CN114436999B - Method for preparing epoxypropane - Google Patents
Method for preparing epoxypropane Download PDFInfo
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- CN114436999B CN114436999B CN202011193818.1A CN202011193818A CN114436999B CN 114436999 B CN114436999 B CN 114436999B CN 202011193818 A CN202011193818 A CN 202011193818A CN 114436999 B CN114436999 B CN 114436999B
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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
- 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
- Y02P20/50—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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a process for preparing propylene oxide, which comprises: s1, enabling propane to contact with a nano carbon-based material at the temperature of 300-800 ℃ and under the pressure of 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 be in contact with oxygen at 0-80 ℃ and 0.1-10 MPa for carrying out a second reaction. The method 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 preparing propylene oxide.
Background
Propylene Oxide (PO) is a large chemical raw material, and is a second largest organic chemical product with the yield of propylene derivatives being inferior to that of polypropylene among 50 chemicals with the largest global yield. PO has very 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 effects on the development of chemical industry and national economy.
At present, the industrial production of propylene oxide mainly adopts a chlorohydrin method and a co-oxidation method, and the production capacity of the two methods accounts for more than 80% of the total world production capacity. The chlorohydrin method is applied to production earlier, and the method uses chlorine, has serious corrosion and generates a large amount of chlorine-containing wastewater polluting the environment, does not meet the requirements of green chemistry and clean production, so that the process is finally eliminated with the increasing environmental protection requirements. The co-oxidation process uses mainly ethylbenzene peroxide or t-butyl hydroperoxide as an oxygen source to indirectly oxidize propylene to PO. The co-oxidation method overcomes the defects of environmental pollution, equipment corrosion and the like of the chlorohydrin method, and is a relatively cleaner production process than the chlorohydrin method. But co-production of a large amount of low-cost byproducts such as styrene or tertiary butanol, which are difficult to digest, and long process and large construction investment scale, and economic factors are main reasons for restricting the development of the low-cost byproducts.
The method using hydrogen peroxide as oxidant and titanium silicalite molecular sieve as catalyst can have higher propylene conversion rate and PO selectivity. The method is simple and convenient, does not pollute the environment, is a PO production process with great competitiveness, meets the requirements of modern green chemistry and atomic economy development concepts, is considered as a green new process for producing PO, and is a third largest PO production method at present. However, due to H 2 O 2 Is extremely unstable, is exposed to heat and light, has rough surfaces, can decompose heavy metals and other impurities, is corrosive, and needs special safety measures in packaging, storage and transportation. Is limited by cost and safety issues, and prepares H 2 O 2 The need of separate equipment and a circulating system has the disadvantages of high cost and high on-site production cost, and the economic advantage is not obvious before stricter environmental regulations are not put out, which is one of the important reasons that a plurality of production devices adopting hydrogen peroxide as an oxidant are not put into production or are fully produced at present.
Molecular oxygen is cheap and easy to obtain, has no pollution and is the most ideal oxygen source. But utilize O 2 Propylene oxide is difficult to be effectively prepared by directly oxidizing propylene. The success of shale gas revolution, the supply of propane is greatly increased, and how to utilize propane is also a problem of urgent need of thinking in the industry at present, and the new process for preparing propylene oxide by directly oxidizing propane is compatible with the two processes, so that the method has great research and industrialization 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 producing propylene oxide, comprising:
s1, enabling propane to contact with a nano carbon-based material at the temperature of 300-800 ℃ and under the pressure of 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 be in contact with oxygen at 0-80 ℃ and 0.1-10 MPa for carrying out 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 airspeed of propane is 1-100 h -1 。
Optionally, in step S2, the molar ratio of the first reaction product to the oxygen amount is 1: (0.1 to 2), preferably 1: (0.2-1);
the conditions of the second reaction include: the temperature is 20-60 ℃ and the time is 0.5-5 MPa.
Optionally, the carbon nano tube is roasted for 1-24 hours at 200-1000 ℃ in an ammonia atmosphere with 0.1-5% by volume, and the nano carbon-based material is obtained.
Optionally, the bifunctional molecular sieve catalyst contains one or more noble metal elements of 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.
Optionally, the bifunctional molecular sieve catalyst is prepared by a method comprising the steps of: soaking titanium-silicon molecular sieve in solution containing noble metal element at 20-80 deg.c for 1-12 hr; the ratio of silicon to titanium of the titanium silicon molecular sieve is 10-100.
Optionally, the total gas space velocity of the second reaction is 10 to 10000h -1 Preferably 100 to 5000h -1 。
Optionally, in step S2, the second reaction is performed 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, preferably methanol and/or deionized water.
Optionally, the weight ratio of the solvent to the amount of the bifunctional molecular sieve catalyst is (10-1000): 1, preferably (20 to 500): 1.
alternatively, the selectivity of the propylene oxide is 50-100%, and the conversion rate of the propane is 20-50%.
Through the technical scheme, the method directly takes propane and oxygen as raw materials, and can prepare 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 specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The present invention provides a process for preparing propylene oxide, the process comprising:
s1, enabling propane to contact with a nano carbon-based material at the temperature of 300-800 ℃ and under the pressure of 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 be in contact with oxygen at 0-80 ℃ and 0.1-10 MPa for carrying out a second reaction.
The method directly takes propane and oxygen as raw materials to prepare the propylene oxide, is simple and easy to operate, has low cost, can prepare the propylene oxide with higher conversion rate and selectivity, and is particularly suitable for industrialized production of the propylene oxide taking propane as an initial raw material.
In a preferred embodiment, in step S1, the temperature of the first reaction is 400 to 700℃and the pressure is 0 to 5MPa, and the volume space velocity of propane is 1 to 100h -1 Preferably 5 to 50 hours -1 。
According to the invention, in step S2, the molar ratio of the first reaction product to the amount of oxygen may vary within a wide range, for example 1: (0.1 to 2), preferably 1: (0.2-1). In a preferred embodiment, in step S2, the second reaction is carried out at a temperature of 20 to 60℃and a pressure of 0.5 to 5MPa.
The apparatus used for the first reaction and the second reaction according to the present invention is not particularly limited, and the apparatus used for the first reaction and the second reaction may each be independently a fixed bed reactor, a moving bed reactor, a micro reactor or other various types of reactors. 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 above process further increasing the conversion of the feedstock and the selectivity to propylene oxide.
According to the invention, the nano carbon-based material can be a commercial product or a modified product obtained by modifying the commercial product, and preferably, the nano carbon-based material is a multiwall carbon nanotube subjected to ammonia nitrogen activation modification. In one embodiment, the modified multiwall carbon nanotubes are prepared by a process comprising the steps of: the carbon nanotubes are calcined at 200-1000 c, preferably 400-600 c, for 1-24h under an ammonia atmosphere of 0.1-5 vol%, preferably 1-2.5 vol%. Preferably, the carbon nanotubes are multiwall carbon nanotubes. The ammonia atmosphere may also contain nitrogen and/or an inert gas, which is well known to those skilled in the art, and may be, for example, 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 noble metal elements contained in the bifunctional catalyst may vary within a wide range, for example, may be from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, based on the dry weight of the bifunctional catalyst, with the remainder being titanium silicalite and optional binders.
In one embodiment, the dual function catalyst may be prepared by a process comprising the steps of: soaking titanium-silicon molecular sieve in solution containing noble metal element at 20-80 deg.c for 1-12 hr; the noble metal in the noble metal-containing solution may be present in the form of one or more of nitrate, acetate, complex, hydrochloride, and the like.
Titanium silicalite molecular sieves are well known to those skilled in the art and may be obtained by self-synthesis or commercially available routes in accordance with the present invention. The ratio of titanium to silicon of the titanium-silicon molecular sieve may vary within a wide range, for example, may be 10 to 100, and preferably 20 to 50.
According to the invention, the total gas space velocity of the second reaction may be from 10 to 10000h -1 Preferably 100 to 5000h -1 Total gas refers to the total amount of the first reaction product and oxygen.
According to the invention, in step S2, a second reaction is carried out in the presence of a solvent; in a specific embodiment, the solvent is selected from inorganic solvents and/or organic solvents; the inorganic solvent may be deionized water; the organic solvent can be selected from one or more of alcohol, ketone and nitrile, for example, one or more of 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 solvent to bifunctional catalyst can be (10-1000): 1, preferably (20 to 500): 1.
according to the present invention, the conversion of propane may be 5 to 80%, the selectivity of propylene oxide may be 50 to 100%, preferably the conversion of propane is 20 to 50%, and the selectivity of propylene oxide is 80 to 100%.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The reagents used in the examples were all commercially available chemically pure reagents.
The nano carbon material is a multiwall carbon nanotube modified by ammonia nitrogen (CNT is modified by activation). The preparation method comprises the following steps: the multi-walled carbon nanotubes were baked at 600℃for 4 hours in an ammonia atmosphere of 1% by volume (the balance being nitrogen gas) using a tube furnace.
Titanium silicalite molecular sieves (TS-1) are samples of (TS-1) molecular sieves prepared as described in the prior art Zeolite, 1992, vol.12, pages 943-950.
The contents of the components in the obtained reaction product were analyzed by gas chromatography, and on the basis of this, the conversion of propane and the selectivity of propylene oxide were calculated using the following formulas, respectively:
propane conversion = [ (molar amount of propane added-molar amount of unreacted propane)/molar amount of propane added ] ×100%;
propylene oxide selectivity= [ molar amount of propylene oxide produced by reaction/(molar amount of propane added-molar amount of unreacted propane) ]x100%.
Example 1
The preparation of the bifunctional (0.5 wt% Pd/TS) catalyst is as follows:
10 g of titanium silicalite molecular sieve (silicon-titanium ratio 80) was added to 20mL of PdCl with a concentration of 0.01g/mL 2 Stirring the mixture in water solution for 24 hours at 40 ℃, sealing the mixture appropriately, naturally drying the mixture at room temperature for 48 hours to obtain the bifunctional (0.5 wt% Pd/TS) catalyst, and carrying out reduction activation for 3 hours at 300 ℃ in a mixed atmosphere of 5 vol% hydrogen (the balance being nitrogen) before use.
The process for preparing propylene oxide is as follows:
at normal pressure 600 ℃, the volume space velocity of propane is 100h -1 Firstly, propane is subjected to a first reaction through a fixed bed micro-reactor taking a nano carbon-based material as a catalyst bed layer, and the obtained first reaction product, oxygen, methanol serving as a solvent and a bifunctional catalyst are arranged in a slurry bed reactor according to the mole ratio of the first reaction product to the oxygen of 4:1, the weight ratio of the solvent methanol to the bifunctional catalyst is 50, and the total gas volume space velocity is 1000h at the temperature of 60 ℃ and the pressure of 0.5MPa -1 The reaction was carried out as follows. The reaction mixture obtained after the completion of the reaction was analyzed by gas chromatography, and the conversion of propane and the selectivity of propylene oxide were calculated. The results are listed in table 1.
Example 2
Propylene oxide was produced in the same manner as in example 1 except that the volume space velocity of propane was 5 hours at 400℃under normal pressure -1 Then, the propane is directly subjected to a first reaction by a fixed bed micro reactor with a nano carbon-based material as a catalyst bed layer, and the obtained productThe molar ratio of the first reaction product to oxygen, the solvent methanol and the bifunctional catalyst is 2:1, the weight ratio of the solvent methanol to the bifunctional catalyst is 20, and the total gas volume space velocity is 200h at the temperature of 40 ℃ and the pressure of 2.5MPa -1 The reaction was carried out as follows.
Example 3
Propylene oxide was produced in the same manner as in example 1 except that the volume space velocity of propane was 25 hours at 500℃under normal pressure -1 Then, propane is subjected to direct first reaction through a fixed bed micro reactor with a nano carbon-based material as a catalyst bed layer, and the obtained first reaction product is reacted with oxygen, methanol serving as a solvent and a bifunctional catalyst according to the mole 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, and the total gas volume space velocity is 100h at 50 ℃ and 1.5MPa -1 The reaction proceeds as follows.
Example 4
Propylene oxide was produced in the same manner as in example 1 except that the volume space velocity of propane was 8h at 6MPa and 400 ℃ -1 And then, propane is subjected to a first reaction through a fixed bed micro-reactor taking the nano carbon-based material as a catalyst bed layer.
Example 5
Propylene oxide was prepared in the same manner as in example 1 except that the molar ratio of the first reaction product to oxygen was 6:1.
example 6
Propylene oxide was produced in the same manner as in example 1 except that 10 g of a titanium silicalite molecular sieve was added to 10mL of PdCl having a concentration of 0.008g/mL 2 Stirring the mixture in water solution for 24 hours at 40 ℃, sealing the mixture appropriately, naturally drying the mixture at room temperature for 48 hours to obtain the bifunctional (0.1 wt% Pd/TS) catalyst, and carrying out reduction activation for 3 hours at 300 ℃ in a mixed atmosphere of 5 vol% hydrogen (the balance being nitrogen) before use.
Example 7
By the same procedure as in example 1Propylene oxide was prepared in the same manner 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 a 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 can be seen from the results of the comparative examples and examples, the present invention can directly prepare propylene oxide from propane and oxygen, and the process is simple and easy to operate, has low cost, and has high propane conversion rate and propylene oxide selectivity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (13)
1. A process for preparing propylene oxide, the process comprising:
s1, enabling propane to contact with a 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 for a second reaction;
and roasting the carbon nano tube for 1-24 hours at 200-1000 ℃ in an ammonia atmosphere with the volume percent of 0.1-5%, so as to obtain the nano carbon-based material.
2. The method according to 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 airspeed 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);
the conditions of the second reaction include: the temperature is 20-60 ℃ and the time is 0.5-5 MPa.
4. A method according to claim 3, wherein in step S2 the molar ratio of the first reaction product to the amount of oxygen is 1: (0.2-1).
5. The method according to claim 1, wherein the bifunctional molecular sieve catalyst contains one or more noble metal elements of 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 method of claim 5, wherein the dual function molecular sieve catalyst is prepared by a process comprising the steps of: soaking a titanium-silicon molecular sieve in a solution containing noble metal elements, and carrying out soaking reaction for 1-12 hours at 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 to 10000h -1 。
8. The method of claim 7, wherein the total gas space velocity of the second reaction is 100-5000 h -1 。
9. The method according to claim 1, wherein in step S2, the second reaction is performed 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 one or more selected from methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile.
10. The method of claim 9, wherein the solvent is methanol and/or deionized water.
11. The method of claim 9, wherein the weight ratio of the solvent to the amount of the bifunctional molecular sieve catalyst is (10-1000): 1.
12. the method of claim 11, wherein the weight ratio of the solvent to the amount of the bifunctional molecular sieve catalyst is (20-500): 1.
13. the method of claim 1, wherein the propylene oxide selectivity is 50-100% and the propane conversion is 20-50%.
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