CN107778145B - Method for producing 1, 4-butanediol and/or sec-butanol - Google Patents
Method for producing 1, 4-butanediol and/or sec-butanol Download PDFInfo
- Publication number
- CN107778145B CN107778145B CN201610768476.9A CN201610768476A CN107778145B CN 107778145 B CN107778145 B CN 107778145B CN 201610768476 A CN201610768476 A CN 201610768476A CN 107778145 B CN107778145 B CN 107778145B
- Authority
- CN
- China
- Prior art keywords
- reaction
- acid
- butanediol
- carried out
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing 1, 4-butanediol and/or sec-butanol. The method for preparing 1, 4-butanediol comprises the following steps: (1) performing addition reaction on succinic acid and C2-C6 olefin, and collecting dibutyl succinate; (2) and (2) carrying out hydrogenation reaction on the dibutyl succinate obtained in the step (1), and collecting 1, 4-butanediol and/or sec-butanol. The method provides a technical route with high efficiency and low cost for producing the 1, 4-butanediol and/or the sec-butanol. The addition reaction and the hydrogenation reaction in the method have high selectivity, high atom utilization rate and environment-friendly preparation process. The method has high succinic acid conversion rate and dibutyl succinate selectivity. The method has the advantages of adjustable acid content, high product selectivity, no corrosion to equipment and cyclic use of the catalyst.
Description
Technical Field
The invention relates to a chemical raw material 1, 4-butanediol and/or sec-butyl alcohol, in particular to a method for preparing 1, 4-butanediol and/or sec-butyl alcohol.
Background
1, 4-Butanediol (BDO) is a very important organic and fine chemical raw material, can be used for producing chemicals such as Tetrahydrofuran (THF), gamma-butyrolactone (GBL) and the like, and is also an important precursor for synthesizing materials such as polybutylene terephthalate engineering plastics and fibers, polyurethane artificial leather, polyurethane elastomer, polybutylene succinate resin (PBS) and the like. Among them, PBS is a new type of biodegradable polymer material, which is obtained by condensation polymerization of succinic acid and 1, 4-butanediol, and is one of the currently recognized biodegradable plastics with the best comprehensive performance in the world. Due to the large number of applications and potential market value at present, the market demand for BDO is large.
BDO is currently produced mainly by the petrochemical route, and several methods are available for its production: reppe process, cis-anhydride process, allyl alcohol process and butadiene process. The production capacity of the BDO industry is mainly concentrated on some large enterprises, such as BASF, LIANDEBAISEL and the like. Most of BDO production devices in China introduce foreign technologies, the product price is in disadvantage in international competition due to expensive technical use cost, and the large-scale commercialized popularization of PBS is limited. More importantly, most of the traditional petroleum-based BDO production routes have the defects of long flow, complex process, harsh reaction conditions, lack of acetylene and butadiene resources and the like, and have high cost and serious pollution. With the development of national economy and the increasing demand of degradable high molecular material PBS, the development of BDO green preparation technology is necessary.
Currently, about dozens of known 1, 4-butanediol synthesis routes exist, wherein one of the routes is to take maleic anhydride as a raw material, carry out esterification and hydrogenation on low-carbon alcohol to obtain 1, 4-butanediol and recycle the low-carbon alcohol. This has been described in detail in a number of patents, such as US 4795824, WO 90/08127, US 4751334, US 4584419, etc., which are hereby incorporated by reference.
The maleic anhydride esterification hydrogenation process was developed successfully by Davy Mckee, UK, and is called Davy. The hydrogenation reaction is carried out in gas phase or liquid phase, a copper catalyst is adopted, and the reaction condition is milder than that of a direct hydrogenation method of maleic anhydride. The process mainly comprises three steps, wherein the first step is that maleic anhydride and ethanol are subjected to esterification reaction to generate maleic acid monoethyl ester; the second step is that maleic acid monoethyl ester and ethanol are subjected to double esterification reaction in the presence of an ion exchange resin catalyst to generate maleic acid diethyl ester; the third step is that diethyl maleate is hydrogenated to generate diethyl succinate, and then the diethyl succinate is hydrogenolyzed to generate BDO.
On the basis of the above, Davy Mckee company in UK develops a maleic anhydride esterification process using methanol as an esterifying agent. The process has the advantages that the separation of methanol and water after esterification is easy, the volatility of diethyl maleate is increased, the operation range of gas phase hydrogenation is widened, the esterification conversion rate of the methanol is improved (up to 99.5 percent), the purification of diethyl maleate does not exist, unreacted maleic anhydride and monomethyl ester are not needed to be circulated, and only pure methanol is circulated, so the process is greatly simplified, and the total engineering investment is greatly reduced compared with the former.
However, these routes use feedstocks such as maleic anhydride, maleic acid, and the like that are relatively expensive from petroleum, and it is desirable to produce 1, 4-butanediol from feedstocks that can conserve a significant amount of petroleum resources and reduce the pollution produced by petrochemical processes.
Succinic Acid (SA) is a basic organic chemical raw material and important C4A platform compound. The succinic acid can be prepared by three production methods, namely a chemical synthesis method, a biological conversion method and a microbial fermentation method. Microbial fermentation processes can convert reducing sugars from biomass (e.g., starch, cellulose) to SA. The SA produced by microbial fermentation has the advantages of utilizing renewable resources and fixing greenhouse gas CO2And the like.
Compared with the traditional petroleum-based BDO production method, the BDO prepared by the bio-based SA has the advantages of renewable raw materials, green process, short flow and the like. The research on the preparation of SA by biological fermentation is well established, and SA fermentation commercialization is currently conducted in China, surgical research and industry (such as the department of energy, Dismann, Rogat, France, BioAmber, USA). With the breakthrough of the technology for producing SA by a biological fermentation method and the reduction of the production cost, the global bio-based SA project starts to be constructed on a large scale and put into operation successively, and SA gradually becomes a cheap and abundant raw material product. The catalytic conversion technology is utilized to carry out derivation conversion on the SA to prepare BDO, the additional value and the application range of the BDO are improved, and the BDO has important research significance and good application prospect.
In recent years, with the rapid development of petrochemical industry, petroleum pyrolysis gas generates a large amount of unsaturated hydrocarbons, and olefins have become an abundant and cheap chemical raw material. The direct esterification of C4 and C5 olefins to carboxylic esters has been particularly attractive. However, because the four carbon components contain isobutene, the esterification reaction product contains tert-butyl ester which has low industrial application value, and the sec-butyl acetate can be synthesized only after isobutene is removed, so that the process route is long and the economical efficiency is limited. With the construction of the MTBE plant and the demand for butene-1 from polyethylene, the n-butene concentration in the remaining C4 component was increased. Therefore, the process route for synthesizing carboxylic ester by direct addition esterification of carboxylic acid and olefin has been remarkably developed in recent years.
A process for directly esterifying carboxylic acid and olefin has been researched and reported abroad, and the reaction temperature is generally between 100 and 200 ℃ and the reaction pressure is about 1.0 MPa. According to the literature, the process mainly has two different process realization modes of fixed bed continuous reaction and autoclave batch reaction. The key to achieving this process is the development and development of catalysts, which include mineral acids and sulfonic acids, metal sulfates, clay minerals, oxides, zeolite molecular sieves, heteropoly compounds, ion exchange resin catalysts, and the like, in the literature.
US 5334779 discloses a catalyst composition and its use in the hydrogenation of carboxylic acid esters, the catalyst consisting of copper oxide, zinc oxide and a third component (an oxide of aluminium, magnesium, zirconium or mixtures thereof). The carboxylic acid used in the catalyst and method is dimethyl cyclohexanedicarboxylate, lower alkyl esters of C10-C20 carboxylic acids, di-lower alkyl esters of adipic acid and di-lower alkyl esters of maleic acid.
As can be seen from published documents, the prior art does not disclose any information about the joint production of 1, 4-butanediol and sec-butanol by dibutyl phthalate hydrogenation.
Disclosure of Invention
The invention provides a method for preparing 1, 4-butanediol and/or sec-butanol.
The method for preparing 1, 4-butanediol and/or sec-butanol comprises the following steps: (1) performing addition reaction on succinic acid and C2-C6 olefin, and collecting dibutyl succinate; (2) and (2) carrying out hydrogenation reaction on the dibutyl succinate obtained in the step (1), and collecting 1, 4-butanediol and/or sec-butanol.
The succinic acid is preferably 1, 4-succinic acid.
The C2-C6 olefin can be one or more selected from ethylene, propylene, butylene, pentene, hexene and cyclohexene, preferably butylene-1 and/or butylene-2, and most preferably butylene-1.
The addition reaction in step (1) is preferably carried out in the presence of an acid catalyst, which may be one or more selected from the group consisting of a strongly acidic ion exchange resin, a solid super acid, an ionic liquid, a modified molecular sieve, a heteropolyacid, sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, preferably one or more selected from the group consisting of a strongly acidic ion exchange resin, a heteropolyacid and a solid super acid, and most preferably a strongly acidic ion exchange resin.
The strong acid ion exchange resin is preferably a strong acid cation exchange resin, such as styrene-divinylbenzene copolymer resin and perfluoro resin sulfonic acid, and the trade marks include D002, D72, NKC-9, A-16W, DNW, etc.
The solid super acid can be TiO2-SO4 2-And/or ZrO2-SO4 2-。
The ionic liquid can be Et3NHCl-AlCl3-CuCl2、SbF5、BF3、AlCl3And SbF5-one or more of HF.
The modified molecular sieve can be a sulfonic acid modified molecular sieve, and the modification method can be referred to CN 102924272A.
The heteropoly acid can be HPW/SiO2、H3PW12O40And H3PMo12O40One or more of (a).
In the addition reaction of the step (1), water and/or alcohol is preferably added, the alcohol is preferably one or more of methanol, ethanol and propanol, and the adding amount of the water and/or alcohol is 0.5-10 times, preferably 1-5 times of the mass of the succinic acid. When water and/or alcohol is added in the addition reaction of the step (1), the water and/or alcohol is preferably added after mixing with succinic acid.
The addition reaction in the step (1) may be a continuous reaction or a batch reaction. The continuous reaction may be carried out in a catalytic distillation reactor; the batch reaction may be carried out in a tank reactor.
The reaction conditions of the addition reaction in the step (1) are as follows: the reaction temperature is 50-200 ℃, the reaction pressure is 0.1-3MPa, and the molar ratio of the succinic acid to the C2-C6 olefin is 1: 0.1-10. When the addition reaction is carried out in a continuous reactor, the space velocity is 0.5-10h-1When the reaction is carried out in a batch reaction kettle, the residence time is 0.5 to 4 hours.
The addition reaction in step (1) is preferably carried out in a catalytic distillation reactor.
The catalytic distillation reactor at least comprises a tower kettle, a stripping section, a rectifying section and a tower top reflux condenser, wherein the tower kettle is filled with an acid catalyst, and the operation conditions are as follows: the pressure at the top of the tower is 0.2-0.9MPa, the temperature at the top of the tower is 50-90 ℃, the temperature at the middle part of the reaction section is 80-120 ℃, the temperature at the bottom of the tower is 120-180 ℃, the reflux ratio is 0.2-0.8, the molar ratio of the succinic acid to the C2-C6 olefin is 1: 0.1-10, the succinic acid feeding airspeed is 0.2-10h-1。
The tower kettle is preferably filled with strong acid cation exchange resin.
In the step (1), dibutyl succinate can be obtained by distillation or rectification after succinic acid and C2-C6 olefin are subjected to addition reaction.
The hydrogenation reaction in step (2) is preferably carried out in the presence of a hydrogenation catalyst, the hydrogenation catalyst may be selected from group VIII metal and/or group IB metal catalysts, for example, one or more of copper-based, palladium-based, ruthenium-based and platinum-based metal catalysts may be selected, preferably copper-based and/or ruthenium-based catalysts, and most preferably copper-based catalysts, for example, one or more of copper-zinc-aluminum, copper-zinc-chromium, lanthanum-modified copper-zinc-aluminum, framework copper and amorphous copper may be selected, and the preparation method of these copper-based catalysts may be referred to CN 86105765a and ZL 200810226922.9.
The reaction conditions of the hydrogenation reaction in the step (2) are as follows: the reaction temperature is 100--1。
In the hydrogenation reaction in the step (2), preferably, the dibutyl succinate obtained in the step (1) and hydrogen are subjected to hydrogenation reaction, wherein the molar ratio of the hydrogen to the dibutyl succinate obtained in the step (1) is 1-1000: 1.
in the step (2), after the dibutyl succinate obtained in the step (1) is subjected to hydrogenation reaction, 1, 4-butanediol and/or sec-butanol can be obtained by a distillation or rectification method.
The method provides a technical route with high efficiency and low cost for producing the 1, 4-butanediol and/or the sec-butanol. The addition reaction and the hydrogenation reaction in the method have high selectivity, high atom utilization rate and environment-friendly preparation process. The method has high succinic acid conversion rate and dibutyl succinate selectivity.
The method has the advantages of adjustable acid content, high product selectivity, no corrosion to equipment and cyclic use of the catalyst.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1-addition reaction of 51, 4-succinic acid with butene-1
Examples 1 to 5 are addition reactions of 1, 4-butanedioic acid with butene-1. 20mL of macroporous strongly acidic ion exchange resin (types D002, D72, NKC-9, and A-16W, DNW, respectively) was charged
Inert quartz sand is filled in the middle part and two ends of the stainless steel reactor with the jacket. Ethanol and water solution of succinic acid (the mass ratio of succinic acid/ethanol/water is 50/30/20) and butene-1 are respectively added into a reactor for reaction. And (3) condensing the reaction product, sampling, performing off-line chromatographic analysis, and calculating the conversion rate of succinic acid and the selectivity of dibutyl succinate according to the composition of the product. The specific data are shown in Table 1.
TABLE 1 Synthesis of dibutyl succinate by addition reaction of succinic acid with butene-1
Example 61 addition reaction of 4, 4-butanedioic acid with butene-1
Example 6 is the addition reaction of 1, 4-butanedioic acid with butene-1. Adding crystal water-free dodecasilicotungstic acid (H)4SiW12O40) Catalyst loading
Inert quartz sand is filled in the middle part and two ends of the stainless steel reactor with the jacket. Respectively pumping ethanol and water solution of succinic acid (the mass ratio of succinic acid/ethanol/water is 50/50) and butene-1 into a reactor for reaction, wherein the reaction temperature is 140 ℃, the reaction pressure is 0.2Mpa, the flow rate of the succinic acid solution is 60mL/h, and the feeding amount of the butene-1 is 120 mL/h. And (3) condensing the reaction product, sampling, performing off-line chromatographic analysis, and calculating the conversion rate of succinic acid and the selectivity of dibutyl succinate according to the composition of the product. The specific data are shown in Table 2.
Example 71 addition reaction of 4, 4-butanedioic acid with butene-1
Example 7 is the addition reaction of 1, 4-butanedioic acid with butene-1. Filling ZSM-5 molecular sieve modified by sulfonic acid
Inert quartz sand is filled in the middle part and two ends of the stainless steel reactor with the jacket. Respectively pumping ethanol and water solution of succinic acid (the mass ratio of succinic acid/ethanol/water is 50/30/20) and butene-1 into a reactor for reaction, wherein the reaction temperature is 140 ℃, the reaction pressure is 0.2Mpa, the flow rate of the succinic acid solution is 60mL/h, and the feeding amount of the butene-1 is 120 mL/h. And (3) condensing the reaction product, sampling, performing off-line chromatographic analysis, and calculating the conversion rate of succinic acid and the selectivity of dibutyl succinate according to the composition of the product. The specific data are shown in Table 2.
Example 81 addition reaction of 4, 4-butanedioic acid with butene-1
Example 8 is the addition reaction of 1, 4-butanedioic acid with butene-1. ZrO to be enclosed in a glass tube for preservation2-SO4 2-The catalyst is charged under nitrogen atmosphere
Inert quartz sand is filled in the middle part and two ends of the stainless steel reactor with the jacket. Respectively adding ethanol, water solution (mass ratio of succinic acid/ethanol is 50/50) and butene-1 into a reactor for reaction at 140 deg.C and 0.2Mpa under succinic acid solutionThe liquid flow rate was 60mL/h and the butene-1 feed was 120 mL/h. And (3) condensing the reaction product, sampling, performing off-line chromatographic analysis, and calculating the conversion rate of succinic acid and the selectivity of dibutyl succinate according to the composition of the product. The specific data are shown in Table 2.
TABLE 2 Synthesis of dibutyl succinate by addition reaction of succinic acid with butene-1
Example 91 addition reaction of 4-butanedioic acid with butene-1
Example 9 is the addition reaction of 1, 4-succinic acid with butene-1. Weighing Ionic liquid Et3NHCl-AlCl3-CuCl25.0g, adding into a 250mL autoclave, weighing 50g of 1, 4-succinic acid, 30g of ethanol and 20g of water at room temperature, placing into the 250mL autoclave, introducing 150g of butylene into the autoclave once again, reacting for 6h at 140 ℃ and 2.0Mpa, extracting an upper organic liquid, and analyzing the product components by gas chromatography to obtain the result: the conversion rate of 1, 4-succinic acid is 78.9 percent, and the selectivity of dibutyl succinate is 83.2 percent.
Example 101, addition reaction of 4-butanedioic acid with butene-1
Example 10 is the addition reaction of 1, 4-butanedioic acid with butene-1. Weighing ionic liquid AlCl35.0g, adding into a 250mL autoclave, weighing 50g of 1, 4-succinic acid, 30g of ethanol and 20g of water at room temperature, placing into the 250mL autoclave, introducing 150g of butylene into the autoclave once again, reacting for 6h at 140 ℃ and 2.0Mpa, extracting an upper organic liquid, and analyzing the product components by gas chromatography to obtain the result: the conversion rate of 1, 4-succinic acid is 76.3 percent, and the selectivity of dibutyl succinate is 80.8 percent.
EXAMPLE 11 hydrogenation of dibutyl succinate
Lanthanum-modified copper-zinc-aluminum as hydrogenation catalyst is used in the hydrogenation of dibutyl succinate, and its synthesis method is described in example 1 of CN 201410092477.7, and its composition is CuO 45.0%, ZnO27.5%, Al2O325.4％、La2O32.1％。
20g of the above lanthanum-modified Cu-Zn-Al hydrogenation catalyst was charged
The middle part and two ends of the stainless steel reactor are filled with inert quartz sand. Introducing hydrogen, reducing at 300 deg.C and 1.0MPa for 24 hr, reducing to 240 deg.C and 260 deg.C, and increasing hydrogen pressure to 6.0 MPa. 99.5 percent of dibutyl succinate obtained by rectifying the product obtained in the example 5 is pumped into a reactor by a metering pump for reaction. And (3) sampling and performing off-line chromatographic analysis on the reaction product after condensation, and calculating the conversion rate of dibutyl succinate and the selectivity of 1, 4-butanediol according to the composition of the product. The specific data are shown in Table 3.
TABLE 3
EXAMPLE 12 hydrogenation of dibutyl succinate
Copper-zinc-aluminum is used as hydrogenation catalyst in the hydrogenation reaction of dibutyl succinate, and the synthesis method is shown in example 2 in CN 201410408854.3, and the composition of the catalyst is 40.0 percent of CuO, 21.5 percent of ZnO21, and Al2O338.5％。
Loading the above Cu-Zn-Al hydrogenation catalyst
The middle part and two ends of the stainless steel reactor are filled with inert quartz sand. Introducing hydrogen, reducing at 300 deg.C and 1.0MPa for 24 hr, reducing to 240 deg.C and 260 deg.C, and increasing hydrogen pressure to 6.0 MPa. 99.5 percent of dibutyl succinate obtained by rectifying the product obtained in the example 4 is pumped into a reactor by a metering pump for reaction. And (3) sampling and performing off-line chromatographic analysis on the reaction product after condensation, and calculating the conversion rate of dibutyl succinate and the selectivity of 1, 4-butanediol according to the composition of the product. The specific data are shown in Table 4.
TABLE 4
EXAMPLE 13 hydrogenation of dibutyl succinate
Amorphous copper is used as a hydrogenation catalyst in the hydrogenation of dibutyl succinate, and the synthesis method is shown in example 1 in ZL200810226922.9, and the composition of the amorphous copper is Cu85Mo2.8Al12.2。
Weighing 5.0g of the amorphous copper catalyst, adding the amorphous copper catalyst into a 250mL autoclave, weighing 50g of 99.5% dibutyl succinate obtained by rectifying the product obtained in the embodiment 8 at room temperature, placing 150g of ethanol into the 250mL autoclave, reacting for 6h under the hydrogen pressure of 4.0Mpa and at 220 ℃, condensing the reaction product, sampling, performing offline chromatographic analysis, and calculating the conversion rate of dibutyl succinate and the selectivity of 1, 4-butanediol according to the composition of the product. The conversion rate of dibutyl succinate is 97%, the selectivity of 1, 4-butanediol is 97.8%, and the selectivity of sec-butyl alcohol is 97.4%.
Comparative example 1
1, 4-butanediol was prepared according to the method disclosed in Green chem. (2015,17,1341-1361) by dissolving 1, 4-butanedioic acid in Pd-Re/TiO2The gamma-butyrolactone is hydrogenated to generate the gamma-butyrolactone under the action of the catalyst, and then the gamma-butyrolactone is hydrogenated to generate the 1, 4-butanediol under the action of the nickel catalyst.
The method comprises the following specific steps: in a 300mL autoclave, 150g of 1, 4-succinic acid was added, followed by 10g of Pd-Re/TiO2The catalyst of (1% by mass of Pd and 4% by mass of Re) in the presence of H at 7.0MPa2The reaction is carried out for 4 hours under the pressure and at the temperature of 200 ℃. The results were analyzed by chromatography. The results show that the conversion rate of 1, 4-butanedioic acid is 90 percent, and the selectivity of gamma-butyrolactone is 89 percent.
Then 5g of nickel catalyst is added into the intermediate raw material, and hydrogenation reaction is carried out for 5h at 180 ℃ and under the hydrogen pressure of 4 Mpa. The chromatographic analysis result shows that the conversion rate of the gamma-butyrolactone is 90 percent, and the selectivity of the 1, 4-butanediol reaches 85 percent.
As can be seen from the comparison of the examples with the comparative examples, the process of the present invention has more mild reaction conditions, higher conversion and higher selectivity for 1, 4-butanediol.
Claims (16)
1. A process for producing 1, 4-butanediol and sec-butanol comprising: (1) performing addition reaction on succinic acid and butene-1 and/or butene-2, and collecting dibutyl succinate; (2) carrying out hydrogenation reaction on dibutyl succinate obtained in the step (1), and collecting 1, 4-butanediol and sec-butyl alcohol; the addition reaction in the step (1) is carried out in the presence of an acid catalyst; the acid catalyst is selected from one or more of strong acid ion exchange resin, solid super acid, ionic liquid, modified molecular sieve, heteropoly acid, sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; the reaction conditions of the addition reaction in the step (1) are as follows: the reaction temperature is 50-200 ℃, the reaction pressure is 0.1-3MPa, and the molar ratio of the succinic acid to the butene-1 and/or butene-2 is 1: 0.1-10.
2. The process of claim 1, wherein the acid catalyst is selected from one or more of a strongly acidic ion exchange resin, a heteropolyacid, and a solid superacid.
3. The method of claim 1, wherein the strong acid ion exchange resin is a strong acid cation exchange resin and the solid super acid is TiO2-SO4 2-And/or ZrO2-SO4 2-The ionic liquid is Et3NHCl-AlCl3-CuCl2、SbF5、BF3、AlCl3And SbF5-one or more of HF, the modified molecular sieve is a sulfonic acid modified molecular sieve, and the heteropolyacid is selected from HPW/SiO2、H3PW12O40And H3PMo12O40One or more of (a).
4. The method according to claim 1, wherein water and/or alcohol is added in the addition reaction of the step (1).
5. The method of claim 4, wherein the alcohol is one or more of methanol, ethanol, and propanol.
6. The method according to claim 4, wherein the water and/or alcohol is added in an amount of 0.5 to 10 times the mass of the succinic acid.
7. The method according to claim 1, wherein the addition reaction in the step (1) is a continuous reaction or a batch reaction.
8. The process according to claim 7, wherein the continuous reaction is carried out in a catalytic distillation reactor; the batch reaction is carried out in a tank reactor.
9. The process according to claim 8, wherein the addition reaction is carried out in a continuous reactor at a space velocity of 0.5 to 10h-1When the reaction is carried out in a batch reaction kettle, the residence time is 0.5 to 4 hours.
10. The process according to claim 1, wherein the addition reaction in step (1) is carried out in a catalytic distillation reactor.
11. The process of claim 10 wherein said catalytic distillation reactor comprises at least a bottom, a stripping section, a rectifying section and an overhead reflux condenser, the bottom being filled with an acid catalyst under the operating conditions: the pressure at the top of the tower is 0.2-0.9MPa, the temperature at the top of the tower is 50-90 ℃, the temperature at the middle part of the reaction section is 80-120 ℃, the temperature at the bottom of the tower is 120-: 0.1-10, the succinic acid feeding airspeed is 0.2-10h-1。
12. The process according to claim 1, wherein the hydrogenation in the step (2) is carried out in the presence of a hydrogenation catalyst.
13. The process of claim 12 wherein the hydrogenation catalyst is selected from group VIII metal and/or group IB metal catalysts.
14. The process of claim 12, wherein the hydrogenation catalyst is selected from one or more of copper-based, palladium-based, ruthenium-based, and platinum-based metal catalysts.
15. The process of claim 12, wherein the hydrogenation catalyst is selected from one or more of the group consisting of copper zinc aluminum, copper zinc chromium, lanthanum modified copper zinc aluminum, skeletal copper, and amorphous copper.
16. The method according to claim 1, wherein the hydrogenation in the step (2) is carried out under reaction conditions of: the reaction temperature is 100--1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610768476.9A CN107778145B (en) | 2016-08-30 | 2016-08-30 | Method for producing 1, 4-butanediol and/or sec-butanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610768476.9A CN107778145B (en) | 2016-08-30 | 2016-08-30 | Method for producing 1, 4-butanediol and/or sec-butanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107778145A CN107778145A (en) | 2018-03-09 |
| CN107778145B true CN107778145B (en) | 2020-11-13 |
Family
ID=61440781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610768476.9A Active CN107778145B (en) | 2016-08-30 | 2016-08-30 | Method for producing 1, 4-butanediol and/or sec-butanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107778145B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594462A (en) * | 1984-06-26 | 1986-06-10 | Basf Aktiengesellschaft | Preparation of butane-1,4-diol |
| CN1116616A (en) * | 1994-08-10 | 1996-02-14 | 中国石油化工总公司 | Method for preparing 1,4-butanediol |
| CN1358702A (en) * | 2000-12-15 | 2002-07-17 | 中国石油化工股份有限公司 | Process for preparing 1,4-butanediol |
| CN101307042A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone |
| CN101343211A (en) * | 2008-08-21 | 2009-01-14 | 四川德莱投资有限公司 | Method for preparing BDO or succinic diester with by-product from maleic anhydride |
| CA2657666A1 (en) * | 2008-03-13 | 2009-09-13 | Bioamber S.A.S. | Process for the direct production of esters of carboxylic acids from fermentation broths |
-
2016
- 2016-08-30 CN CN201610768476.9A patent/CN107778145B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594462A (en) * | 1984-06-26 | 1986-06-10 | Basf Aktiengesellschaft | Preparation of butane-1,4-diol |
| CN1116616A (en) * | 1994-08-10 | 1996-02-14 | 中国石油化工总公司 | Method for preparing 1,4-butanediol |
| CN1358702A (en) * | 2000-12-15 | 2002-07-17 | 中国石油化工股份有限公司 | Process for preparing 1,4-butanediol |
| CN101307042A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone |
| CA2657666A1 (en) * | 2008-03-13 | 2009-09-13 | Bioamber S.A.S. | Process for the direct production of esters of carboxylic acids from fermentation broths |
| CN101343211A (en) * | 2008-08-21 | 2009-01-14 | 四川德莱投资有限公司 | Method for preparing BDO or succinic diester with by-product from maleic anhydride |
Non-Patent Citations (1)
| Title |
|---|
| 丁烯与醋酸酯化反应研究;周永敏;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140115;56-66 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107778145A (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617518B (en) | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation | |
| CN101475442B (en) | Method for preparing ethylene glycol from oxalic ester | |
| US20100056832A1 (en) | Method of making 2-butanol | |
| TWI612031B (en) | Method and device for co-production of cyclohexanol and alkanol | |
| CN102372596B (en) | Method for producing glycol product by separating synthetic gas | |
| CN1683293A (en) | Process for producing diatomic alcohol and polyol from cracking sorbierite | |
| CN110818566A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN102344364A (en) | Method for producing sec-butyl acetate by synthesizing acetic acid and mixed C4 | |
| CN101402566A (en) | Method for producing high-purity low-class fatty acid ester | |
| CN102649081B (en) | Reducing method for preparation of ethylene glycol catalyst by oxalate through hydrogenation | |
| CN103936574B (en) | A kind of method being prepared high-purity methyl iso-butyl ketone (MIBK) by industrial by-product waste liquid acetone | |
| CN109970511B (en) | Method for synthesizing 1, 3-propylene glycol by resource utilization of HPPO byproduct | |
| CN109704902B (en) | Ionic liquid catalytic deoxidation method in lignin derivative hydrodeoxygenation process | |
| CN103342624A (en) | Preparation method of high purity cyclopentene | |
| CN102234230A (en) | Process method for synthesizing sec-butyl acetate from C4 fractions | |
| CN102372599B (en) | Method for separating glycol and butylene glycol | |
| CN102219641B (en) | Method for purifying ethylene glycol | |
| CN102219640A (en) | Method for improving selectivity for making glycol by adding hydrogen in oxalate | |
| CN101121656A (en) | Method for synthesizing sec-butyl acetate from acetic acid and linear butylene | |
| CN107778145B (en) | Method for producing 1, 4-butanediol and/or sec-butanol | |
| CN102372598A (en) | Method for separating glycol from butanediol | |
| CN102070390B (en) | The method of refinery's mixed c 4 propylene | |
| CN111039754A (en) | Method for producing ethylene glycol from formaldehyde | |
| CN102276418B (en) | Ethylene glycol purification method | |
| CN101993345A (en) | Method for improving selectivity of glycol prepared by adding hydrogen into oxalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |