CN110743580A - Catalyst for preparing methyl ethyl ketone by dehydrating 2, 3-butanediol and preparation method thereof - Google Patents
Catalyst for preparing methyl ethyl ketone by dehydrating 2, 3-butanediol and preparation method thereof Download PDFInfo
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- CN110743580A CN110743580A CN201910965440.3A CN201910965440A CN110743580A CN 110743580 A CN110743580 A CN 110743580A CN 201910965440 A CN201910965440 A CN 201910965440A CN 110743580 A CN110743580 A CN 110743580A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
A catalyst for preparing methyl ethyl ketone by efficiently dehydrating 2, 3-butanediol and a preparation method thereof are summarized as follows: the invention discloses a catalyst for preparing methyl ethyl ketone by dehydrating 2, 3-butanediol and a preparation method thereof. The catalyst takes alkaline earth metal salt barium phosphate as an active component for the first time, takes active carbon as a carrier, has the loading capacity of 2-10 percent, is preferably 8 percent, and is applied to the dehydration reaction of preparing methyl ethyl ketone in a fixed bed by using 2, 3-butanediol. The catalyst disclosed by the invention is simple in preparation process, low in preparation cost, high in catalytic activity, good in stability, green and environment-friendly, and can be recycled, and the result shows that the conversion rate of the 2, 3-butanediol is 100.0%, and the yield of the methyl ethyl ketone can reach 95.2%.
Description
Technical Field
The invention relates to a catalyst, a preparation method and application, and belongs to the technical field of chemical industry.
Background
Methyl ethyl ketone is an organic solvent which is widely used, and many high molecular compounds such as digestive cellulose, vinyl resin, polyurethane, magnetic tape, paint, adhesive, ink, pharmaceutical production, and lubricant dewaxing have good solubility in methyl ethyl ketone. Meanwhile, methyl ethyl ketone molecules contain carbonyl functional groups, and the methyl ethyl ketone molecules can be used as raw materials for producing products such as spices, adhesive tapes, adhesives, synthetic leather and the like, and in addition, the shadow can be seen in the industrial fields of preparing catalysts, antioxidants, corrosion inhibitors and the like. Currently, the production method of methyl ethyl ketone mainly comprises more than ten methods, such as a n-butene two-step method, a n-butane liquid phase oxidation method, a butene liquid phase oxidation method, a butadiene catalytic hydrolysis method, an isobutylbenzene method, an isobutylaldehyde isomerization method, a mixed C4 hydrocarbon oxidation method, a biological fermentation method and the like, wherein the three methods, namely the n-butane liquid phase oxidation method, the n-butene method and the isobutylbenzene method, are most commonly used. In recent years, the industrial production of methyl ethyl ketone at home and abroad mainly adopts a n-butene method, but the process has complex operation flow and serious pollution, and raw materials come from non-renewable fossil resources, so that the large-scale development of the methyl ethyl ketone is limited. The method is particularly important for exploring and developing an environment-friendly and efficient production process route of the methyl ethyl ketone by combining the pursuit of energy conservation and green science and technology at present.
With the gradual decrease of fossil resources, the process of the biological fermentation method is gradually mature and is valued by scientific researchers, and the technical route for converting biomass resources into high-value derived chemicals can reduce the consumption and the dependence on the traditional fossil resources. The 2, 3-butanediol is a bio-based platform compound, has wide source and low cost. Therefore, the process for preparing methyl ethyl ketone by catalyzing 2, 3-butanediol dehydration becomes a research hotspot and a work focus of domestic and foreign researchers.
Shaoyuan and the like use p-toluenesulfonic acid as a catalyst, and a stainless steel theta environment packed tower is selected as a reaction device, and the results show that the optimal yield of the methyl ethyl ketone can reach 78.9%. The method has the advantages of high catalyst activity, low energy consumption and the like (Shaoyuan, Fangyun and the like, reaction research on the preparation of methyl ethyl ketone by 2, 3-butanediol liquid phase dehydration, 2013, 54 (4): 227 plus 230.) however, in the preparation process, sulfuric acid is selected as the catalyst, which not only easily corrodes equipment, but also easily causes three wastes because excessive alkali is needed for post-treatment of the product after the reaction, and does not accord with the environment-friendly green chemical concept. Huanghe et al (patent CN101293817A, 2008) use ZSM-5 and NaY molecular sieve catalyst to catalyze 2, 3-butanediol to dehydrate to prepare methyl ethyl ketone by using N2In order to carry protective gas to react in a fixed bed, the result shows that the conversion rate of the 2, 3-butanediol can reach 90.5-100%, and the selectivity of the methyl ethyl ketone can reach 83.7-91.3%. However, the concentration of the raw materials is low (30-200 g/L), and a large amount of water solution which does not participate in the reaction needs to be heated to 200-300 ℃ in the reaction process, so that more energy consumption is generated.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of a catalyst for preparing methyl ethyl ketone by efficiently dehydrating 2, 3-butanediol.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a catalyst for preparing methyl ethyl ketone by dehydrating 2, 3-butanediol comprises the following steps:
soaking activated carbon in barium phosphate hydrochloric acid solution in an equivalent amount for 2-12 hours at room temperature;
drying the activated carbon impregnated in the step (1) at 100-150 ℃ for 2-12 h;
step (3), adding the dried active carbon into N2Roasting for 2-6 h under the protection of inert gas to obtain Ba3（PO4）2Activated Carbon (AC) catalyst.
In the step (1) of the invention, the loading amount, namely the mass ratio of the barium phosphate to the activated carbon is 2-10%, preferably 8%, and according to the maximum water absorption of the activated carbon, the activated carbon is equivalently immersed in barium phosphate hydrochloric acid solution and immersed for 12 hours at room temperature.
In the step (2) of the present invention, the drying temperature is 120 ℃ and the drying time is 12 hours.
In step (3) of the present invention, N2The flow rate of (2) is 10-40 ml/min, and roasting is carried out for 4 hours.
The invention also provides Ba3（PO4）2The application of the/AC catalyst in the reaction of preparing methyl ethyl ketone by dehydrating 2, 3-butanediol. The reaction process is as follows: carrying out continuous reaction in a fixed bed reactor, placing the catalyst in the middle of a quartz tube, filling the catalyst at two ends with inert ceramic rings, placing the quartz tube in a tubular heating electric furnace, and introducing N2After activation with protective gas, then in N2And carrying out catalytic dehydration reaction on the 2, 3-butanediol in the protective gas atmosphere.
Preferably, the activation temperature is 250-350 ℃, N2The flow rate of the protective gas is 10-30 ml/min, and the activation treatment time is 1-4 h.
Preferably, the catalytic dehydration reaction temperature is 220-340 ℃, and N is2The flow rate of the protective gas is 10-30 ml/min, and the reaction time is 8-20 h.
Preferably, 2, 3-butanediylThe mass space velocity of the alcohol reaction liquid is 0.25-2.5 h-1。
Compared with the prior art, the invention has the following beneficial effects:
1) the invention adopts 2, 3-butanediol as raw material to prepare methyl ethyl ketone, thus avoiding the dependence of the domestic and foreign methyl ethyl ketone production industry on petroleum non-renewable energy sources.
2) The catalyst provided by the invention has the advantages of simple preparation process and low preparation cost. And the method does not corrode equipment, is environment-friendly and accords with the green chemical concept.
3) The catalyst provided by the invention has good activity and stability in the reaction of preparing methyl ethyl ketone by catalytic dehydration of 2, 3-butanediol, and is high in recovery rate and utilization rate, and suitable for industrial application.
4) Compared with the traditional n-butene two-step method, the method has the advantages of simple process, capability of effectively avoiding the introduction and generation of toxic and harmful substances, high operability and contribution to the realization of industrial production.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments.
The catalyst of the invention is Ba3（PO4）2the/AC can realize excellent catalytic reaction performance when being used for the catalytic dehydration reaction of the 2, 3-butanediol, and comprises high catalytic reaction activity, high methyl ethyl ketone selectivity and the like. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Examples
Example 1
(1) According to the maximum water absorption of the activated carbon, in the embodiment, the maximum water absorption is 2, 100g of the activated carbon is taken, 8g of barium phosphate and 192g of hydrochloric acid solution (1M) are taken according to the load of 8wt%, 200g of barium phosphate hydrochloric acid solution is prepared, the activated carbon is equivalently immersed in the barium phosphate hydrochloric acid solution, and the barium phosphate hydrochloric acid solution is immersed for 12 hours at room temperature;
(2) drying the impregnated activated carbon in the step (1) at 120 ℃ for 12 hours;
(3) adding the dried activated carbon obtained in the step (2) into N2Roasting at 450 ℃ for 4h under the protection of inert gas to obtain 8wt% of Ba3（PO4）2an/AC catalyst; the catalyst is numbered BaP-C-1.
Example 2
The loading of step (1) in example 1 was changed to 2%, and the other steps were the same as in example 1. The catalyst is numbered BaP-C-2.
Example 3
The loading of step (1) in example 1 was changed to 4%, and the other steps were the same as in example 1. The catalyst is numbered BaP-C-3.
Example 4
The loading of step (1) in example 1 was changed to 6%, and the other steps were the same as in example 1. The catalyst is numbered BaP-C-4.
Example 5
The loading of the step (1) in the example 1 is changed to 10%, and other steps are the same as the example 1. The catalyst is numbered BaP-C-4.
Example 6
The calcination temperature of the catalyst in the step (3) of the example 1 was changed, the catalyst was calcined at 350 ℃ for 4 hours, and the loading and other steps were the same as those of the example 1. The catalyst is numbered BaP-C-6.
Example 7
The calcination temperature of the catalyst in the step (3) of the example 1 was changed, the catalyst was calcined at 400 ℃ for 4 hours, and the loading and other steps were the same as those of the example 1. The catalyst is numbered BaP-C-7.
Example 8
The calcination temperature of the catalyst in the step (3) of the example 1 was changed, the catalyst was calcined at 500 ℃ for 4 hours, and the loading and other steps were the same as those of the example 1. The catalyst is numbered BaP-C-8.
Example 9
The calcination temperature of the catalyst in the step (3) of the example 1 was changed, the catalyst was calcined at 550 ℃ for 4 hours, and the loading and other steps were the same as those of the example 1. The catalyst is numbered BaP-C-9.
Application example
Application example 1
Use of self-made catalyst BaP-C-1 in 2Preparing methyl ethyl ketone by gas-phase catalytic dehydration of 3-butanediol, carrying out the reaction in a fixed bed reactor, taking 20g of catalyst BaP-C-1, activating for 1 h at 350 ℃, introducing N2Protecting gas and controlling the flow rate to be 20ml/min, then reducing the temperature of the reactor to 220 ℃, and controlling the mass space velocity of the 2, 3-butanediol reaction liquid to be 0.75 h-1During the reaction N2The guard gas flow rate was 20 ml/min. The reaction was terminated after 10h and the product was analyzed by gas chromatography.
Application examples 2 to 9
The self-made catalysts Ba-P-2 to Ba-P-9 are used for preparing the methyl ethyl ketone by gas-phase catalytic dehydration of the 2, 3-butanediol, and the operation steps are the same as the application example 1. The dehydration efficiency and selectivity of the catalyst are shown in table 1.
Comparative example
Comparative example 1
The step (1) of the example 1 is changed, the activated carbon is not loaded, and other steps are the same as the example 1.
The catalyst was used in the production of methyl ethyl ketone by vapor phase catalytic dehydration of 2, 3-butanediol, and the activity thereof was evaluated by using a fixed bed reactor in the same manner as in application example 1, and the results are shown in Table 2.
Comparative example 2
The reaction temperature conditions, the reaction temperature of 240 ℃, the loading amount, the calcination temperature and other conditions in example 1 were changed and the same as in example 1 was applied.
Comparative example 3
The reaction temperature conditions, the reaction temperature of 260 ℃, the loading amount, the calcination temperature and other conditions in example 1 were changed and the same as in example 1 was applied.
Comparative example 4
The reaction temperature conditions, the reaction temperature of 280 ℃, the loading amount, the calcination temperature and other conditions in example 1 were changed and the other steps were the same as in example 1.
Comparative example 5
The reaction temperature conditions, reaction temperature of 300 ℃, loading amount, baking temperature and other conditions in example 1 were changed and the same procedure as in example 1 was followed.
Comparative example 6
The reaction temperature conditions, the reaction temperature of 320 ℃, the loading amount, the calcination temperature and other conditions in example 1 were changed and the other steps were the same as in example 1.
Comparative example 7
The mass space velocity of the 2, 3-butanediol reaction liquid in the sample 1 is changed, and the mass space velocity of the 2, 3-butanediol reaction liquid is controlled to be 0.25 h-1The conditions such as loading amount and calcination temperature and other steps are the same as those in application example 1.
Comparative example 8
The mass space velocity of the 2, 3-butanediol reaction liquid in the sample 1 is changed, and the mass space velocity of the 2, 3-butanediol reaction liquid is controlled to be 0.5h-1The conditions such as loading amount and calcination temperature and other steps are the same as those in application example 1.
Comparative example 9
The mass space velocity of the 2, 3-butanediol reaction liquid in the sample 1 is changed, and the mass space velocity of the 2, 3-butanediol reaction liquid is controlled to be 1.0h-1The conditions such as loading amount and calcination temperature and other steps are the same as those in application example 1.
Comparative example 10
The mass space velocity of the 2, 3-butanediol reaction liquid in the sample 1 is changed, and the mass space velocity of the 2, 3-butanediol reaction liquid is controlled to be 1.25 h-1The conditions such as loading amount and calcination temperature and other steps are the same as those in application example 1.
The reaction product was analyzed by gas chromatography and the results are shown in Table 2.
TABLE 1 conversion of 2, 3-butanediol and selectivity to methyl ethyl ketone for different catalysts
TABLE 2 comparative examples different reaction conditions for 2, 3-butanediol conversion and methyl ethyl ketone selectivity
The invention uses alkaline earth metal salt as active component for the first time, which is different from the prior Lewis acid catalyst. The raw material is taken from the byproduct 2, 3-butanediol of 1, 3-propanediol produced by an industrial glycerol fermentation method, downstream products can be effectively developed, the problem of surplus 2, 3-butanediol in the industry is solved, the market requirement of methyl ethyl ketone is wide, and certain economic benefit can be driven.
Claims (10)
1. Ba3（PO4）2A preparation method of an AC catalyst, which is used for preparing methyl ethyl ketone by dehydrating 2, 3-butanediol, is characterized by comprising the following steps:
step (1), dipping activated carbon in barium phosphate hydrochloric acid solution for 2-12 h at room temperature;
drying the activated carbon impregnated in the step (1) at 100-150 ℃ for 2-12 h;
step (3), adding the dried active carbon into N2Roasting for 2-6 h under the protection of inert gas to obtain Ba3（PO4）2an/AC catalyst.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the barium phosphate to the activated carbon is 2 to 10%, preferably 8%.
3. The method of claim 1, wherein the activated carbon is equally immersed in the barium phosphate hydrochloric acid solution at room temperature for 12 hours according to the maximum water absorption of the activated carbon.
4. The method according to claim 1, wherein in the step (2), the drying temperature is 120 ℃ and the drying time is 12 hours.
5. The method of claim 1, wherein in step (3), N is2The flow rate of (2) is 10-40 ml/min, and roasting is carried out for 4 hours.
6. A catalyst prepared by the process of any one of claims 1 to 5.
7. Use of a catalyst prepared according to any one of claims 1 to 5 in the production of methyl ethyl ketone by dehydration of 2, 3-butanediol.
8. The use according to claim 7, wherein the reaction is carried out by: placing the catalyst in the middle of a quartz tube, filling the two ends with inert ceramic rings, placing in a tubular heating electric furnace, introducing N2After activation with protective gas, then in N2And carrying out catalytic dehydration reaction on the 2, 3-butanediol in the protective gas atmosphere.
9. The use according to claim 8, wherein the activation temperature is 250 to 350 ℃ and N2The flow rate of the protective gas is 10-30 ml/min, and the activation treatment time is 1-4 h.
10. The use according to claim 8, wherein the catalytic dehydration reaction temperature is 220 to 340 ℃, N2The flow rate of the protective gas is 10-30 ml/min, and the reaction time is 8-20 h; the mass space velocity of the 2, 3-butanediol reaction liquid is 0.25-2.5 h-1。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047276A (en) * | 1989-05-19 | 1990-11-28 | 国际壳牌研究有限公司 | The catalytic alkoxylating method of barium phosphate |
| US20150218062A1 (en) * | 2014-02-03 | 2015-08-06 | Battelle Memorial Institute | Conversion of 2,3-butanediol to butadiene |
| CN209338125U (en) * | 2018-12-14 | 2019-09-03 | 桂东县湘浙活性炭有限公司 | A kind of Activated Carbon Production dephosphorylation device |
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2019
- 2019-10-12 CN CN201910965440.3A patent/CN110743580B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047276A (en) * | 1989-05-19 | 1990-11-28 | 国际壳牌研究有限公司 | The catalytic alkoxylating method of barium phosphate |
| US20150218062A1 (en) * | 2014-02-03 | 2015-08-06 | Battelle Memorial Institute | Conversion of 2,3-butanediol to butadiene |
| CN105873885A (en) * | 2014-02-03 | 2016-08-17 | 巴特尔纪念研究院 | Conversion of 2,3-butanediol to butadiene |
| CN209338125U (en) * | 2018-12-14 | 2019-09-03 | 桂东县湘浙活性炭有限公司 | A kind of Activated Carbon Production dephosphorylation device |
Non-Patent Citations (3)
| Title |
|---|
| ANDREAS GEORG THOME等: "Dehydration of 2,3-Butanediol: A Catalytical and Theoretical Approach", 《CATAL LETT》 * |
| 廉志红等: "铕在硼磷酸钡玻璃中的空气下还原及其发光性质", 《无机化学学报》 * |
| 马洋博等: "负载型固体碱催化合成三氟碘甲烷", 《化学试剂》 * |
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