CN111908999B - Method for preparing 1, 3-butanediol - Google Patents
Method for preparing 1, 3-butanediol Download PDFInfo
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Abstract
The invention provides a method for preparing 1, 3-butanediol. The method comprises the following steps: (1) butadiene, water and an aldehyde ketone compound are subjected to condensation cyclization reaction in the presence of hydrogen peroxide and a catalyst A according to a certain material ratio to obtain a reaction solution containing an intermediate I; (2) and mixing the reaction liquid containing the intermediate I with a certain amount of water, and carrying out hydrolysis reaction in the presence of a catalyst B to obtain the 1, 3-butanediol and the corresponding aldehyde ketone compound. Compared with the existing production method, the method has the advantages of easily available reaction raw materials, high reaction conversion rate, high selectivity and the like, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing 1, 3-butanediol.
Background
1, 3-butanediol (1,3-Butylene Glycol, 1,3-BG) has the reactivity of dihydric alcohol, the industrial-grade product can be used as the raw material of polyester resin, alkyd resin and the like, and various monocarboxylic acid monoesters thereof are excellent plasticizers of PVC resin and plastics. The 1,3-BG can also be made into unsaturated polyester resin with phthalic anhydride, maleic anhydride and other monomers. 1,3-BG has antibacterial effect, and can be used as antibacterial agent for dairy products and meat products. The toxicity of the 1,3-BG on higher animals is very low and is equivalent to that of glycerol, the toxicity is lower than that of 1, 4-butanediol, the LD50 (rat) is 22.8-29.5 g/kg, and the LD50 (mouse) is 23.4 g/kg. In the field of cosmetics, 1,3-BG is a high-end humectant applied by formulators for a long time due to the characteristics of transparency, colorlessness, extremely light taste and the like, and can also be used as an emollient, a solvent, an essence cosolvent and the like.
At present, the industrial preparation method of 1,3-BG mainly comprises (1) a biological fermentation method; (2) condensing and hydrolyzing propylene and formaldehyde; (3) acetaldehyde condensation hydrogenation method. The acetaldehyde condensation hydrogenation method is a main stream production process of 1, 3-butanediol, and comprises two steps of condensation and hydrogenation, wherein acetaldehyde is firstly used as a raw material and is subjected to self-condensation under an alkaline catalyst to generate 3-hydroxybutyraldehyde, and then the 3-hydroxybutyraldehyde is hydrogenated to obtain the 1, 3-butanediol.
In patents disclosed by Liaoning Colon Fine chemical Co., Ltd. (CN105585448A), Japan xylonite Co., Ltd. (US5345004, US6376725, US6900360) and US Seranian corporation (CN100450986C), the condensation step uses an aqueous solution of an inorganic alkali as a catalyst, acetic acid is used for neutralization to neutrality after the condensation is finished, and a desalting step is required in the later product refining process, thereby increasing additional investment. The yield of the final product is about 70 percent.
Considering that the inorganic aqueous alkali solution as a catalyst requires addition of a neutralization step after condensation, the Wu Yanghui issue group of Tongji university (research on acetaldehyde liquid phase and gas phase condensation reaction, Baisu, Shuo academic thesis of Tongji university, 2011; chemical reaction engineering and technology, Vol 29, No. 1) examined the possibility of using an anion exchange resin as a catalyst. The experimental result shows that the basic resin is used as the catalyst, the resin is deactivated after the reaction, the color of the anion exchange resin is changed from light yellow to dark red or black, the reaction performance cannot be recovered after the regeneration is tried, and the main reason is that the resin has poor tolerance to aldehyde organic systems. Furthermore, the group of the Wuhan brilliance subjects investigated the medium-strong alkaline solid base containing alkali metal, alkaline earth metal or amphoteric metal oxide, and the experimental results show that the medium-strong alkaline solid base is used as a catalyst, the reaction temperature is required to be high, and the product is mainly the dehydrated product butenal.
The biological fermentation method takes crops such as sugarcane core, corncob and the like as raw materials, converts starch in the crops into glucose through fermentation, and then further obtains the 1, 3-BG. The manufacturer of this method is the Japanese Kokyu Alcohol company, which is the first plant-derived 1,3-BG on the market. The method has the advantages that the capacity is difficult to expand, the capacity is not matched with the global market capacity, the production cost is high, the product price is high, and the price is more than 100000 yuan/ton of RMB.
The condensation hydrolysis method of propylene and formaldehyde is that propylene and formaldehyde are condensed in an acid catalyst to obtain 4-methyl-1, 3-dioxane, which is hydrolyzed under an acid condition to obtain 1, 3-BG. The specific process of condensation and hydrolysis of propylene and formaldehyde adopts two-step method, uses H+Type cation exchange resin instead of H2SO4A catalyst. The first step is as follows: condensing propylene and formaldehyde aqueous solution to obtain 4-methyl-1, 3-dioxane; the second step is that: 4-methyl-1, 3-dioxane is hydrolyzed in the presence of methanol. The methanol is used for condensing and preparing easily separated methylal with formaldehyde hydrolyzed.
In addition to the two-step condensation-hydrolysis method, a method for preparing 1,3-BG from propylene and formaldehyde in one step has been reported, which essentially couples the two-step condensation and hydrolysis reactions. Wang et al (J.Am. chem.Soc.2013,135,1506-1515) of the institute of Connectories of the Chinese academy of sciences reported a one-step process for the preparation of 1,3-BG from propylene and formaldehyde. The adopted catalyst is a Lewis acid catalyst CeO2The reaction is carried out at 180 ℃ and 0.8MPa by taking water as a solvent, and the propylene and the formaldehyde are converted into the 1,3-BG in one step. However, this process gave a 1,3-BG yield of only 60%, 26% of 4-methyl-1, 3-dioxane which had not been hydrolyzed, 11% of p-hydroxy-1-oxacyclohexane and 4% of other by-products. Patent applied to the same subject group (CN 10531513)0B) Reported in (1) using Y2O3-ZrO2The composite oxide catalyst catalyzes formaldehyde and propylene to produce 1,3-BG by condensation, the conversion rate of the formaldehyde is only 42 percent, and the selectivity of the 1,3-BG is 90 percent.
In conclusion, the propylene formaldehyde condensation method has low product yield and higher production cost. The production process was industrialized in the 70 th century, but is no longer used by suppliers today.
Therefore, the acetaldehyde condensation hydrogenation method has the defects of difficult separation of homogeneous catalysts, high-pressure equipment, high production cost of a biological fermentation method, low product yield of a propylene formaldehyde condensation method and the like. Therefore, a new method for preparing 1, 3-butanediol is required to be sought, and the problems that the homogeneous catalyst is difficult to separate, the reaction pressure is high, the production cost is high, the product yield is low and the like in the existing production method are solved.
Disclosure of Invention
The invention aims to provide a method for preparing 1, 3-butanediol, which solves the problems of difficult separation of a homogeneous catalyst, high reaction pressure (acetaldehyde condensation hydrogenation method), high production cost (biological fermentation method), low product yield (propylene formaldehyde condensation method) and the like in the existing production method, has the advantages of easily obtained reaction raw materials, high reaction conversion rate, high selectivity and the like, and is suitable for industrial production.
In order to achieve the purpose, the invention provides the following technical scheme:
a method of making 1, 3-butanediol comprising the steps of:
(1) butadiene, water and an aldehyde ketone compound are subjected to condensation cyclization reaction in the presence of hydrogen peroxide and a catalyst A according to a certain material ratio to obtain a reaction solution containing an intermediate I;
(2) mixing the reaction liquid containing the intermediate I with a certain amount of water, carrying out hydrolysis reaction in the presence of a catalyst B to obtain 1, 3-butanediol and a corresponding aldehyde ketone compound,
wherein R is1And R2Independently of one another, from linear or branched C1-C6 alkyl or H, and R1And R2At least one is an alkyl group, preferably methyl, ethyl or propyl.
The reaction equation is shown as follows:
the aldehyde ketone compound has a structural formula
Wherein R is1And R2Independently of one another, from linear or branched C1-C6 alkyl or H, and R1And R2At least one is an alkyl group, preferably methyl, ethyl or propyl. Since the hydrolysis reaction preferably adopts a reactive distillation process, the aldehyde ketone compound is required to be easily separated, and acetaldehyde, propionaldehyde, acetone, butyraldehyde or butanone is preferred. Formaldehyde is not an option because it is difficult to purify in the aqueous systems of the present invention.
In the step (1), the molar ratio of the raw materials of butadiene, water and the aldehyde ketone compound is 1: 1.0-1.5: 1.0-2.0, preferably 1: 1.1-1.2: 1.1-1.5.
The reaction temperature in the step (1) is 30-150 ℃, and preferably 60-120 ℃.
The catalyst A adopted in the step (1) is solid acid, and the solid acid is one or more of cation exchange resin, acidic mineral, acidic metal oxide and modified zeolite; cation exchange resin and acidic alumina are preferred.
In the step (1) of the invention, the amount of the catalyst A is 0.1-10%, preferably 1-5%, based on the mass percentage of the catalyst in the total reaction materials (the sum of butadiene, water and the aldehyde ketone compound).
The hydrogen peroxide adopted in the step (1) is preferably mixed with water to prepare a 0.01-2 wt%, preferably 0.1-0.5 wt% hydrogen peroxide aqueous solution. It is known that butadiene as a conjugated olefin has two types of addition reactions, namely 1, 2-addition and 1, 4-addition, and thus there are two types of addition reactions between butadiene and water, and the product is a mixture of 1,2-, 1,3-, 2, 3-butanediol without hydrogen peroxide, and since the boiling points of the three diols are close to each other, there is a certain difficulty in separation. The specific reaction equation is as follows:
in the step (1), a certain amount of hydrogen peroxide is introduced in the addition reaction of butadiene and water, so that an unexpected result can be achieved, butadiene hydration has higher selectivity of 1-butenol, more 1, 3-butanediol is generated after condensation hydrolysis with aldehyde, and a specific reaction mechanism is shown as follows.
By introducing hydrogen peroxide, a reaction intermediate is a free radical, and the addition rule is an inverse Markov rule. The product selectivity can be effectively controlled, the hydrogen peroxide is unstable, the hydrogen peroxide can be gradually consumed and decomposed in the reaction process, the problem of terminating free radicals is not considered, the convenience of the reaction is improved, and the cost is reduced.
As a preferable scheme, the step (1) adopts a kettle type reaction process, and the specific operation steps are as follows: firstly, adding a hydrogen peroxide aqueous solution with a certain concentration and a catalyst A into a reaction kettle, starting stirring, introducing butadiene after the temperature is raised to the reaction temperature and kept constant for 5-10 min, starting adding an aldehyde ketone compound after 0.5-1 min, and controlling the feeding speed of the butadiene and the aldehyde ketone compound to ensure that the feeding time of the butadiene (from the beginning of feeding the butadiene to the end of feeding) is the same as the feeding time of the aldehyde ketone compound (from the beginning of feeding the aldehyde ketone compound to the end of feeding), and the total feeding time (from the beginning of feeding the butadiene to the end of feeding the aldehyde ketone compound) is 2-4 h. And after the feeding is finished, keeping the reaction temperature, continuing to react for 0.5-1 h, stopping stirring, and filtering to remove the catalyst to obtain a reaction solution containing the intermediate I.
The reaction solution obtained in step (1) of the present invention may be purified by conventional vacuum distillation means to obtain intermediate I for use in step (2), or may be used directly in step (2) without purification, preferably, the reaction solution obtained in step (1) is filtered to remove the catalyst and then used directly in step (2).
The reaction material ratio required in the step (2) is that the molar ratio of the intermediate I to water is 1: 2-10, preferably 1: 3-8, wherein the amount of the intermediate I is calculated by the theoretical generation amount in the step (1).
The catalyst B adopted in the step (2) is a zirconium system super acid, preferably a molecular sieve modified zirconium system super acid. The preparation method refers to a preparation method of molecular sieve modified zirconium super acid disclosed in Chinese patent CN104557777A, and the preparation method comprises the following steps: a certain mass of zirconium oxychloride octahydrate (ZrOCl)2·8H2O) is dissolved in water, ZrOCl is added after the hydrolysis is completed2·8H2The molecular sieve is 2.5-3 times of the mass of O, the used molecular sieve is one or two or more of 3A type molecular sieve, 4A type molecular sieve, 5A type molecular sieve, 13X type molecular sieve, glass hollow molecular sieve and MCM-41 type molecular sieve, preferably MCM-41 type molecular sieve, after soaking for 0.5-2 hours, ammonia water with the mass fraction of 20wt% is dripped under the stirring condition to adjust the pH value to 8-10, precipitates are separated and washed by distilled water until no chloride ion exists, the precipitates are dried at 100-120 ℃, then the precipitates are soaked for 1-3 hours by sulfuric acid with a certain concentration, the concentration of the sulfuric acid is 0.1-4 mol/L, preferably 0.5-2 mol/L, and the precipitates are dried and then roasted for 2-4 hours at 500-700 ℃ to obtain the molecular sieve modified zirconium system superacid.
The molecular sieve modified zirconium super acid is prepared through loading zirconium oxide onto molecular sieve, sulfuric acid treatment to prepare catalyst with high specific surface area and certain pore structure, and mixing the molecular sieve with SO and its porosity, structural regularity and high specific surface area4 2-/ZrO2Are combined to prepare the product with SO4 2-/ZrO2Molecular sieve structureThe structure characteristic molecular sieve modified zirconium super acid. The super acid surface contains more Bronsted acid (B acid, giving proton) and Lewis acid (L acid, accepting electron) centers than before modification, mainly L acid, and the acid strength range of the surface is Ho<-12.14. The molecular sieve modified zirconium super acid has great surface area and high acidity, and is especially suitable for hydrolysis reaction.
The molecular sieve modified zirconium super acid can provide a large amount of L acid centers, which is beneficial to the adsorption of 1, 3-dioxane compounds on a hydrolysis catalyst and the hydrolysis reaction of raw materials. In addition, the super acid can provide a certain amount of B acid. The B acid is effective in catalyzing the hydrolysis of the acetal. If the amount of L acid in the super acid is too large and the amount of B acid is too small, hydrolysis reaction is not easily caused, and the hydrolysis rate is slow, and therefore, the molar ratio of B acid to L acid can be selected to be 1:80 to 1: 30.
The acid strength of the molecular sieve modified zirconium system super acid has a great relationship with the concentration of sulfuric acid and the roasting temperature, and the roasting temperature and the sulfuric acid concentration can be adjusted by adjusting the roasting temperature and the sulfuric acid concentration.
The concentration of sulfuric acid has a large influence on the acid strength of the solid super acid. The concentration is too low, the acidity of the solid super acid is insufficient, the acid amount is insufficient, the distribution is uneven, and the acid strength is low; when the concentration is too high, the ions of the impregnation liquid can block the small holes of the metal oxide and even react with the oxide to generate salt, so that solid super acid cannot be obtained. In addition, the calcination temperature has an important influence on the strength of the solid acid. Too high a calcination temperature can cause sulfur species to decompose and lose sulfur, thereby reducing acid strength; too low a calcination temperature does not form the desired acid structure, and the solid acid strength does not reach the super acid level. In order to ensure the acid strength of the super acid carrier, the concentration of sulfuric acid is strictly controlled to be 0.5-2 mol/L in order to obtain proper acid strength.
Calcination temperature vs. SO4 2-/ZrO2The B acid/L acid ratio of the solid acid is decisively influenced. The roasting temperature of the invention can convert amorphous oxides into crystals and promote the reaction of sulfuric acid and the oxidesBonding sulfuric acid on the surface of the oxide to generate a corresponding acid site B; can promote in-situ generation of SO3After absorption, pyrosulfuric acid is formed, forming an L-acid site. In order to control the acid ratio of B acid to L acid, the roasting temperature needs to be controlled at 500-600 ℃.
The step (2) of the present invention is carried out in a rectifying column packed with a catalyst. The step (2) is a reversible reaction, and the reaction process and the separation process need to be combined together, so that the low-boiling-point aldehyde ketone compound and the 1,3-BG are quickly separated, the reaction equilibrium is moved to the positive reaction, the reaction is completely converted, and the reaction yield is high. The specific operation is that reaction liquid containing the intermediate I is fed into a tower plate higher than the catalyst layer, water is fed into a tower plate lower than the catalyst layer, low-boiling point aldehyde ketone compound and water are continuously extracted from the tower top, and reaction liquid containing 1, 3-butanediol is continuously obtained from the tower bottom.
In the step (2), the temperature of the bed layer of the rectifying tower is 100-200 ℃, preferably 120-160 ℃. The catalyst treatment amount of the step (2) is 1-10.0 g of intermediate I/(g of catalyst per hour), preferably 2.0-5.0 g of intermediate I/(g of catalyst per hour).
In the preparation method, the 1, 3-butanediol crude product obtained in the step (2) is further separated and purified, preferably rectified under reduced pressure, and then a qualified product meeting the downstream application can be obtained.
The yield of the intermediate I in the step (1) is not lower than 97 percent, calculated by butadiene; the yield of the 1, 3-butanediol in the step (2) is not lower than 98 percent based on the intermediate I; the total yield of the 1, 3-butanediol can reach more than 95 percent based on the butadiene.
The preparation method of the invention has the advantages that: the reaction raw materials are wide in source, cheap and easily available, high-pressure equipment is not needed, the production cost is low, the yield is high, the product is easy to purify, and the method is suitable for industrial production.
Drawings
FIG. 1 is an infrared spectrum of intermediate I of example 1;
FIG. 2 is H of 1, 3-butanediol of example 11NMR spectrum.
Detailed Description
The present invention is further illustrated by the following examples, which should be construed as limiting the scope of the invention.
The main raw materials involved in the invention are as follows:
butadiene, Dalian specialty gas Co., Ltd;
water, preparation of a laboratory water purifier;
40% aqueous acetaldehyde solution, manufactured by West Longsu science corporation;
propionaldehyde, acetone, butyraldehyde, butanone, chemical reagents of the national drug group, ltd;
1# condensation catalyst: acidic alumina powder, dalianhaixin;
2# condensation catalyst: 732 sulfonic acid type cation exchange resin, wherein the exchange capacity of the dry base resin is more than or equal to 4.5 mmol/ml;
the gas chromatography analysis used in this example was carried out as follows: 30m DB-WAX, ID.: 0.32mm, FD.: 0.25 μm; 80-230 ℃,3 ℃/min, nitrogen flow rate: 30mL/min, hydrogen flow rate: 40mL/min, air flow rate: 400 mL/min; sample introduction amount: 0.2. mu.L. GC was tested using Agilent7820 and samples were diluted 3-fold with chromatographic methanol.
Preparation of solid super acidic catalyst:
161g of ZrOCl2·8H2Dissolving O in water, adding 430g of MCM-41 type molecular sieve after complete hydrolysis, dipping for 1 hour, and dropping ammonia water with the mass fraction of 20wt% under the stirring condition to adjust the pH value to about 9. The precipitate is filtered off with suction and washed free of chloride ions with copious amounts of distilled water. Drying the filter residue at 100 ℃, soaking the filter residue for 2h by using sulfuric acid with certain concentration, drying the filter residue at 100 ℃, and roasting the filter residue for 3h at high temperature to obtain the solid super acidic catalyst.
The acid quantity ratio determination method of the B acid to the L acid comprises the following steps: IR spectrum, L acid center (1446.2 cm) of the assay support after desorption at 300 ℃ under vacuum-1) B acid center (1546.2 cm)-1)。
Acid strength H of different superacids measured by indicator methodoThe preparation conditions and results of the various solid super acidic catalysts are shown in Table 1.
TABLE 1 preparation conditions and results for different solid superacid catalysts
Example 1
(1) Preparation of intermediate (I): 39.80g of 0.5wt% hydrogen peroxide aqueous solution (the amount of water is 2.2mol) and 12.0g of acidic alumina powder are weighed and added into a reaction kettle, stirring is started, after the temperature is raised to 120 ℃ and kept at the constant temperature for 5min, butadiene (the density is 2.41g/L) is introduced at 250ml/min by using a gas flow meter, acetaldehyde is dropwise added at 0.54g/min by using an advection pump after 0.8min, the total feeding time is 3h, wherein 108g (2.0mol) of butadiene is fed, and 96.8g (2.2mol) of acetaldehyde is fed. After the completion of the feeding, the reaction temperature was maintained, and after the reaction was continued for 0.75 hour, the stirring was stopped, and the catalyst was filtered off to obtain 240.0g of a reaction solution containing the intermediate (I), and the content of the intermediate I was 94.83% by gas chromatography, and the yield was 98.10% in terms of butadiene.
FT-IR (CCl) of intermediate I4Solution method, σ/cm-1)：2976(C-H st)，2854(C-H st)， 1410(C-Hδ)，1381(C-Hδ)，1173(C-O st)，1139(C-O st)。
(2) Preparation of 1, 3-BG: the synthesis reaction of the 1,3-BG is carried out in a rectifying tower filled with a catalyst, the inner diameter of the rectifying tower is 25mm, and the length of the rectifying tower is 1000 mm; 400g of catalyst-1 is filled in the middle of the rectifying tower, and filler theta rings are filled at the upper end and the lower end of a catalyst bed layer.
Keeping the bed temperature of a rectifying tower at 120 ℃, feeding the reaction liquid containing the intermediate (I) prepared in the step (1) at the upper end of a catalyst bed layer, continuously feeding the reaction liquid through a feeding pump, wherein the liquid air speed WHSV is 2.0g/gcat/h, simultaneously feeding water at the lower end of the catalyst bed layer, continuously feeding the reaction liquid through the feeding pump, the molar ratio of the intermediate I to the water is 1:3, extracting a low-boiling-point aldehyde ketone compound and water from the tower top, and obtaining the reaction liquid containing 1, 3-butanediol from the tower bottom. GC analysis is carried out on the reaction liquid, the reaction conversion rate reaches 99.90 percent, and the selectivity of 1,3-BG reaches 99.00 percent.
The nuclear magnetic data are as follows: h1NMR (solvent: CDCl)3)，δ(ppm)：1.177～1.246(d,3H， CH2OHCH2CHOHCH3)，1.563～1.765(t,2H，CH2OHCH2CHOHCH3)，3.713～4.119 (m，3H，CH2OHCH2CHOHCH3)
Examples 2 to 20
The operation process is the same as that of example 1, except that the reaction conditions, the types of the reaction materials and the amounts of the materials are shown in tables 2 to 3, and the reaction results are shown in table 4.
Table 2 examples 2-20 reaction conditions for step (1)
Table 3 examples 2-20 step (2) reaction conditions
Table 4 examples 2-20 reaction results
| Examples | Step 1) intermediate yield/% | Step 2) conversion/%) | Step 2) selectivity/%% | 1,3-BG yield/%) |
| 2 | 97.51 | 99.91 | 99.01 | 96.46 |
| 3 | 98.32 | 99.96 | 99.05 | 97.35 |
| 4 | 97.34 | 99.90 | 99.15 | 96.42 |
| 5 | 97.65 | 99.92 | 99.24 | 96.83 |
| 6 | 98.16 | 99.90 | 99.17 | 97.25 |
| 7 | 97.37 | 99.96 | 99.06 | 96.42 |
| 8 | 97.61 | 99.91 | 99.08 | 96.62 |
| 9 | 97.82 | 99.94 | 99.31 | 97.09 |
| 10 | 97.56 | 99.92 | 99.34 | 96.84 |
| 11 | 97.17 | 99.96 | 99.27 | 96.42 |
| 12 | 97.89 | 99.98 | 99.34 | 97.22 |
| 13 | 97.92 | 99.93 | 99.19 | 97.06 |
| 14 | 97.67 | 99.91 | 99.25 | 96.85 |
| 15 | 97.52 | 99.91 | 99.17 | 96.62 |
| 16 | 97.41 | 99.95 | 99.04 | 96.43 |
| 17 | 97.85 | 99.94 | 99.08 | 96.89 |
| 18 | 97.65 | 99.96 | 99.18 | 96.81 |
| 19 | 98.06 | 99.97 | 99.04 | 97.09 |
| 20 | 98.15 | 99.98 | 99.05 | 97.20 |
Comparative example 1
The operation process is the same as that of example 1, except that in the step (1), 0.5% hydrogen peroxide aqueous solution is replaced by water. The reaction solution obtained in the final step (2) contained 1, 3-butanediol (35.9%), 1, 2-butanediol (35.8%) and 2, 3-butanediol (28.3%).
Comparative example 2
The operation process is the same as that of example 1, except that in the step (1), 0.5% hydrogen peroxide solution is replaced by 3% hydrogen peroxide solution. And (3) finally, the water and the aldehyde ketone compound extracted from the upper end of the reactive distillation tower in the step (2) contain 1% of acetic acid. It is known that excessive hydrogen peroxide oxidizes aldehydes.
Comparative example 3
The procedure is as in example 1, except that in step (2), catalyst-1 is replaced by comparative catalyst-1. The final step (2) reaction conversion was 23.21%.
Comparative example 4
The procedure is as in example 1, except that in step (2), catalyst-1 is replaced by comparative catalyst-2. The final step (2) reaction conversion was 41.25%.
Claims (14)
1. A method of preparing 1, 3-butanediol comprising the steps of:
(1) butadiene, water and aldehyde ketone compounds
Carrying out condensation cyclization reaction in the presence of hydrogen peroxide and a catalyst A according to a certain material ratio to obtain a reaction solution containing an intermediate I;
(2) mixing the reaction liquid containing the intermediate I with a certain amount of water, and carrying out hydrolysis reaction in the presence of a catalyst B to obtain 1, 3-butanediol and a corresponding aldehyde ketone compound;
wherein R is1And R2Independently of one another, selected from linear or branched C1-C6 alkyl or H, and R1And R2At least one is an alkyl group, the catalyst A in the step (1) is cation exchange resin and/or acidic alumina, and the catalyst B in the step (2) is molecular sieve modified zirconium super acid; the preparation method of the molecular sieve modified zirconium super acid comprises the following steps: dissolving a certain mass of zirconium oxychloride octahydrate in water, and adding ZrOCl after the zirconium oxychloride octahydrate is completely hydrolyzed2·8H2And (2) a molecular sieve with the mass 2.5-3 times of that of O, wherein the molecular sieve is one or more of a 3A type molecular sieve, a 4A type molecular sieve, a 5A type molecular sieve, a 13X type molecular sieve, a glass hollow molecular sieve and an MCM-41 type molecular sieve, the molecular sieve is soaked for 0.5-2 hours, ammonia water with the mass fraction of 20wt% is dripped under the stirring condition to adjust the pH value to 8-10, precipitates are separated and washed by distilled water until no chloride ion exists, the precipitates are dried at 100-120 ℃, then the precipitates are soaked for 1-3 hours by sulfuric acid with a certain concentration, the concentration of the sulfuric acid is 0.5-2 mol/L, and the precipitates are dried and then roasted for 2-4 hours at 500-600 ℃ to obtain the molecular sieve modified zirconium-based superacid.
2. The method of claim 1, wherein the alkyl group is selected from methyl, ethyl, and propyl.
3. The method of claim 1, wherein the aldehyde ketone compound is selected from acetaldehyde, propionaldehyde, acetone, butyraldehyde, or butanone.
4. The method according to claim 1, wherein in the step (1), the molar ratio of the raw materials of butadiene, water and the aldehyde ketone compound is 1: 1.0-1.5: 1.0-2.0.
5. The method according to claim 1, wherein in the step (1), the molar ratio of the raw materials of butadiene, water and the aldehyde ketone compound is 1: 1.1-1.2: 1.1-1.5.
6. The method according to claim 1, wherein the reaction temperature in the step (1) is 30 to 150 ℃.
7. The method according to claim 1, wherein the reaction temperature in the step (1) is 60 to 120 ℃.
8. The method according to claim 1, wherein the hydrogen peroxide in the step (1) accounts for 0.01-2 wt% of the sum of the mass of the water and the hydrogen peroxide.
9. The method according to claim 1, wherein the hydrogen peroxide in the step (1) accounts for 0.1-0.5 wt% of the sum of the mass of the water and the mass of the hydrogen peroxide.
10. The method of claim 1, wherein the step (1) adopts a tank reaction process comprising the steps of: adding a hydrogen peroxide aqueous solution and a catalyst A into a reaction kettle, starting stirring, introducing butadiene after the temperature is raised to the reaction temperature and kept constant for 5-10 min, starting adding an aldehyde ketone compound after 0.5-1 min, controlling the feeding speed of butadiene and the aldehyde ketone compound to ensure that the feeding time of butadiene is the same as that of the aldehyde ketone compound, keeping the total feeding time for 2-4 h, keeping the reaction temperature after the feeding is finished, and continuing to react for 0.5-1 h.
11. The method according to claim 1, wherein the molar ratio of the intermediate I and the water in the step (2) is 1: 2-10.
12. The method according to claim 1, wherein the molar ratio of the intermediate I and the water in the step (2) is 1: 3-8.
13. The method according to claim 1, wherein the step (2) is carried out in a rectifying tower filled with a catalyst, and the bed temperature of the rectifying tower in the step (2) is 100-200 ℃; the catalyst treatment amount in the step (2) is 1-10.0 g of intermediate I/(g of catalyst for hours).
14. The method according to claim 1, wherein the step (2) is carried out in a rectifying tower filled with a catalyst, and the bed temperature of the rectifying tower in the step (2) is 120-160 ℃; the treatment amount of the catalyst in the step (2) is 2.0-5.0 g of intermediate I/(g of catalyst for hours).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5459208A (en) * | 1977-10-17 | 1979-05-12 | Mitsubishi Petrochem Co Ltd | Preparation of butanediol |
| CN105315130A (en) * | 2014-07-22 | 2016-02-10 | 中国科学院大连化学物理研究所 | Method used for preparing 1,3-dihydric alcohol via Prins condensation reaction |
| CN107108397A (en) * | 2015-02-23 | 2017-08-29 | 维尔萨利斯股份公司 | Method for producing alkadienes |
| CN110790634A (en) * | 2019-10-14 | 2020-02-14 | 万华化学集团股份有限公司 | Preparation method of 1, 3-butanediol |
| CN111036296A (en) * | 2019-11-28 | 2020-04-21 | 万华化学集团股份有限公司 | Supported condensation catalyst, preparation method thereof and application of supported condensation catalyst in synthesis of 1, 3-butanediol |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5459208A (en) * | 1977-10-17 | 1979-05-12 | Mitsubishi Petrochem Co Ltd | Preparation of butanediol |
| CN105315130A (en) * | 2014-07-22 | 2016-02-10 | 中国科学院大连化学物理研究所 | Method used for preparing 1,3-dihydric alcohol via Prins condensation reaction |
| CN107108397A (en) * | 2015-02-23 | 2017-08-29 | 维尔萨利斯股份公司 | Method for producing alkadienes |
| CN110790634A (en) * | 2019-10-14 | 2020-02-14 | 万华化学集团股份有限公司 | Preparation method of 1, 3-butanediol |
| CN111036296A (en) * | 2019-11-28 | 2020-04-21 | 万华化学集团股份有限公司 | Supported condensation catalyst, preparation method thereof and application of supported condensation catalyst in synthesis of 1, 3-butanediol |
Non-Patent Citations (2)
| Title |
|---|
| Hydroboration. XII. The hydroboration of dienes with diborane;Zweifel, George等;《Journal of the American Chemical Society》;19621231;第84卷;全文 * |
| Hydroboration. XIII. Hydroboration of dienes with disiamylborane. A convenient procedure for the conversion of selected dienes into unsaturated alcohols;Zweifel, George等;《Journal of the American Chemical Society》;19621231;第84卷(第2期);全文 * |
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