CN114436999A - Method for preparing propylene oxide - Google Patents
Method for preparing propylene oxide Download PDFInfo
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- CN114436999A CN114436999A CN202011193818.1A CN202011193818A CN114436999A CN 114436999 A CN114436999 A CN 114436999A CN 202011193818 A CN202011193818 A CN 202011193818A CN 114436999 A CN114436999 A CN 114436999A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/22—Synthesis of the oxirane ring by oxidation of saturated compounds with air or molecular oxygen
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a process for the preparation of propylene oxide, which process comprises: s1, contacting propane and the nano carbon-based material at 300-800 ℃ and 0-10 MPa to perform a first reaction to obtain a first reaction product; s2, in the presence of a bifunctional catalyst and an optional solvent, enabling the first reaction product to contact with oxygen at 0-80 ℃ and 0.1-10 MPa to carry out a second reaction. The method of the invention directly takes propane and oxygen as raw materials, and can prepare propylene oxide with higher conversion rate and selectivity.
Description
Technical Field
The present invention relates to a process for the preparation of propylene oxide.
Background
Propylene Oxide (PO) is a large chemical raw material, is the second largest organic chemical product of propylene derivatives with the second highest yield than polypropylene, and is the highest 50 chemicals in the world. PO has active chemical property and wide application, is widely applied to the industries of chemical industry, light industry, medicine, food, textile and the like, and has profound influence on the development of chemical industry and national economy.
At present, the chlorohydrin method and the co-oxidation method are mainly adopted for industrially producing the propylene oxide, and the production capacity of the chlorohydrin method and the co-oxidation method accounts for more than 80 percent of the total world production capacity. The chlorohydrin method is earlier applied to production, uses chlorine, is seriously corroded, generates a large amount of chlorine-containing wastewater polluting the environment, does not meet the requirements of green chemistry and clean production, and therefore, the process is finally eliminated along with the increasing requirement of environmental protection. The co-oxidation method indirectly oxidizes propylene to PO mainly using ethylbenzene peroxide or tert-butyl hydroperoxide as an oxygen source. The co-oxidation method overcomes the defects of environmental pollution, equipment corrosion and the like of the chlorohydrin method, and is a production process which is relatively cleaner than the chlorohydrin method. But a large amount of cheap byproducts such as styrene or tert-butyl alcohol and the like are co-produced, the market of the byproducts is difficult to digest, and the economic factors are the main reasons for restricting the development of the byproducts due to the long process and large construction investment scale.
The method using hydrogen peroxide as oxidant and titanium-silicon molecular sieve as catalyst can obtain higher propylene conversion rate and PO selectivity. The method is simple and convenient, does not pollute the environment, is a very competitive PO production process, meets the requirements of the modern green chemistry and atomic economic development concept, is considered as a green new process for producing PO, and is the third largest PO production method at present. However, due to H2O2Extremely unstable, subject to heat, light, rough surfaces, decomposition of heavy metals and other impurities, and corrosive, special safety measures are required in packaging, storage, and transportation. Subject to cost and safety concerns, and preparation of H2O2The requirement of separate equipment and a circulating system has high cost and high field production cost, and the economic advantage is not obvious before stricter environmental protection regulations are released, which is one of the important reasons that a plurality of production devices adopting hydrogen peroxide as an oxidizing agent are not put into operation or are full production at present.
Molecular oxygen is cheap, easy to obtain and pollution-free, and is the most ideal oxygen source. But using O2Propylene oxide is difficult to be efficiently produced by direct oxidation of propylene. The success of shale gas revolution, the supply of propane is greatly increased, and how to utilize propane is also a question of urgent need in the industryThe new process for preparing the propylene oxide by direct oxidation by taking the propane as the raw material is both considered, and has great research and industrial application prospects.
Disclosure of Invention
The invention aims to provide a method for preparing propylene oxide, which can directly prepare propylene oxide by taking propane and oxygen as raw materials.
In order to achieve the above object, the present invention provides a method for preparing propylene oxide, comprising:
s1, contacting propane and the nano carbon-based material at 300-800 ℃ and 0-10 MPa to perform a first reaction to obtain a first reaction product;
and S2, in the presence of a bifunctional catalyst and an optional solvent, contacting the first reaction product with oxygen at 0-80 ℃ and 0.1-10 MPa to perform a second reaction.
Optionally, in step S1, the conditions of the first reaction include: the temperature is 400-700 ℃, the time is 0-5 MPa, and the volume space velocity of propane is 1-100 h-1。
Optionally, in step S2, the molar ratio of the first reaction product to the amount of oxygen used is 1: (0.1-2), preferably 1: (0.2 to 1);
the conditions of the second reaction include: the temperature is 20-60 ℃, and the time is 0.5-5 MPa.
Optionally, the carbon nanotube is baked for 1-24 hours at 200-1000 ℃ in an ammonia atmosphere of 0.1-5 vol% to obtain the nanocarbon-based material.
Optionally, the bifunctional molecular sieve catalyst contains one or more noble metal elements selected from Pd, Pt, Au, Ag and Ru; based on the dry basis weight of the bifunctional molecular sieve catalyst, the content of the noble metal element is 0.05-10 wt%.
Alternatively, the bifunctional molecular sieve catalyst is prepared by a process comprising the steps of: dipping a titanium silicalite molecular sieve into a solution containing a noble metal element, and carrying out dipping reaction for 1-12 hours at the temperature of 20-80 ℃; the silicon-titanium ratio of the titanium-silicon molecular sieve is 10-100.
Optionally, the second reactionThe total air space velocity of the gas is 10-10000 h-1Preferably 100 to 5000 hours-1。
Alternatively, in step S2, the second reaction is carried out in the presence of a solvent;
the solvent is selected from inorganic solvents and/or organic solvents; the inorganic solvent is deionized water; the organic solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile, and preferably methanol and/or deionized water.
Optionally, the weight ratio of the solvent to the bifunctional molecular sieve catalyst is (10-1000): 1, preferably (20-500): 1.
optionally, the selectivity of the propylene oxide is 50-100%, and the conversion rate of the propane is 20-50%.
By adopting the technical scheme, the method directly takes the propane and the oxygen as raw materials, and can prepare the propylene oxide with higher conversion rate and selectivity.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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.
The present invention provides a process for producing propylene oxide, the process comprising:
s1, contacting propane and the nano carbon-based material at 300-800 ℃ and 0-10 MPa to perform a first reaction to obtain a first reaction product;
s2, in the presence of a bifunctional catalyst and an optional solvent, enabling the first reaction product to contact with oxygen at 0-80 ℃ and 0.1-10 MPa to carry out a second reaction.
The method of the invention directly takes propane and oxygen as raw materials to prepare the propylene oxide, has simple and easy operation and low cost, can prepare the propylene oxide with higher conversion rate and selectivity, and is particularly suitable for the industrial production of the propylene oxide taking the propane as the initial raw material.
In a preferred embodiment, in step S1, the temperature of the first reaction is 400-700 ℃, the pressure is 0-5 MPa, and the volume space velocity of propane is 1-100 h-1Preferably 5 to 50 hours-1。
According to the invention, the molar ratio of the first reaction product to the amount of oxygen used in step S2 may vary within a wide range, and may be, for example, 1: (0.1-2), preferably 1: (0.2 to 1). In a preferred embodiment, in step S2, the temperature of the second reaction is 20 to 60 ℃ and the pressure is 0.5 to 5 MPa.
According to the present invention, the apparatus used for the first reaction and the second reaction is not particularly limited, and the apparatus used for the first reaction and the second reaction may be a fixed bed reactor, a moving bed reactor, a microreactor, or other various reactors, independently of each other. In a preferred embodiment, the first reaction is carried out in a fixed-bed microreactor and the second reaction is carried out in a slurry-bed reactor, with the process described above the conversion of the starting materials and the selectivity to propylene oxide being further increased.
According to the invention, the nanocarbon-based material can be a commercially available product or a modified product obtained by modifying the commercially available product, and preferably, the nanocarbon-based material is a multi-walled carbon nanotube modified by ammonia nitrogen activation. In one embodiment, the modified multi-walled carbon nanotubes are prepared by a method comprising the steps of: the carbon nanotubes are baked for 1-24h at 200-5 vol%, preferably 1-2.5 vol% ammonia gas atmosphere at 1000-400-600 ℃. Preferably, the carbon nanotubes are multi-walled carbon nanotubes. The ammonia gas atmosphere may also contain nitrogen and/or inert gases, which are well known to those skilled in the art, such as helium, argon, etc.
According to the invention, the bifunctional catalyst can contain one or more noble metal elements of Pd, Pt, Au, Ag and Ru, preferably Pd; the content of the noble metal element contained in the bifunctional catalyst can vary within a wide range, for example, 0.05 to 10 wt%, preferably 0.1 to 5 wt%, based on the dry weight of the bifunctional catalyst, and the balance of the titanium silicalite molecular sieve and the optional binder.
In one embodiment, the bifunctional catalyst may be prepared by a process comprising the steps of: dipping a titanium silicalite molecular sieve into a solution containing a noble metal element, and carrying out dipping reaction for 1-12 hours at the temperature of 20-80 ℃; the noble metal in the solution containing the noble metal element can exist in one or more of nitrate, acetate, complex, hydrochloride and the like.
Titanium silicalite molecular sieves according to the present invention are well known to those skilled in the art and can be obtained by either self-synthesis or commercially available routes. The ratio of silicon to titanium in the titanium silicalite molecular sieve can vary widely, and can be, for example, 10 to 100, preferably 20 to 50.
According to the invention, the total gas space velocity of the second reaction can be 10-10000 h-1Preferably 100 to 5000 hours-1The total gas refers to the total amount of the first reaction product and oxygen.
According to the present invention, in step S2, the second reaction is carried out in the presence of a solvent; in one embodiment, the solvent is selected from inorganic and/or organic solvents; the inorganic solvent may be deionized water; the organic solvent may be one or more selected from alcohols, ketones and nitriles, and may be one or more selected from methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile, preferably methanol and/or deionized water.
According to the invention, the weight ratio of the solvent to the bifunctional catalyst can be (10-1000): 1, preferably (20-500): 1.
according to the invention, the conversion rate of the propane can be 5-80%, the selectivity of the propylene oxide can be 50-100%, preferably, the conversion rate of the propane is 20-50%, and the selectivity of the propylene oxide is 80-100%.
The invention is further illustrated by the following examples, but is not limited thereto.
The reagents used in the examples are all commercially available, chemically pure reagents.
The nano carbon material is a multi-wall carbon nano tube modified by ammonia nitrogen (CNT is activated and modified). The preparation method comprises the following steps: the multi-walled carbon nanotubes were calcined in a tubular furnace at 600 ℃ for 4h under an atmosphere of 1% by volume of ammonia (balance nitrogen).
The titanium silicalite molecular sieve (TS-1) was a sample of (TS-1) molecular sieve prepared as described in Zeolite, 1992, Vol.12, pp 943-950 of the prior art.
The contents of the respective components in the obtained reaction product were analyzed by gas chromatography, and on the basis thereof, the conversion of propane and the selectivity of propylene oxide were calculated by the following formulas, respectively:
propane conversion ═ [ (molar amount of propane charged-molar amount of unreacted propane)/molar amount of propane charged ] × 100%;
propylene oxide selectivity ═ 100% by mole [ molar amount of propylene oxide produced by the reaction/(molar amount of propane added-molar amount of unreacted propane) ].
Example 1
The bifunctional (0.5 wt% Pd/TS) catalyst was prepared as follows:
taking 10 g of titanium silicalite molecular sieve (the ratio of silicon to titanium is 80), adding the titanium silicalite molecular sieve into 20mL of PdCl with the concentration of 0.01g/mL2Stirring the mixture in the aqueous solution at the temperature of 40 ℃ for 24 hours, sealing the mixture properly, and naturally drying the mixture at room temperature for 48 hours to obtain the bifunctional (0.5 wt% Pd/TS) catalyst, wherein the bifunctional (0.5 wt% Pd/TS) catalyst is subjected to reduction activation in a mixed atmosphere of 5 vol% hydrogen (the balance being nitrogen) at the temperature of 300 ℃ for 3 hours before use.
The process for preparing propylene oxide is as follows:
at the normal pressure of 600 ℃ and the propane volume space velocity of 100h-1Then, the propane firstly passes through a fixed bed microreactor which takes a nano carbon-based material as a catalyst bed layer to carry out a first reaction, and the obtained first reaction product, oxygen, a solvent methanol and a bifunctional catalyst are subjected to a first reaction in a slurry bed reactor according to the mol ratio of the first reaction product to the oxygen being 4: 1, the weight ratio of the solvent methanol to the bifunctional catalyst is 50, the temperature is 60 ℃, the pressure is 0.5MPa, and the space velocity of the total gas volume is 1000h-1Is going on in reverseShould be used. And (3) carrying out gas chromatography analysis on the reaction mixture obtained after the reaction is finished, and calculating the conversion rate of propane and the selectivity of propylene oxide. The results are listed in table 1.
Example 2
Propylene oxide was prepared in the same manner as in example 1, except that the space velocity of propane volume was 5 hours at 400 ℃ under normal pressure-1Then, the propane firstly passes through a fixed bed micro-reactor with a nano carbon-based material as a catalyst bed layer to carry out direct first reaction, and the obtained first reaction product, oxygen, a solvent methanol and a bifunctional catalyst are mixed according to the mol ratio of the first reaction product to the oxygen of 2: 1, the weight ratio of the solvent methanol to the bifunctional catalyst is 20, the temperature is 40 ℃, the pressure is 2.5MPa, and the space velocity of the total gas volume is 200h-1The reaction was carried out as follows.
Example 3
Propylene oxide was prepared in the same manner as in example 1 except that the space velocity of propane volume was 25 hours at 500 ℃ under normal pressure-1Then, the propane firstly passes through a fixed bed micro-reactor with a nano-carbon-based material as a catalyst bed layer to carry out direct first reaction, and the obtained first reaction product, oxygen, a solvent methanol and a bifunctional catalyst are mixed according to the mol ratio of the first reaction product to the oxygen of 10: 1, the weight ratio of the solvent methanol to the bifunctional catalyst is 40, the temperature is 50 ℃, the pressure is 1.5MPa, and the space velocity of the total gas volume is 100h-1The reaction proceeds as follows.
Example 4
Propylene oxide was prepared in the same manner as in example 1, except that the space velocity of propane volume was 8 hours at 400 ℃ under 6MPa-1Then, the propane firstly passes through a fixed bed micro-reactor with a nano-carbon-based material as a catalyst bed layer to carry out a first reaction.
Example 5
Propylene oxide was prepared by the same method as in example 1, except that the molar ratio of the first reaction product to oxygen was 6: 1.
example 6
The same as in example 1 was usedThe difference of the method for preparing the propylene oxide is that 10 g of titanium silicalite molecular sieve is added into 10mL of PdCl with the concentration of 0.008g/mL2Stirring the mixture in the aqueous solution at the temperature of 40 ℃ for 24 hours, sealing the mixture properly, and naturally drying the mixture at room temperature for 48 hours to obtain the bifunctional (0.1 wt% Pd/TS) catalyst, wherein the bifunctional (0.1 wt% Pd/TS) catalyst is subjected to reduction activation in a mixed atmosphere of 5 vol% hydrogen (the balance being nitrogen) at the temperature of 300 ℃ for 3 hours before use.
Example 7
Propylene oxide was prepared in the same manner as in example 1, except that the total gas volume space velocity was 6000h-1。
Comparative example 1
Propylene oxide was prepared in the same manner as in example 1, except that the nanocarbon-based material was not used.
Comparative example 2
Propylene oxide was prepared in the same manner as in example 1, except that the bifunctional catalyst was not used.
Comparative example 3
Propylene oxide was prepared in the same manner as in example 1, except that the nanocarbon-based material and the bifunctional catalyst were not used.
TABLE 1
As is apparent from the results of the comparative example and examples, the present invention can directly produce propylene oxide from propane and oxygen, and has the advantages of simple and easy process, low cost, and high propane conversion and propylene oxide selectivity.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A process for the preparation of propylene oxide, the process comprising:
s1, contacting propane and the nano carbon-based material at 300-800 ℃ and 0-10 MPa to perform a first reaction to obtain a first reaction product;
s2, in the presence of a bifunctional catalyst and an optional solvent, enabling the first reaction product to contact with oxygen at 0-80 ℃ and 0.1-10 MPa to carry out a second reaction.
2. The method of claim 1, wherein in step S1, the conditions of the first reaction include: the temperature is 400-700 ℃, the time is 0-5 MPa, and the volume space velocity of propane is 1-100 h-1。
3. The method of claim 1, wherein in step S2, the molar ratio of the first reaction product to the amount of oxygen is 1: (0.1-2), preferably 1: (0.2 to 1);
the conditions of the second reaction include: the temperature is 20-60 ℃, and the time is 0.5-5 MPa.
4. The method as claimed in claim 1, wherein the carbon nanotubes are baked at 200-1000 ℃ for 1-24h under 0.1-5 vol% ammonia gas atmosphere to obtain the nanocarbon-based material.
5. The method of claim 1, wherein the bifunctional molecular sieve catalyst comprises one or more noble metal elements selected from Pd, Pt, Au, Ag, and Ru; the content of the noble metal element is 0.05-10 wt% based on the dry weight of the bifunctional molecular sieve catalyst.
6. The process of claim 5 wherein the bifunctional molecular sieve catalyst is prepared by a process comprising: dipping a titanium silicalite molecular sieve into a solution containing a noble metal element, and carrying out dipping reaction for 1-12 hours at the temperature of 20-80 ℃; the silicon-titanium ratio of the titanium-silicon molecular sieve is 10-100.
7. The method of claim 1, wherein the total gas space velocity of the second reaction is 10-10000 h-1Preferably 100 to 5000 hours-1。
8. The method of claim 1, wherein, in step S2, the second reaction is carried out in the presence of a solvent;
the solvent is selected from inorganic solvent and/or organic solvent; the inorganic solvent is deionized water; the organic solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile, and preferably methanol and/or deionized water.
9. The method of claim 8, wherein the weight ratio of the solvent to the bifunctional molecular sieve catalyst is (10-1000): 1, preferably (20 to 500): 1.
10. the method according to claim 1, wherein the selectivity of propylene oxide is 50 to 100% and the conversion of propane is 20 to 50%.
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| US10385032B1 (en) * | 2018-07-06 | 2019-08-20 | Uchicago Argonne, Llc | Selective oxidation of propane to propylene oxide |
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| US5973171A (en) * | 1998-10-07 | 1999-10-26 | Arco Chemical Technology, Lp | Propylene oxide production |
| CN1387948A (en) * | 2002-02-05 | 2003-01-01 | 石家庄炼油化工股份有限公司 | Formula and preparation process of catalyst for preparing epoxypropane by propylene epoxidation in oxyhydrogen atmosphere |
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