CN112341314B - Method for preparing 2-methyl-1, 3-propylene glycol from isobutene - Google Patents
Method for preparing 2-methyl-1, 3-propylene glycol from isobutene Download PDFInfo
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Abstract
The invention discloses a method for preparing 2-methyl-1, 3-propylene glycol from isobutene. Mixing isobutene with acetic acid and oxygen, and performing an acetylation reaction under the action of a supported palladium-molybdenum catalyst to obtain 2-methylenepropane-1, 3-diacetoxy, namely a compound (C); performing ester exchange reaction on the compound (C) under the action of a basic catalyst to obtain 2-methylene-1, 3-propylene glycol, namely a compound (D); and (3) carrying out hydrogenation reaction on the compound (D) to obtain the 2-methyl-1, 3-propylene glycol. The method can generate the 2-methyl-1, 3-propanediol with high selectivity, has high atom utilization rate of the whole process, is green and environment-friendly, and is suitable for large-scale industrial application.
Description
Technical Field
The invention belongs to the field of preparation of 2-methyl-1, 3-propanediol, and particularly relates to a method for preparing 2-methyl-1, 3-propanediol from isobutene.
Background
In 1990, the American ARCO chemical company introduces 2-methyl-1, 3-propanediol as a new diol into chemical industry for the first time, and the diol has two primary hydroxyl groups and a unique methyl branched chain structure, so that a product based on the 2-methyl-1, 3-propanediol has the main performance advantages of non-crystallinity, weather resistance, good compatibility with monomers, tensile resistance, strong bending resistance and the like. The product has a unique structure, and has the characteristics of transparency, low toxicity, aroma enhancement, antibiosis, hydration, biodegradation and the like, so that the product has a plurality of unexpected excellent properties, the product has good application in the fields of polyester resin, plasticizer, white electric appliance exterior paint, printing ink, personal care products, transparent resin artware and the like, the application in water-soluble polyester has attracted attention, the product is superior to l, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, diethylene glycol and the like which are widely used at present in many aspects, and the application research of the product has gradually attracted attention. However, 2-methyl-1, 3-propanediol has hitherto been mainly derived from by-products formed in the production of 1, 4-butanediol and has been imported from foreign countries.
Currently, there are two main methods for preparing 2-methyl-1, 3-propanediol. The reaction scheme of the first method is shown as follows:
U.S. Pat. No. 3, 4096192A discloses a process for preparing 1, 4-butanediol and 2-methyl-1, 3-propanediol from acrolein and 1, 3-butanediol by cyclization, hydroformylation and hydrolysis-hydrogenation. The introduction of 1, 3-butanediol in the process increases the cost of separation, and acrolein itself is a highly toxic, flammable and explosive substance and is difficult to store and transport. Furthermore, the main product of the process is 1, 4-butanediol, 2-methyl-1, 3-propanediol, the selectivity of which is only 32% at the most.
The reaction scheme of the second method is shown as follows:
the literature (Ind. Eng. chem. Res.1991,30,1389-1390) reports a reaction route to 1, 4-butanediol and 2-methyl-1, 3-propanediol by hydroformylation and hydrogenation of allyl alcohol as a starting material. The method is the main source of 2-methyl-1, 3-propanediol on the market at present, but the main product of the process is 1, 4-butanediol, and the 2-methyl-1, 3-propanediol is only generated as a byproduct, and the selectivity is only 37 percent at most.
In the two methods, the selectivity of the 2-methyl-1, 3-propanediol is low, and the prices of the reaction raw materials of acrolein and allyl alcohol are high, so that the method is not beneficial to the large-scale production of the 2-methyl-1, 3-propanediol. Therefore, it is necessary to develop a new process for producing 2-methyl-1, 3-propanediol to realize industrial application thereof.
Disclosure of Invention
The invention provides a method for preparing 2-methyl-1, 3-propylene glycol from isobutene, which comprises the following steps:
(1) mixing isobutene (i.e. the compound (A)) with acetic acid and oxygen, and carrying out an oxyacetylation reaction under the action of a supported palladium-molybdenum catalyst to obtain 2-methylene propane-1, 3-diacetoxy, i.e. a compound (C);
(2) performing ester exchange reaction on the compound (C) under the action of a basic catalyst to obtain 2-methylene-1, 3-propylene glycol, namely a compound (D);
(3) and (3) carrying out hydrogenation reaction on the compound (D) to obtain 2-methyl-1, 3-propanediol, namely the compound (E).
In one embodiment, the reactants in step (1) further comprise 2-methyl propenol acetate (compound (B)). Preferably, the molar ratio of isobutene to compound (B) may be (1-10): (0-10), preferably (1-5): (0-5), exemplarily 1:1, 2:1, 1:2, 1: 3.
In one embodiment, in the step (1), 2-methyl allyl alcohol acetate is used as a raw material instead of isobutene, and is reacted with acetic acid and oxygen to obtain the compound (C).
The addition of 2-methylpropenylol acetate in the step (1) can increase the space-time yield of the compound (C).
In one embodiment, the molar ratio of isobutylene, or a mixture of isobutylene and compound (B), or compound (B), to oxygen and acetic acid is (5-12):1 (1.5-5), e.g., (7-10):1 (2-4), illustratively 8:1: 2.
According to an embodiment of the present invention, the reaction of isobutylene with acetic acid and oxygen can yield 2-methylpropenyl alcohol acetate (i.e., compound (B)) and compound (C). The reaction route is as follows:
in one embodiment of the present invention, the 2-methylpropenyl acetate used in the step (1) is separated from the mixture of the compound (B) and the compound (C) as described above, for example, by distillation.
According to an embodiment of the present invention, in step (1), nitrogen is used as a carrier gas. Preferably, the molar ratio of nitrogen to oxygen is (12-20):1, e.g., (14-18):1, illustratively 16: 1.
According to an embodiment of the invention, in step (1), the supported palladium-molybdenum catalyst is KOAc/Pd/MoO3/SiO2A catalyst. Preferably, said KOAc/Pd/MoO3/SiO2The mass content of potassium acetate in the catalyst is 1-10%, such as 2-8%, illustratively 1%, 2%, 4%, 5%, 6%, 8%, 10%.
According to an embodiment of the invention, said KOAc/Pd/MoO3/SiO2The catalyst is prepared by adopting a continuous impregnation method. For example, the KOAc/Pd/MoO3/SiO2The preparation method of the catalyst comprises the following steps:
(a) soaking ammonium molybdate water solution on spherical silicon oxide carrier by wet method, drying and calcining to obtain MoO3/SiO2；
(b) Soaking an aqueous solution of sodium tetrachloropalladate in the MoO by a wet method3/SiO2Drying, calcining and hydrazine hydrate reducing to obtain Pd/MoO3/SiO2Wherein the mass content of the palladium is 0.1-10 percent;
(c) soaking potassium acetate solution in Pd/MoO solution via wet process3/SiO2To obtain the product after dryingKOAc/Pd/MoO3/SiO2A catalyst.
Wherein in step (a), step (b) and/or step (c), the time of impregnation is 1-18h, for example 3-15 h.
Wherein, in the step (a) and/or the step (b), the drying temperature is 100-; further, the drying time is 10 hours or more, for example, 12 hours, 15 hours, and 20 hours.
Wherein, in step (a) and/or step (b), the temperature of the calcination is 300-900 deg.C, such as 400-800 deg.C, and exemplary temperatures are 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C.
Wherein in step (a) and/or step (b), the calcination time is 1-10h, for example 2-8 h.
Wherein, the MoO3/SiO2The molybdenum content is 0.1-10% by mass, such as 2-8%, illustratively 1%, 2%, 4%, 5%, 6%, 8%, 10%.
Wherein in step (b), the time for reducing the hydrazine hydrate is 1-10h, such as 2-8 h.
Wherein, the Pd/MoO3/SiO2The mass content of palladium in (C) is 0.1-10%, such as 2-8%, illustratively 1%, 2%, 4%, 5%, 6%, 8%, 10%.
Wherein in step (c) the drying temperature is 50-80 ℃, for example 60-70 ℃; further, the drying time is 10 hours or more, for example, 12 hours, 15 hours, and 20 hours.
According to an embodiment of the present invention, in step (1), the temperature of the oxoacetylation reaction is 100-.
According to an embodiment of the invention, in step (1), the pressure of the oxoacetylation reaction is 0.5 to 2.0MPa, such as 0.75 to 1.8MPa, exemplary 0.5MPa, 0.75MPa, 1MPa, 1.5MPa, 1.6MPa, 2.0 MPa.
According to an embodiment of the present invention, in step (1), the oxoacetylation reaction may be performed in a fixed bed continuous reactor.
According to an embodiment of the present invention, in the step (2), the alcohol used in the transesterification reaction is C1-4The alkyl alcohol is, for example, at least one of methanol, ethanol, and n-propanol.
According to an embodiment of the present invention, in step (2), the compounds (C) and C1-4The molar ratio of alkyl alcohol is 1 (5-15), such as 1 (7-12), illustratively 1: 10.
According to an embodiment of the present invention, in the step (2), the basic catalyst is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
According to an embodiment of the invention, in step (2), the temperature of the transesterification reaction is in the range of 30 to 80 ℃, such as 40 to 70 ℃, exemplary 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃.
According to an embodiment of the invention, in step (2), the pressure of the transesterification reaction is between 0.1 and 1.0MPa, such as between 0.2 and 0.8MPa, exemplary 0.1MPa, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1.0 MPa.
According to an embodiment of the present invention, in the step (3), the hydrogenation reaction is preferably carried out by reacting the compound (D) with hydrogen in the presence of a catalyst. The catalyst is preferably a supported palladium catalyst, for example Pd/Al2O3A catalyst. Preferably, the supported palladium catalyst has a palladium content of 0.1 to 10% by mass, for example 1 to 8% by mass.
Preferably, the Pd/Al2O3The catalyst is prepared by adopting an impregnation method. Further, the Pd/Al2O3The preparation process of the catalyst comprises the following steps: soaking the water solution of palladium nitrate on alumina carrier, preferably spherical alumina carrier, via wet process, soaking, drying, calcining and hydrogen reducing to obtain Pd/Al2O3A catalyst. Preferably, the time of the impregnation is 1 to 18 h. The drying temperature is 100-140 ℃. Preferably, the temperature of the calcination is 300-900 deg.C, such as 400-800 deg.C. Preferably, the temperature of the hydrogen reduction is 30-600 ℃, and the time is 1-10 h.
According to an embodiment of the present invention, in step (3), the reaction temperature of the hydrogenation reaction is 30 to 150 ℃, for example 50 to 100 ℃.
According to an embodiment of the invention, in step (3), the hydrogen pressure in the hydrogenation reaction is in the range of from 0.1 to 5.0MPa, for example from 1 to 4 MPa.
The invention has the beneficial effects that:
the invention provides a method for preparing 2-methyl-1, 3-propylene glycol from isobutene. In the prior art, 2-methyl-1, 3-propanediol is only used as a byproduct in the production of 1, 4-butanediol, and the yield is limited by the market of 1, 4-butanediol. In the invention, the 2-methyl-1, 3-propanediol is taken as a main product of the reaction, the production is not limited by other products, the atom utilization rate is high, and the method is green and environment-friendly and is suitable for large-scale industrial application.
The invention selects a supported palladium-molybdenum catalyst in the oxygen acetylation reaction of isobutene, acetic acid and oxygen, preferably KOAc/Pd/MoO3/SiO2The catalyst can improve the selectivity of the compound (C).
The present invention also promotes the production of the compound (C) by using the compound (B) produced by the oxoacetylation reaction and isobutylene as raw materials, thereby obtaining 2-methyl-1, 3-propanediol in high yield.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
First step of the Oxyacetylation reaction
The oxyacetylation reaction adopts KOAc/Pd/MoO3/SiO2The preparation method of the catalyst comprises the following steps: 150mL of an aqueous solution of ammonium molybdate was impregnated by a wet method on 100g of the spherical silica support for 12 hours. Drying in a 120 ℃ oven for 12h, calcining in a muffle furnace at 400 ℃ for 5h to obtain MoO3/SiO2Wherein the mass content of molybdenum is 1 percent; 150mL of an aqueous solution of sodium tetrachloropalladate was impregnated in the prepared MoO by a wet method3/SiO2The dipping time is 12h, the mixture is dried in a 120 ℃ oven for 12h, calcined in a muffle furnace at 400 ℃ for 5h, and reduced by hydrazine hydrate for 5h to obtain Pd/MoO3/SiO2Wherein the mass content of palladium is 1 percent; 150mL of an aqueous solution of potassium acetate was impregnated in the prepared Pd/MoO by a wet method3/SiO2Soaking for 12h, and drying in a vacuum oven at 70 deg.C for 12h to obtain KOAc/Pd/MoO3/SiO2The catalyst comprises 5% of potassium acetate by mass.
The device for the oxyacetylation is a fixed bed continuous reactor, isobutene, oxygen, acetic acid and nitrogen are introduced into the reactor for reaction at the temperature of 160 ℃ and the reaction pressure of 1.6MPa, and the isobutene, the oxygen, the acetic acid and the N are reacted2The gas space velocity was 2000/h at 8:1:2:16 (molar ratio). The conversion of isobutene was 10% and the space-time yield of 2-methylpropenylolacetate in the product was 35.5g/gPdThe space-time yield of the/h, 2-methylenepropane-1, 3-diacetoxy group was 21.3g/gPd/h。
Second step of transesterification
Potassium hydroxide is used as a catalyst to catalyze the ester exchange reaction of 2-methylene propane-1, 3-diacetoxy (compound (C)) and methanol. The reaction is carried out in a kettle type reactor, the reaction temperature is 60 ℃, the reaction pressure is 0.1MPa, and the molar ratio of 2-methylene propane-1, 3-diacetoxy to methanol is 1: 10. After reacting for 1h, 2-methylene-1, 3-propanediol is obtained, namely the compound (D). In this step, the conversion of 2-methylenepropane-1, 3-diacetoxy was 99.5%, the selectivity of 2-methylene-1, 3-propanediol was 98%, and the yield was 97.5%.
The third step is 2-methylene-1, 3-propanediol hydrogenation reaction
Hydrogenation catalyst Pd/Al2O3The preparation steps are as follows: soaking palladium nitrate water solution on a spherical alumina carrier for 12 hours by a wet method, drying in a 120 ℃ oven for 12 hours after soaking, calcining in a muffle furnace at 400 ℃ for 5 hours, and reducing in a tubular furnace by hydrogen at 300 ℃ for 3 hours to obtain Pd/Al2O3The catalyst comprises 2% of palladium by mass.
The hydrogenation reaction of 2-methylene-1, 3-propanediol (compound (D)) adopts a fixed bed continuous reactor, the reaction temperature is 60 ℃, the hydrogen pressure is 2.0MPa, the gas space velocity is 1000/h, and the liquid space velocity is 3/h. In the step, the conversion rate of the 2-methylene-1, 3-propanediol is 99 percent; the selectivity of 2-methyl-1, 3-propanediol was 98% and the yield was 97%.
Example 2
In the first step of the oxyacetylation reaction of this example, compared with example 1, 2-methyl allyl alcohol acetate obtained by distilling and separating the product obtained by the isopropenyl oxyacetylation reaction in example 1 at 100 ℃ is also introduced into the reactor, the molar ratio of isobutene to 2-methyl allyl alcohol acetate is 2:1, and the reaction raw material (isobutene + 2-methyl allyl alcohol acetate), oxygen, acetic acid and N2Other conditions were unchanged as 8:1:2:16 (molar ratio). The space-time yield of 2-methylenepropane-1, 3-diacetoxy (compound (C)) in the final product was 29.0g/gPd/h。
The second transesterification and the third hydrogenation were as in example 1.
Example 3
In the first step of the oxoacetylation reaction of this example, the molar ratio of isobutylene to 2-methylpropanol acetate in the starting material used was changed to 1:1 as compared with example 2, and the other conditions were not changed. The space-time yield of 2-methylenepropane-1, 3-diacetoxy in the final product was 37.8g/gPd/h；
The second transesterification and the third hydrogenation were as in example 1.
Example 4
In the first step of the oxoacetylation reaction of this example, the molar ratio of isobutylene to 2-methylpropanol acetate in the starting material used was changed to 1:2 as compared with example 2, and other conditions were not changedAnd (6) changing. The space-time yield of 2-methylenepropane-1, 3-diacetoxy in the final product was 46.6g/gPd/h；
The second transesterification and the third hydrogenation were as in example 1.
Example 5
In the first step of the oxoacetylation reaction of this example, the molar ratio of isobutylene to 2-methylpropanol acetate in the starting material used was changed to 1:3 as compared with example 2, and the other conditions were not changed. The space-time yield of 2-methylenepropane-1, 3-diacetoxy in the final product was 54.5g/gPd/h；
The second transesterification and the third hydrogenation were as in example 1.
Example 6
In the first step of the oxyacetylation reaction of this example, 2-methyl propenol acetate was fed into the reactor, but isobutylene was not fed, and the reaction raw material 2-methyl propenol acetate, oxygen, acetic acid, N, was fed2Other conditions were unchanged as 8:1:2:16 (molar ratio). The space-time yield of 2-methylenepropane-1, 3-diyl oxalate in the final product was 60.2g/gPd/h；
The second transesterification and the third hydrogenation were as in example 1.
Example 7
The first step of the oxoacetylation was the same as in example 2;
the catalyst for the second transesterification reaction was changed to sodium hydroxide, and the other conditions were the same as in example 1. After reacting for 1h, 2-methylene-1, 3-propanediol is obtained. In the step, the conversion rate of the 2-methylene propane-1, 3-diacetoxy is 97%; the selectivity of 2-methylene-1, 3-propanediol is 97%, and the yield is 94.1%;
the third hydrogenation step was the same as in example 1.
Example 8
The first step of the oxoacetylation was the same as in example 2;
the catalyst for the second transesterification reaction was changed to sodium carbonate, and the other conditions were the same as in example 1. After reacting for 1h, 2-methylene-1, 3-propanediol is obtained. In the step, the conversion rate of the 2-methylene propane-1, 3-diacetoxy is 96%; the selectivity of 2-methylene-1, 3-propanediol is 99%, and the yield is 95.0%;
the third hydrogenation step was the same as in example 1.
Example 9
The first step of the oxoacetylation was the same as in example 2;
the catalyst for the second transesterification reaction was changed to potassium carbonate, and the other conditions were the same as in example 1. After reacting for 1h, 2-methylene-1, 3-propanediol is obtained. In the step, the conversion rate of the 2-methylene propane-1, 3-diacetoxy is 95%; the selectivity of 2-methylene-1, 3-propanediol is 99%, and the yield is 94.1%;
the third hydrogenation step was the same as in example 1.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (19)
1. A process for the preparation of 2-methyl-1, 3-propanediol from isobutylene, comprising the steps of:
(1) mixing isobutene (i.e. the compound (A)) with acetic acid and oxygen, and carrying out an oxyacetylation reaction under the action of a supported palladium-molybdenum catalyst to obtain 2-methylene propane-1, 3-diacetoxy, i.e. a compound (C);
the supported palladium-molybdenum catalyst is KOAc/Pd/MoO3/SiO2A catalyst; the KOAc/Pd/MoO3/SiO2The mass content of potassium acetate in the catalyst is 1-10%;
the KOAc/Pd/MoO3/SiO2The preparation method of the catalyst comprises the following steps:
(a) soaking ammonium molybdate water solution on spherical silicon oxide carrier by wet method, drying and calcining to obtain MoO3/SiO2；
(b) Soaking an aqueous solution of sodium tetrachloropalladate in the MoO by a wet method3/SiO2Drying, calcining and hydrazine hydrate reducing to obtain Pd/MoO3/SiO2；
(c) Soaking potassium acetate solution in Pd/MoO solution via wet process3/SiO2Drying to obtain the KOAc/Pd/MoO3/SiO2A catalyst;
the pressure of the oxygen acetylation reaction is 0.5-2.0 MPa;
the reactant in the step (1) also comprises 2-methyl allyl alcohol acetate, namely a compound (B);
or, in the step (1), 2-methyl allyl alcohol acetate is used as a raw material to replace isobutene, and the raw material reacts with acetic acid and oxygen to obtain a compound (C); the 2-methyl allyl alcohol acetate is separated from a product obtained by isobutenyloxy acetylation reaction;
the molar ratio of the isobutene to the compound (B) is (1-5) to (0-5);
the molar ratio of the isobutene or the mixture of the isobutene and the compound (B) or the compound (B) to the oxygen and the acetic acid is (5-12) to 1 (1.5-5);
(2) performing ester exchange reaction on the compound (C) under the action of a basic catalyst to obtain 2-methylene-1, 3-propylene glycol, namely a compound (D);
(3) and (3) carrying out hydrogenation reaction on the compound (D) to obtain 2-methyl-1, 3-propanediol, namely the compound (E).
2. The process according to claim 1, wherein the molar ratio of isobutene to compound (B) is 1:1, 2:1, 1:2 or 1: 3.
3. The method according to claim 1, wherein the molar ratio of isobutene or the mixture of isobutene and compound (B) or compound (B) to oxygen and acetic acid is (7-10):1 (2-4).
4. The process according to claim 3, wherein the molar ratio of isobutene or the mixture of isobutene and compound (B) or compound (B) to oxygen and acetic acid is 8:1: 2.
5. The method according to any one of claims 1 to 4, wherein nitrogen is used as the carrier gas in step (1).
6. The method of claim 5, wherein the molar ratio of nitrogen to oxygen is (12-20): 1.
7. The process according to any one of claims 1 to 4, wherein the temperature of the oxyacetylation reaction in step (1) is 100-200 ℃.
8. The process as claimed in claim 7, wherein the temperature of the oxoacetylation reaction is 120-180 ℃.
9. The process according to any one of claims 1 to 4, wherein in step (1), the pressure of the oxoacetylation reaction is 0.75 to 1.8 MPa; the oxyacetylation reaction is carried out in a fixed bed continuous reactor.
10. The process according to any one of claims 1 to 4, wherein in the step (2), the alcohol used in the transesterification reaction is C1-4An alkyl alcohol.
11. The method according to claim 10, wherein the alcohol used in the transesterification reaction is at least one of methanol, ethanol and n-propanol.
12. The method according to claim 10, wherein in step (2), the compounds (C) and C1-4The molar ratio of the alkyl alcohol is 1 (5-15).
13. The process according to any one of claims 1 to 4, wherein in the step (2), the basic catalyst is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
14. The process according to any one of claims 1 to 4, wherein the temperature of the transesterification reaction in the step (2) is 30 to 80 ℃.
15. The process according to any one of claims 1 to 4, wherein the pressure of the transesterification reaction in the step (2) is 0.1 to 1.0 MPa.
16. The process according to any one of claims 1 to 4, wherein in the step (3), the hydrogenation reaction is a reaction of the compound (D) with hydrogen in the presence of a catalyst; the catalyst is preferably a supported palladium catalyst.
17. The method of claim 16, wherein the supported palladium catalyst is Pd/Al2O3A catalyst.
18. The method according to claim 16 or 17, wherein the supported palladium catalyst has a palladium content of 0.1 to 10% by mass.
19. The method according to any one of claims 1 to 4, wherein in the step (3), the reaction temperature of the hydrogenation reaction is 30 to 150 ℃;
in the step (3), the hydrogen pressure in the hydrogenation reaction is 0.1-5.0 MPa.
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