%.

Example 31

2g of the solid acid catalyst obtained in Example 14 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 31 of the present invention, the selectivity of isoprene in terms of formaldehyde is 65.4%.

Example 32

2g of the solid acid catalyst obtained in Example 15 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 32 of the present invention, the selectivity of isoprene in terms of formaldehyde is 59.2%.

Example 33

2g of the solid acid catalyst obtained in Example 16 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 33 of the present invention, the selectivity of isoprene in terms of formaldehyde is 63.8%.

Example 34

2g of the solid acid catalyst obtained in Example 17 was placed in the fixed-bed reactor shown in Figure 1. According to the reaction conditions provided in Example 19 of the present invention, isobutylene and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 34 of the present invention, the selectivity of isoprene in terms of formaldehyde is 64.5%.

Example 35

2 g of the solid acid catalyst obtained in Example 1 was placed in the fixed-bed reactor shown in Figure 1, and according to the reaction conditions provided in Example 26, isobutylene was condensed with acetaldehyde to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains 2-methyl-1,3-pentadiene.

The present invention calculates the selectivity of 2-methyl-1,3-pentadiene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of 2-methyl-1,3-pentadiene in Example 35 of the present invention is 66.2% based on acetaldehyde.

Example 36

2 g of the solid acid catalyst obtained in Example 1 was placed in the fixed-bed reactor shown in Figure 1, and according to the reaction conditions provided in Example 18, isobutene was condensed with isobutyraldehyde to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains 2,5-dimethyl-1,3-hexadiene.

The present invention calculates the selectivity of 2,5-dimethyl-1,3-hexadiene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of 2,5-dimethyl-1,3-hexadiene in Example 36 of the present invention is 69.0% based on isobutyraldehyde.

Example 37

2 g of the solid acid catalyst obtained in Example 1 was placed in the fixed-bed reactor shown in Figure 1, and according to the reaction conditions provided in Example 18, α-methylstyrene was condensed with formaldehyde to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains 2-phenyl-1,3-butadiene.

The present invention calculates the selectivity of 2-phenyl-1,3-butadiene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of 2-phenyl-1,3-butadiene in Example 37 of the present invention is 78.3% based on formaldehyde.

Example 38

The solid acid catalyst that 2g embodiment 1 obtains is placed in the fixed-bed reactor shown in Fig. 1, according to the reaction condition that embodiment 18 provides, 2,3-dimethyl-1-butene and formaldehyde carry out condensation reaction, get the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains 3,4-dimethyl-1,3-pentadiene.

The present invention calculates the selectivity of 3,4-dimethyl-1,3-pentadiene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of 3,4-dimethyl-1,3-pentadiene in Example 38 of the present invention is 81.2% based on formaldehyde.

Example 39

2g of the solid acid catalyst obtained in Example 1 was placed in the fixed-bed reactor shown in Figure 1, and according to the reaction conditions provided in Example 18, methyl tert-butyl ether and formaldehyde were condensed to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the experimental results of the reactions of alkenyl (ether) aldehydes in Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of isoprene in terms of formaldehyde in Example 39 of the present invention is 58.1%.

Example 40

2g of the solid acid catalyst obtained in Example 1 was placed in the fixed-bed reactor shown in Figure 1, and the reaction conditions provided in accordance with Example 18, the difference was that the fixed-bed reactor was replaced by a fluidized bed reaction with a reaction tube of Φ20mm The other conditions are the same as the experimental conditions of the fixed-bed reactor, and the condensation reaction of isobutene and formaldehyde is carried out to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 40 of the present invention, the selectivity of isoprene in terms of formaldehyde is 57.4%.

Example 41

The solid acid catalyst that 2g embodiment 2 obtains is placed in the fixed-bed reactor shown in Fig. 1, according to the reaction condition that embodiment 19 provides, difference is, the gas-solid contact time in the condensation reaction process is 0.2s, isobutylene and Formaldehyde undergoes a condensation reaction to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 41 of the present invention, the selectivity of isoprene in terms of formaldehyde is 77.3%.

Example 42

The solid acid catalyst that 2g embodiment 2 obtains is placed in the fixed-bed reactor shown in Fig. 1, according to the reaction condition that embodiment 19 provides, difference is, the gas-solid contact time in the condensation reaction process is 0.4s, isobutylene and Formaldehyde undergoes a condensation reaction to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of isoprene in terms of formaldehyde in Example 42 of the present invention is 65.7%.

Example 43

The solid acid catalyst that 2g embodiment 2 obtains is placed in the fixed-bed reactor shown in Fig. 1, according to the reaction condition that embodiment 19 provides, difference is, the gas-solid contact time in the condensation reaction process is 1.0s, isobutylene and Formaldehyde undergoes a condensation reaction to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 43 of the present invention, the selectivity of isoprene in terms of formaldehyde is 53.0%.

Example 44

Put 2 g of the solid acid catalyst obtained in Example 2 in the fixed-bed reactor shown in Figure 1, and follow the reaction conditions provided in Example 19, the difference is that the reaction temperature of the condensation reaction is 250 ° C, and the condensation reaction of isobutylene and formaldehyde is carried out , to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 44 of the present invention, the selectivity of isoprene in terms of formaldehyde is 77.3%.

Example 45

Put 2 g of the solid acid catalyst obtained in Example 2 in the fixed-bed reactor shown in Figure 1, and follow the reaction conditions provided in Example 19, the difference is that the reaction temperature of the condensation reaction is 270 ° C, and the condensation reaction of isobutylene and formaldehyde is carried out , to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 45 of the present invention, the selectivity of isoprene in terms of formaldehyde is 66.0%.

Example 46

Put 2 g of the solid acid catalyst obtained in Example 2 in the fixed-bed reactor shown in Figure 1, and follow the reaction conditions provided in Example 19, the difference is that the reaction temperature of the condensation reaction is 340 ° C, and the condensation reaction of isobutylene and formaldehyde is carried out , to obtain the product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 46 of the present invention, the selectivity of isoprene in terms of formaldehyde is 49.5%.

Example 47

The solid acid catalyst that 2g embodiment 2 obtains is placed in the fixed-bed reactor shown in Fig. 1, according to the reaction condition that embodiment 19 provides, difference is, the isobutylene and formaldehyde that molar ratio is 2:1 carry out condensation reaction, obtain product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that the selectivity of isoprene in terms of formaldehyde in Example 47 of the present invention is 71.0%.

Example 48

The solid acid catalyst that 2g embodiment 2 obtains is placed in the fixed-bed reactor shown in Fig. 1, according to the reaction condition that embodiment 19 provides, difference is, the isobutylene and formaldehyde that molar ratio is 4:1 carry out condensation reaction, obtain product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 48 of the present invention, the selectivity of isoprene in terms of formaldehyde is 65.9%.

Example 49

The solid acid catalyst that 2g embodiment 2 obtains is placed in the fixed-bed reactor shown in Fig. 1, according to the reaction condition that embodiment 19 provides, difference is, the isobutylene that molar ratio is 10:1 and formaldehyde carry out condensation reaction, obtain product.

The present invention analyzes the obtained product through gas chromatography, and the result shows that the product contains isoprene.

The present invention calculates the selectivity of isoprene, and the results are shown in Table 1. Table 1 shows the calculation results of the alkenyl (ether) aldehyde reactions of Examples 18-49 of the present invention.

It can be seen from Table 1 that in Example 49 of the present invention, the selectivity of isoprene in terms of formaldehyde is 54.8%.

Table 1 The experimental results of the reaction of 18-49 alkenyl (ether) aldehydes of the present invention

Example 50

In the present invention, a solid acid catalyst is prepared according to the technical scheme described in Example 2, and isobutylene and formaldehyde undergo condensation reaction to obtain a product. After the condensation reaction, the used solid acid catalyst was directly calcined at 500° C. for 50 min, and air was introduced during the calcining process at a rate of 20 L/hr. After regeneration, the solid acid catalyst was obtained.

The obtained regenerated solid acid catalyst was subjected to a condensation reaction of isobutylene and formaldehyde under the same reaction conditions as those provided in Example 1 to obtain a product.

The experimental results of this example are shown in Figure 2, Figure 2 is the regeneration and life evaluation diagram of the solid acid catalyst obtained in Example 50 of the present invention, wherein Curve 1 is the conversion rate, Curve 2 is the selectivity, and Curve 3 is the yield.

It can be seen from Fig. 2 that the solid acid catalyst provided by the present invention has a long service life and good regeneration performance.

Example 51

The catalyst obtained in Example 1, Example 2 and Example 3 was carried out in a fixed-bed reactor and a fluidized-bed reactor in an amplification experiment, and the amplification factor was 10 times.

The present invention measures the product, and the experimental result shows that the difference between the enlarged test result and the small test result is no more than 2%.

As can be seen from the above examples, the present invention provides a solid acid catalyst, including an active component and a carrier; the active component is a heteropolyacid and/or a heteropolyacid salt; the acid group of the heteropolyacid includes a first A central atom and a first coordination atom; the acid group of the heteropolyacid salt includes a second central atom and a second coordination atom; the first central atom and the second central atom are independently selected from P or Si; the The first coordinating atom and the second coordinating atom are independently selected from one or more of W, Mo and V. The solid acid catalyst provided by the invention can catalyze the condensation reaction of a carbonyl-containing compound having a structure represented by formula (I) and a monoolefin compound having a structure represented by formula (II) to prepare a diolefin compound. The solid acid catalyst provided by the invention has higher product selectivity, reduces the occurrence of side reactions in the condensation reaction process, and improves the yield of diolefin compounds. Moreover, the solid acid catalyst provided by the invention has high catalytic activity and high conversion rate. In addition, the solid acid catalyst provided by the invention has the advantages of low toxicity, long service life, good regeneration performance and easy industrial production.

The above is only a preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications are also It should be regarded as the protection scope of the present invention.

Claims (6)

1. 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 monoolefinic compound of structure shown in formula (II) urging Carry out condensation reaction under the effect of agent, obtain double olefin compound；

Described catalyst is solid acid catalyst；

Described solid acid catalyst includes active component and carrier；

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

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

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

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

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

Described carrier includes one or more in the compound of magnesium, the compound of titanium, the compound of silicon and material with carbon element；

The quality of described active component accounts for the percentage composition of solid acid catalyst quality more than or equal to 10% and less than 100%；

The preparation method of described solid acid catalyst comprises the following steps:

A) load after heteropoly compound being mixed in a solvent with carrier, obtain catalyst intermediate；The temperature of described load Degree is 20 DEG C～95 DEG C, and the time of described load is 0.1h～8h；

B) catalyst intermediate that described step a) obtains is carried out the first roasting and the second roasting the most successively, obtain solid Acid catalyst；The temperature of described first roasting is 300 DEG C～350 DEG C, and the time is 0.5h～8h；The temperature of described second roasting is 500 DEG C～550 DEG C, the time is 1h～10h；

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

Preparation method the most according to claim 1, it is characterised in that described heteropoly acid includes phosphotungstic acid, phosphomolybdic acid, silicon tungsten One or more in acid, silicomolybdic acid, molybdovanaphosphoric acid and silicon molybdenum vanadic acid.

Preparation method the most according to claim 1, it is characterised in that described heteropolyacid salt includes heteropoly acid normal salt and miscellaneous many One or more in acid acid salt.

Preparation method the most according to claim 1, it is characterised in that R₁、R₂、R₃And R₄Independently selected from hydrogen, carbon number Be 1～8 straight chained alkyl, carbon number be 1～8 branched alkyl, carbon number be 1～8 the substituted phenyl of straight chained alkyl Or the substituted phenyl of branched alkyl that carbon number is 1～8.

Preparation method the most according to claim 1, it is characterised in that described in have structure shown in formula (I) containing carbonyl Compound and to have the mol ratio of the monoolefinic compound of structure shown in formula (II) be 1:1～12；

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

Preparation method the most according to claim 1, it is characterised in that the temperature of described condensation reaction is 220 DEG C～350 ℃；

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