CN105315130A - Method used for preparing 1,3-dihydric alcohol via Prins condensation reaction - Google Patents

Abstract

The invention relates to a method used for preparing a 1,3-dihydric alcohol via Prins condensation reaction. According to the method, an olefin and a formaldehyde aqueous solution are taken as reaction substrates, and direct preparation of the 1,3-dihydric alcohol is carried out under catalytic effect of an acidic composite metal oxide. The reaction process comprises following steps: the formaldehyde aqueous solution is mixed with a catalyst, and an obtained mixture is delivered into a pressure vessel for sealing; the olefin gas is added, stirring is carried out, and reaction is carried out for more than 2h at a temperature higher than 80 DEG C. After reaction, the catalyst is easily collected via separation from a reaction system, and can be recycled for a plurality of time, and the highest yield of the 1,3-dihydric alcohol is 90%.

Description

A kind of method that prepares 1,3-dibasic alcohol by Prins condensation reaction

technical field

The invention relates to a method for preparing 1,3-diol through Prins condensation reaction, in particular to the preparation of 1,3-diol through condensation and hydrolysis of formaldehyde and olefin.

Background technique

1,3-diol has important uses in medicine, chemical industry, fuel, etc. It is mainly used as a monomer of polyester and polyurethane, as well as a solvent, antifreeze or protective agent, and is also an important pharmaceutical intermediate and organic synthesis intermediate. 1,3-propanediol can be used to synthesize paint, it can also synthesize 3-hydroxypropionic acid and malonic acid through air oxidation, and react with urea to synthesize cyclic carbonate. 1,3-Butanediol can be used as the raw material of polyester resin and alkyd resin, it can also be used for the synthesis of plasticizer, and it can also be used as wetting agent and softener.

Methods for the preparation of 1,3-diols have been reported. CN87105645A In acidic medium, in the presence of rhodium and phosphine, epoxide is reacted with synthesis gas to prepare 1,3-dibasic alcohol. CN1424993 uses a copper-containing catalyst to hydrogenate 3-hydroxyl aldehyde to prepare 1,3-diol. CN1215715 discloses a method for preparing 1,3-diol by using allyl epoxy alcohol and Lewis acid, and the yield is 30%-100%. US013834 adopts cobalt carbonyl catalyst to prepare 1,3-diol and 3-hydroxy aldehyde through hydroformylation of epoxide. CN1733667 uses molecular sieves, oxides or their mixture as a carrier, and nickel-containing supported two-component as a catalyst to convert 3-hydroxy propionaldehyde aqueous solution into 1,3-propanediol through two-stage hydrogenation reaction. CN101139253 prepares 1,3-propanediol through a two-step process. In the first step, 1,3-bromochloropropane and sodium acetate generate a diester under the action of an alcohol catalyst, and in the second step, the above-mentioned diester and methanol are generated under the action of a resin catalyst to generate 1,3-propanediol, and the conversion rate is and high purity. CN1711228A discloses a method for preparing 1,3-propanediol by hydrogenating 3-hydroxypropionic acid, esters of 3-hydroxypropionic acid and other ester mixtures using ruthenium or a mixture of ruthenium and other metals; CN101003462A discloses a The method for preparing 1,3-propanediol by the glycerol method, the conversion rate reaches over 95%; US5345004 reports a three-step method for preparing 1,3-butanediol, the first step is the condensation of acetaldehyde and alcohol to prepare 2,6-dimethyl -1,3-dioxan-4-ol. In the second step, the above product is decomposed to obtain dimerized m-hydroxybutyraldehyde, and finally hydrogenated to obtain 1,3-butanediol. Patent CN1016654409A discloses a method for preparing 1,3-dihydric alcohol or its cyclic acetal by condensing formaldehyde and olefin with an acidic ionic liquid as a catalyst.

At present, there are problems in the preparation route of 1,3-dihydric alcohol, such as long route, low yield, complex catalyst preparation and difficult separation, and easy deactivation of the catalyst. Therefore, the development of a high-efficiency and low-cost technical route for the preparation of 1,3-diols has important application prospects.

Contents of the invention

The significance of the present invention is to overcome the shortcomings in the current preparation of 1,3-diols, and to prepare such compounds with high efficiency and low cost under relatively mild conditions. The preparation of the catalyst is simple and easy to separate from the substrate and can be used multiple times recycle.

A method for preparing 1,3-diol through Prins condensation reaction, characterized in that: after mixing formaldehyde aqueous solution and catalyst, put it into a pressure vessel and seal it, pour olefin gas into it, stir, and the reaction temperature is higher than 80°C, The reaction time is longer than 2h, and the reaction product is 1,3-diol. The mass concentration of the formaldehyde in the initial reaction system is 1wt% to 60wt%, and the molar ratio of water to formaldehyde in the initial reaction system is greater than or equal to 1; the olefins are: ethylene, trimethylethylene, propylene, 1-butane One or more of alkenes, isobutene, and 1,3-butadiene; the catalyst is an acidic composite metal oxide, and the acidic composite metal oxide is: Al ₂ O ₃ -SiO ₂ , TiO ₂ -SiO ₂ , ZrO ₂ -SiO ₂ , TiO ₂ -ZrO ₂ , Al ₂ O ₃ -B ₂ O ₃ , Al ₂ O ₃ -ZnO, Al ₂ O ₃ -TiO ₂ , Al ₂ O ₃ -Fe ₃ O ₄ , SnO ₂ One or more of -ZnO, CeO ₂ -ZrO ₂ , CeO ₂ -La ₂ O ₃ , CeO ₂ -Al ₂ O ₃ , CeO ₂ -Eu ₂ O ₃ , Y ₂ O ₃ -ZrO ₂ ; acidic The composite metal oxide structure can be marked as AB, and the molar ratio of A to B is 1:1 to 20:1; the molar ratio of formaldehyde to olefin is 0.01 to 100; the amount of catalyst used is 0.01g.( mmol formaldehyde) ^-1 ~0.50g·(mmol formaldehyde) ^-1 ; the reaction temperature is 80°C ~ 230°C; the reaction time is 2h ~ 100h.

The mass concentration of the formaldehyde in the initial reaction system is 7wt% to 38wt%, and the molar ratio of water to formaldehyde in the initial reaction system is greater than or equal to 10; the olefin is: one of propylene, isobutene, 1-butene or Two or more; the catalyst is an acidic composite metal oxide, and the acidic composite oxide is: TiO ₂ -ZrO ₂ , Al ₂ O ₃ -B ₂ O ₃ , Al ₂ O ₃ -TiO ₂ , Al ₂ O ₃ -One or more of Fe ₃ O ₄ , SnO ₂ -ZnO, CeO ₂ -ZrO ₂ , CeO ₂ -La ₂ O ₃ , CeO ₂ -Eu ₂ O ₃ , Y ₂ O ₃ -ZrO ₂ ;

The molar ratio of the formaldehyde to the olefin is 0.1～50; the consumption of the catalyst is: 0.05g·(mmol formaldehyde) ^-1 ～0.2g·(mmol formaldehyde) ^-1 ; the reaction temperature is 120°C～200°C ℃;

The reaction time is 8h-50h.

The catalyst is an acidic composite metal oxide, and the acidic composite metal oxide is: TiO ₂ -ZrO ₂ , Al ₂ O ₃ -B ₂ O ₃ , Al ₂ O ₃ -Fe ₃ O ₄ , SnO ₂ -ZnO, One or more of CeO ₂ -ZrO ₂ , CeO ₂ -La ₂ O ₃ , Y ₂ O ₃ -ZrO ₂ ; the molar ratio of formaldehyde to olefin is 0.5 to 5; the amount of catalyst used is : 0.08g·(mmol formaldehyde) ^-1 ~0.1g·(mmol formaldehyde) ^-1 ; the reaction temperature is 150°C-180°C; the reaction time is 10h-20h.

The pathway to form 1,3-diols with formaldehyde and terminal alkenes as reaction substrates is as follows: under the action of an acid catalyst, H ⁺ reacts with formaldehyde to generate formaldehyde carbocations, and then formaldehyde carbocations attack the C of alkenes =C double bond to get enol carbocation, the electrons on the H ₂ O molecule in the aqueous solution attack the enol carbocation, remove H ⁺ , and generate 1,3-diol. In addition, the formaldehyde carbocation ions generated by H ⁺ and formaldehyde attack alkenes to form enolate carbocations, and the enolate carbocations continue to react with formaldehyde to form 1,3-dioxane or its derivatives. Hydrolysis occurs in acidic aqueous solution to produce 1,3-diols.

According to the Thomas rule, adding other oxides with different valences or coordination numbers to metal oxides will generate activated acid centers, so the acidic composite metal oxides used as supports have a certain amount of defect sites that can be used as Lewis acidic acidic sites. The catalytic reaction process and the appropriate acid strength are important factors affecting the catalytic efficiency. When the acid strength is high, it will not only protonate formaldehyde, but also protonate propylene to generate tetrahydropyran-4-ol (an isomer of 4-methyl-1,3-dioxane) , which reduces the selectivity of 1,3-butanediol, or the interconversion reaction between 1,3-diol and 1,3-dioxane and its derivatives, which is more conducive to the formation of dioxane , thereby reducing the selectivity of dihydric alcohols; at the same time, the water molecules dissociate completely after strong adsorption at the Lewis acid site, resulting in the deactivation of the Lewis acid site; when the acidity is weak, the catalyst activity is low, the reaction time is prolonged, and the conversion rate and The selectivity is reduced or even the reaction cannot be carried out. Therefore, choosing a catalyst with appropriate acid strength is the key to increasing the yield of formamide. Preferred acidic oxides in this reaction are: TiO ₂ -ZrO ₂ , Al ₂ O ₃ -B ₂ O ₃ , Al ₂ O ₃ -Fe ₃ O ₄ , SnO ₂ -ZnO, CeO ₂ -ZrO ₂ , CeO ₂ - One or more of La ₂ O ₃ , Y ₂ O ₃ -ZrO ₂ . The consumption of catalyst is: 0.08g·(mmol formaldehyde) ^-1 ～0.1g·(mmol formaldehyde) ^-1 ;

Compared with the existing method for preparing 1,3-diol, the present invention has the following advantages:

1. The catalyst has high activity, the conversion rate of formaldehyde and the selectivity of 1,3-diol are high, and the yield of 1,3-diol can reach up to 90%.

2. The preparation of the catalyst is simple, the preparation raw materials are easy to obtain, and the cost is low. It can be separated from the reaction system through the existing chemical unit operation, and can be recycled for many times;

3. It has a good catalytic conversion effect on most gaseous olefins, especially propylene, isobutene and 1-butene.

detailed description:

In order to further describe the present invention in detail, several specific implementation examples are given below, but the present invention is not limited to these examples.

Example 1

The process of CeO ₂ -ZrO ₂ obtained by the co-precipitation method is as follows: 17.4g of cerium nitrate hexahydrate and 2.31g of zirconyl nitrate (the molar ratio of cerium to zirconium is 4:1) were respectively dissolved in 100mL of water, the two solutions obtained were mixed, ammonia Aqueous solution (the volume ratio of ammonia water to water is 1:1) to adjust the pH=11, stir at room temperature for 4h, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4h , that is, a composite metal oxide CeO ₂ -ZrO ₂ is obtained. In a 250ml Teflon-lined reactor, add 60mmol38% formaldehyde solution, 3g catalyst and 10ml water respectively, pour 0.9MPa isobutylene into it, stir and react at 150°C for 2h, after the reaction, detect the product by chromatography, 3- The yield of methyl-1,3-butanediol is shown in Table 1.

Example 2

The process of CeO ₂ -ZrO ₂ obtained by the co-precipitation method is as follows: 17.4g of cerium nitrate hexahydrate and 2.31g of zirconyl nitrate (the molar ratio of cerium to zirconium is 4:1) were respectively dissolved in 100mL of water, the two solutions obtained were mixed, ammonia Aqueous solution (the volume ratio of ammonia water to water is 1:1) to adjust the pH=11, stir at room temperature for 4h, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4h , that is, a composite metal oxide CeO ₂ -ZrO ₂ is obtained. In a 250ml Teflon-lined reactor, add 60mmol38% formaldehyde solution, 3g catalyst and 10ml water respectively, pour into 0.9Mpa propylene, stir and react at 180°C for 12h, after the reaction, chromatographically detect the product, 1, The yield of 3-butanediol is shown in Table 1.

Example 3

The process of CeO ₂ -ZrO ₂ obtained by the co-precipitation method is as follows: 17.4g of cerium nitrate hexahydrate and 2.31g of zirconyl nitrate (the molar ratio of cerium to zirconium is 4:1) were respectively dissolved in 100mL of water, the two solutions obtained were mixed, ammonia Aqueous solution (the volume ratio of ammonia water to water is 1:1) to adjust the pH=11, stir at room temperature for 4h, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4h , that is, a composite metal oxide CeO ₂ -ZrO ₂ is obtained. In a 250ml Teflon-lined reaction kettle, add 60mmol38% formaldehyde solution, 3g catalyst and 10ml water respectively, pour into 0.9Mpa ethylene, stir and react at 200°C for 12h, after the reaction, chromatographically detect the product, 1, 3-Propanediol yield is shown in Table 1.

Example 4

The process of CeO ₂ -ZrO ₂ obtained by the co-precipitation method is as follows: 21.7g of cerium nitrate hexahydrate and 1.2g of zirconyl nitrate (the molar ratio of cerium to zirconium is 10:1) were dissolved in 100mL of water respectively, and the two solutions obtained were mixed and ammonia Aqueous solution (the volume ratio of ammonia water to water is 1:1) to adjust the pH=11, stir at room temperature for 4h, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4h , that is, a composite metal oxide CeO ₂ -ZrO ₂ is obtained. In a 250ml Teflon-lined reaction kettle, add 60mmol38% formaldehyde solution, 3g catalyst and 10ml water respectively, pour into 0.9Mpa trimethylethylene, stir and react at 150°C for 2h, after the reaction, chromatographically detect the product , The yield of trimethyl-1,3-propanediol is shown in Table 1.

Example 5

The process of CeO ₂ -ZrO ₂ obtained by the co-precipitation method is as follows: 21.7g of cerium nitrate hexahydrate and 1.2g of zirconyl nitrate (the molar ratio of cerium to zirconium is 10:1) were dissolved in 100mL of water respectively, and the two solutions obtained were mixed and ammonia Aqueous solution (the volume ratio of ammonia water to water is 1:1) to adjust the pH=11, stir at room temperature for 4h, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4h , that is, a composite metal oxide CeO ₂ -ZrO ₂ is obtained. In a 250ml Teflon-lined reaction kettle, add 60mmol38% formaldehyde solution, 3g catalyst and 10ml water respectively, pour 0.9MPa1-butene into it, and stir and react at 150°C for 2h. After the reaction, the product is detected by chromatography. The yield of 1,3-pentanediol is shown in Table 1.

Example 6

The CeO ₂ -La ₂ O ₃ process obtained by the sol-gel method is as follows: 17.4g of cerium nitrate hexahydrate and 4.33g of lanthanum nitrate hexahydrate (the molar ratio of cerium and lanthanum is 4) are dissolved in 100mL water respectively, and the two solutions Mix, add 30mL of thickener ethylene glycol, use 1:1 (v:v) ammonia water to adjust pH = 10, stir at 140°C to lose water to form a porous xerogel, and place the resulting xerosol in air at 400°C After treatment at ℃ for 4 hours, the composite metal oxide CeO ₂ -La ₂ O ₃ was obtained. In a 250ml Teflon-lined reactor, add 80mmol38% formaldehyde solution and 0.15mol1-butene respectively, weigh 8g Amberlyst-15 to catalyze the reaction, add 15ml water, stir the reaction at 130°C for 30h, and the reaction ends Finally, the product was detected by chromatography, and the yield of 1,3-pentanediol is shown in Table 1.

Example 7

The CeO ₂ -La ₂ O ₃ process obtained by the sol-gel method is as follows: 8.2g of cerium nitrate hexahydrate and 0.43g of lanthanum nitrate hexahydrate (the molar ratio of cerium to lanthanum is 19) are dissolved in 100mL water respectively, and the two solutions Mix, add 30mL of thickener ethylene glycol, use 1:1 (v:v) ammonia water to adjust pH = 10, stir at 140°C to lose water to form a porous xerogel, and place the resulting xerosol in air at 400°C After treatment at ℃ for 4 hours, the composite metal oxide CeO ₂ -La ₂ O ₃ was obtained. In a 250ml Teflon-lined reaction kettle, add 60mmol38% formaldehyde solution and 90mmol isobutylene respectively, weigh 3g catalyst to catalyze the reaction, add 10ml water, and stir the reaction at 150°C for 2h. After the reaction, chromatographic detection The yield of product, 3-methyl-1,3-butanediol is shown in Table 1.

Example 8

The process of preparing CeO ₂ -La ₂ O ₃ by co-precipitation method is as follows: 8.2 g of cerium nitrate hexahydrate and 0.43 g of lanthanum nitrate hexahydrate (the molar ratio of cerium to lanthanum is 19) were dissolved in 100 mL of water respectively, and the two solutions were mixed. Adjust the pH to 11 with ammonia water, stir at room temperature for 4 hours, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4 hours to obtain the composite metal oxide CeO ₂ -La ₂ O ₃ . In a 250ml Teflon-lined reactor, add 80mmol38% formaldehyde solution and 0.15mol1-butene respectively, weigh 8g Amberlyst-15 to catalyze the reaction, add 15ml water, stir the reaction at 150°C for 30h, and the reaction ends Finally, the product was detected by chromatography, and the yield of 1,3-pentanediol is shown in Table 1.

Example 9

_The CeO2 _- Eu2O3 process obtained by coprecipitation method is as follows: _17.4g of cerium nitrate hexahydrate and 4.5g of europium nitrate hexahydrate (the molar ratio of cerium to europium is 4) are dissolved in 100mL water respectively, and the two solutions are mixed. Use 1:1 (v:v) ammonia water to adjust pH = 10, stir at room temperature for 4 hours, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4 hours to obtain Composite metal oxide CeO ₂ -Eu ₂ O ₃ . In a 250ml Teflon-lined reactor, add 80mmol38% formaldehyde aqueous solution and 0.15mol1-butene respectively, weigh 3g catalyst to catalyze the reaction, add 15ml water, and stir the reaction at 130°C for 30h. , chromatographically detected products, and the yield of 1,3-pentanediol is shown in Table 1.

Example 10

The process of SnO ₂ -ZnO obtained by the hydrothermal method is as follows: 13g of tin chloride and 0.7g of zinc chloride (the molar ratio of tin to zinc is 10) were dissolved in 100mL of water respectively, and after mixing the two solutions, use 1:1 (v : v) Ammonia water to adjust pH=11, stir at room temperature for 4 hours, pour the resulting precipitate and mother liquor into a hydrothermal synthesis kettle, place in an oven at 200°C for 48 hours, naturally cool to room temperature, filter and separate the precipitate, and wash with deionized water three times , drying the filter cake in an oven at 100°C overnight to obtain the composite metal oxide SnO ₂ -ZnO. In a 250ml Teflon-lined reactor, add 80mmol38% formaldehyde solution and 0.15mol1-butene respectively, weigh 2g catalyst to catalyze the reaction, add 15ml water, and stir the reaction at 130°C for 30h. , chromatographically detected products, and the yield of 1,3-pentanediol is shown in Table 1.

Example 11

The process of Y ₂ O ₃ -ZrO ₂ obtained by the hydrothermal method is as follows: 3.9 g of yttrium chloride and 0.18 g of zirconium oxychloride (the molar ratio of yttrium to zirconium is 20) were dissolved in 50 mL of water respectively, and the two solutions were mixed, and 1 :1 (v:v) ammonia water to adjust the pH=11, stir at room temperature for 4 hours, transfer to a hydrothermal synthesis kettle, and treat in an oven at 200° C. for 2 hours. After naturally cooling to room temperature, it was separated by filtration, washed three times with deionized water, and dried overnight at 100° C. to obtain the composite metal oxide Y ₂ O ₃ -ZrO ₂ . In a 250ml Teflon-lined reactor, add 0.2mol 38% formaldehyde aqueous solution and 0.4mol propylene respectively, weigh 5g to catalyze the reaction, add 30ml water, and stir the reaction at 180°C for 10h. After the reaction, the chromatographic The product was detected, and the yield of 1,3-butanediol is shown in Table 1.

Example 12

The process of Y ₂ O ₃ -ZrO ₂ obtained by the hydrothermal method is as follows: 39.2g of yttrium chloride and 3.6g of zirconium oxychloride (the molar ratio of yttrium to zirconium is 10) were dissolved in 100mL of water respectively, the two solutions were mixed, and 1 :1 (v:v) ammonia water to adjust the pH=11, stir at room temperature for 4 hours, transfer to a hydrothermal synthesis kettle, and treat in an oven at 200° C. for 2 hours. After naturally cooling to room temperature, it was separated by filtration, washed three times with deionized water, and dried overnight at 100° C. to obtain the composite metal oxide Y ₂ O ₃ -ZrO ₂ . In a 250ml Teflon-lined reactor, add 80mmol38% formaldehyde solution and 0.15mol1-butene respectively, weigh 2g catalyst to catalyze the reaction, add 15ml water, and stir the reaction at 180°C for 20h. , chromatographically detected products, and the yield of 1,3-pentanediol is shown in Table 1.

Example 13

_The CeO2 _- Eu2O3 process obtained by the co-precipitation method is as follows: _21.7g of cerium nitrate hexahydrate and 4.5g of europium nitrate hexahydrate (the molar ratio of cerium to europium is 5) are dissolved in 100mL water respectively, and the two solutions are mixed. Use 1:1 (v:v) ammonia water to adjust pH = 10, stir at room temperature for 4 hours, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4 hours to obtain Composite metal oxide CeO ₂ -Eu ₂ O ₃ . In a 250ml Teflon-lined reactor, add 0.1mol 38% formaldehyde solution and 0.3mol ethylene respectively, weigh 5g of the catalyst to catalyze the reaction, add 10ml of water, and stir the reaction at 180°C for 18h. , the chromatographically detected product, and the yield of 1,3-propanediol is shown in Table 1.

Example 14

The process of SnO ₂ -ZnO obtained by the hydrothermal method is as follows: 13.4g of tin chloride and 1.4g of zinc chloride (the molar ratio of tin to zinc is 5) are dissolved in 100mL of water respectively, and after mixing the two solutions, use 1:1 (v:v) Adjust the pH to 11 with ammonia water, stir at room temperature for 4 hours, pour the resulting precipitate and mother liquor into a hydrothermal synthesis kettle, place in an oven at 200°C for 48 hours, cool naturally to room temperature, filter and separate the precipitate, and deionized water After washing three times, the filter cake was dried overnight in an oven at 100°C to obtain the composite metal oxide SnO ₂ -ZnO. In a 250ml Teflon-lined reactor, add 60mmol 38% formaldehyde aqueous solution and 90mmol isobutylene respectively, weigh 3g catalyst to catalyze the reaction, add 10mL water, and stir the reaction at 120°C for 10h. After the reaction, chromatographic detection The yield of product, 3-methyl-1,3-butanediol is shown in Table 1.

Example 15

The CeO ₂ -La ₂ O ₃ process obtained by the sol-gel method is as follows: 8.2g of cerium nitrate hexahydrate and 0.43g of lanthanum nitrate hexahydrate (the molar ratio of cerium to lanthanum is 19) are dissolved in 100mL water respectively, and the two solutions Mix, add 30mL of thickener ethylene glycol, use 1:1 (v:v) ammonia water to adjust pH = 10, stir at 140°C to lose water to form a porous xerogel, and place the resulting xerosol in air at 400°C After treatment at ℃ for 4 hours, the composite metal oxide CeO ₂ -La ₂ O ₃ was obtained. In a 250ml polytetrafluoro-lined reactor, add 60mmol38% formaldehyde aqueous solution and 90mmol isobutylene respectively, weigh 3g catalyst to catalyze the reaction, add 10ml water, stir and react at 150°C for 24h, after the reaction, chromatographic detection The yield of product, 3-methyl-1,3-butanediol is shown in Table 1.

Example 16

The process of CeO ₂ -ZrO ₂ obtained by the co-precipitation method is as follows: 17.4g of cerium nitrate hexahydrate and 2.31g of zirconyl nitrate (the molar ratio of cerium to zirconium is 4:1) were respectively dissolved in 100mL of water, the two solutions obtained were mixed, ammonia Aqueous solution (the volume ratio of ammonia water to water is 1:1) to adjust the pH=11, stir at room temperature for 4h, filter and separate the resulting precipitate, wash with deionized water three times, dry the filter cake in an oven at 100°C overnight, and roast at 500°C for 4h , that is, a composite metal oxide CeO ₂ -ZrO ₂ is obtained. In a 250ml Teflon-lined reaction kettle, add 60mmol38% formaldehyde solution, 3g catalyst and 10ml water respectively, pour 0.9MPa isobutylene into it, stir and react at 150°C for 24h, after the reaction, chromatographically detect the product, 3- The yield of methyl-1,3-butanediol is shown in Table 1.

Comparative Example 1:

In a 250ml Teflon-lined reactor, add 60mmol 38% formaldehyde solution and 90mmol isobutylene respectively, weigh 3g CeO ₂ to catalyze the reaction, add 10ml water, and stir the reaction at 150°C for 2h. After the reaction, chromatographic detection The yield of product, 3-methyl-1,3-butanediol is shown in Table 1.

Comparative example 2:

In a 250ml Teflon-lined reactor, add 0.1mol 38% formaldehyde aqueous solution and 0.3mol ethylene respectively, weigh 5g CeO ₂ to catalyze the reaction, add 10ml water, and stir the reaction at 150°C for 18h. After the reaction, The product was detected by chromatography, and the yield of 1,3-propanediol is shown in Table 1.

Table 1 Evaluation results of the direct preparation of 1,3-diols from olefins

Formaldehyde conversion rate/% 1,3-diol selectivity Example 1 84 75 Example 2 45 89 Example 3 28 85 Example 4 70 80 Example 5 80 85 Example 6 75 97 Example 7 90 83 Example 8 85 99 Example 9 78 85 Example 10 87 92 Example 11 42 90 Example 12 78 99 Example 13 twenty three 85 Example 14 83 99 Example 15 90 99 Example 16 85 99 Comparative Example 1 69 63 Comparative Example 2 12 85

The invention relates to the preparation of 1,3-dibasic alcohol through Prins condensation and hydrolysis reaction by adopting formaldehyde aqueous solution and gaseous olefin as reactants under catalysis. The method has the advantages of simple catalyst preparation, high catalytic activity, a product yield of up to 90%, a simple separation process of the product and the catalyst, multiple recycling of the catalyst, and high controllability of the reaction process.

Claims (4)

1. a method for preparing 1,3-dibasic alcohols by Prins condensation reaction, is characterized in that: After mixing the aqueous formaldehyde and the catalyst, put it into a pressure vessel and seal it, pour in olefin gas, stir, the reaction temperature is greater than or equal to 80°C, the reaction time is greater than or equal to 2 hours, and the reaction product is 1,3-diol. 2. according to the described method of claim 1, it is characterized in that: The mass concentration of the formaldehyde in the initial reaction system is 1 wt% to 60 wt%, and the molar ratio of water to formaldehyde in the initial reaction system is greater than or equal to 1; The olefin is: one or more of ethylene, trimethylethylene, propylene, 1-butene, isobutene, and 1,3-butadiene; The catalyst is an acidic composite metal oxide, and the acidic composite metal oxide is: Al ₂ O ₃ -SiO ₂ , TiO ₂ -SiO ₂ , ZrO ₂ -SiO ₂ , TiO ₂ -ZrO ₂ , Al ₂ O ₃ -B ₂ O ₃ , Al ₂ O ₃ -ZnO, Al ₂ O ₃ -TiO ₂ , Al ₂ O ₃ -Fe ₃ O ₄ , SnO ₂ -ZnO, CeO ₂ -ZrO ₂ , CeO ₂ -La ₂ O ₃ , CeO ₂ - One or more of Al ₂ O ₃ , CeO ₂ -Eu ₂ O ₃ , Y ₂ O ₃ -ZrO ₂ ; the acidic composite metal oxide structure can be marked as AB, and the molar ratio of A to B is 1: 1～20:1; The molar ratio of formaldehyde to olefin is 0.01 to 100; The dosage of the catalyst is 0.01g·(mmol formaldehyde) ^-1 ～0.50g·(mmol formaldehyde) ^-1 ; The reaction temperature is 80°C to 230°C; The reaction time is 2h-100h. 3. according to the described method of claim 1 or 2, it is characterized in that: The mass concentration of the formaldehyde in the initial reaction system is 7wt% to 38wt%, and the molar ratio of water to formaldehyde in the initial reaction system is greater than or equal to 10; The olefin is: one or more of propylene, isobutene, and 1-butene; The catalyst is an acidic composite metal oxide, and the acidic composite oxide is: TiO ₂ -ZrO ₂ , Al ₂ O ₃ -B ₂ O ₃ , Al ₂ O ₃ -TiO ₂ , Al ₂ O ₃ -Fe ₃ O _4. One or more of SnO ₂ -ZnO, CeO ₂ -ZrO ₂ , CeO ₂ -La ₂ O ₃ , CeO ₂ -Eu ₂ O ₃ , Y ₂ O ₃ -ZrO ₂ ; The molar ratio of formaldehyde to olefins is 0.1 to 50; The dosage of the catalyst is: 0.05g·(mmol formaldehyde) ^-1 ～0.2g·(mmol formaldehyde) ^-1 ; The reaction temperature is 120°C to 200°C; The reaction time is 8h-50h. 4. according to the described method of claim 1 or 2, it is characterized in that: The catalyst is an acidic composite metal oxide, and the acidic composite metal oxide is: TiO ₂ -ZrO ₂ , Al ₂ O ₃ -B ₂ O ₃ , Al ₂ O ₃ -Fe ₃ O ₄ , SnO ₂ -ZnO, One or more of CeO ₂ -ZrO ₂ , CeO ₂ -La ₂ O ₃ , Y ₂ O ₃ -ZrO ₂ ; The molar ratio of formaldehyde to olefins is 0.5 to 5; The dosage of the catalyst is: 0.08g·(mmol formaldehyde) ^-1 ～0.1g·(mmol formaldehyde) ^-1 ; The reaction temperature is 150°C to 180°C; The reaction time is 10h-20h.