CN101274922A - Preparation for epoxypropane - Google Patents
Preparation for epoxypropane Download PDFInfo
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- CN101274922A CN101274922A CNA2007100649801A CN200710064980A CN101274922A CN 101274922 A CN101274922 A CN 101274922A CN A2007100649801 A CNA2007100649801 A CN A2007100649801A CN 200710064980 A CN200710064980 A CN 200710064980A CN 101274922 A CN101274922 A CN 101274922A
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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
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a method for preparing propylene oxide, which adopts hydrogen peroxide as an oxidizer under the existence of a solvent and prepares propylene oxide through epoxiding propylene. The method of the invention is characterized in that in the method, the active element of catalyst is a Ti-Si molecular sieve with MFI structure, and the crystalline grain of the molecular sieve is hollow in structure; the radial length of the hollow part of the hollow crystalline grain is 5 to 300nm; under the conditions of 25 DEG C, P/P0 being equal to 0.10 and adsorption time being one hour, the adsorptive capacity of the molecular sieve sample tested is at least 70mg/g, and a hysteresis loop exists between the adsorption isotherm and the desorption isotherm absorbed by cryogenic nitrogen of the molecular sieve. The catalyst agent of the method has good stability, and also the method has high selectivity of propylene oxide, high utilization rate of hydrogen peroxide with mild reaction condition and easy operation.
Description
Technical field
The present invention relates to a kind of method for preparing propylene oxide, more specifically to a kind of be the catalytic activity constituent element with the HTS, the method for catalyzing propone and hydrogen peroxide preparing epoxypropane by epoxidation.
Background technology
Propylene oxide (propylene oxide, be called for short PO), it is a kind of important basic Organic Chemicals, output is only second to polypropylene and vinyl cyanide in acryloyl derivative, maximum purposes is to produce polyether glycol, with further processing and manufacturing urethane, also can be used for producing broad-spectrum propylene glycol.In addition, propylene oxide also can be used for producing tensio-active agent, oil field emulsion splitter etc.
Along with the widespread use of polyurethane material and unsaturated polyester, the demand of propylene oxide is rising year by year.At present, industrial production propylene oxide is mainly based on chlorohydrination and common oxygen method.Wherein chlorohydrination is the method that extensively adopts.Though chlorohydrination technology is simple, the yield height, reduced investment, flexible operation, producing a large amount of waste water in the production process is its maximum shortcoming.
As can be seen, existing technology of producing propylene oxide exists drawback, does not especially meet the requirement of Green Chemistry chemical industry.Therefore, people press for the promptly economic and environment amenable again production method of exploitation.
The oxidation of the partial oxidation of the hydroxylation that is found to be alkene epoxidation, benzene and phenol of HTS, hexamethylene ketonize, alkane, alcohol etc. opens up a new way, and particularly aspect alkene epoxidation, has obtained good catalyzed oxidation effect.Be that oxygenant, methyl alcohol are in the reaction system of solvent with the hydrogen peroxide, HTS has advantages of high catalytic activity to propylene, but the propylene oxide that generates is easy to the open loop side reaction further takes place under the effect of catalyzer, thereby greatly reduces the selectivity of propylene oxide.
In order to improve the selectivity of propylene oxide, in propylene ring oxidation reaction, add the organic compound that contains basic group come in and the acid site on the HTS can improve the selectivity (referring to EP0940393, CN1156463C) of propylene oxide.CN1062864C has disclosed a kind of certain density non-basic salt that adds in reaction system, as lithium chloride, SODIUMNITRATE, vitriolate of tartar and primary ammonium phosphate etc., improve optionally method of propylene oxide to improve.Though aforesaid method can improve the selectivity of propylene oxide to a certain extent, propylene oxide optionally improves the cost that is reduced to that is with the hydrogen peroxide utilization ratio.
Adopt metal salt solution pre-processing titanium si molecular sieves (referring to CN1555923A) to be used for propylene ring oxidation reaction, though the utilization ratio that can improve hydrogen peroxide can also improve the selectivity of propylene oxide, but along with the prolongation in reaction times, the selectivity of propylene oxide reduces gradually.Therefore, exist the problem of less stable through pretreated catalyzer.
In sum, in the technology of existing industrial production propylene oxide, exist environmental pollution, do not meet the requirement that contemporary green chemical industry is produced; And in the technology with titanium molecular sieve catalysis propylene and hydrogen peroxide epoxidation production propylene oxide of report, though solved the chlorohydrination environmental pollution problems, but it is lower to exist purpose product propylene oxide selectivity, when perhaps the propylene oxide selectivity improves, but exist the problem of poor catalyst stability.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method of production propylene oxide of environmental protection is provided, catalyst system therefor does not need the modification pre-treatment or need not add inhibitor in reaction system, and the selectivity height and the catalyst stability of purpose product propylene oxide are better.
The method for preparing propylene oxide provided by the invention, be in the presence of solvent, to be oxygenant with the hydrogen peroxide, preparing epoxypropane by epoxidation of propene, it is characterized in that the activity of such catalysts constituent element that adopts is a kind of HTS of the MFI of having structure, its crystal grain is hollow structure, the radical length of the cavity part of this hollow crystal grain is 5～300nm, and this sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under the condition of adsorption time 1h is 70mg/g at least, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of molecular sieve and the desorption isotherm.
In the method provided by the invention, the MFI structure titanium silicon molecular sieve that said crystal grain has hollow structure has had public publish in CN1301599A.
In the method provided by the invention, said solvent is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol or acetone etc., and particular methanol is a solvent.
The reaction process of method provided by the invention can realize according to following A, B dual mode:
A, be reflected at intermittently on tank reactor or the slurry bed reactor and carry out, with former powdery HTS is catalyzer, its advantage is that molecular sieve needn't can use in moulding, preferred reaction conditions is to contain 0.001～0.01g molecular sieve in every milliliter of reaction solution, the mol ratio of solvent and hydrogen peroxide is 10～50, temperature is at 20～35 ℃, and pressure is 0.4～2.0MPa, 10～30 minutes reaction times.
B, be reflected on the fixed-bed reactor and carry out, the HTS that employing has after certain particle diameter, the moulding is a catalyzer, its advantage is, reaction product need not adopt extra separation circuit, the mol ratio that preferred reaction conditions is propylene and hydrogen peroxide is 1.0～4.0, the mol ratio of solvent and propylene is 20～100, and total liquid feeding volume space velocity is at 1.0～30.0h
-1, pressure is 0.4～2.0MPa, temperature is 20～60 ℃.Titanium-silicon molecular sieve catalyst after the said moulding is former powder of HTS and tackiness agent, mixes obtaining as silicon sol, aluminium colloidal sol, and preferred silicon sol is the tackiness agent of shaping of catalyst.
The method for preparing propylene oxide provided by the invention has good hydrogen peroxide utilization ratio, higher propylene oxide selectivity, and catalyst life is stable.With respect to traditional method, problems such as traditional processing technology complexity, equipment corrosion and noxious emission have been overcome; Solved to add inhibitor in HTS (TS-1) the catalytic epoxidation of propone reaction system, though the propylene oxide selectivity is higher, the problem that the hydrogen peroxide utilization ratio is lower; Though and the pre-processing titanium si molecular sieves the two all can take into account the problem that catalyst life is short.
Embodiment
By the following examples the present invention is further described, but content not thereby limiting the invention.
New titanium-silicone molecular sieve used among the embodiment is built the production of long company for the Sinopec Hunan, and trade names are HTS, are the Industrial products of the described HTS of Chinese patent CN1301599A.The HTS that Comparative Examples adopted (TS-1) is according to document Thangaraj A, Kumar R, Mirajkar S P, et al.[J]] .J.Catal.1991,130 (1): 1～8 described method preparation.
The analytical procedure of reaction product:
(1) organic constituent content in the gc analysis product is that internal standard substance carries out quantitative analysis calculating with the methyl tertiary butyl ether.Wherein chromatographiccondition is: Agilent-6890 type chromatographic instrument, 30m * 0.25mmFFAP capillary column, sample size 1.0uL, 180 ℃ of injector temperatures.Column temperature keeps 4min at 60 ℃, and then the speed with 20 ℃/min rises to 200 ℃, and keeps 4min.Fid detector, 240 ℃ of sensing chamber's temperature.
(2) concentration of hydrogen peroxide before and after iodimetric analysis reacts indirectly.
Activity of such catalysts is that the transformation efficiency with hydrogen peroxide is that index is investigated.
Comparative Examples 1
In this Comparative Examples explanation tank reactor, with the process of conventional TS-1 titanium molecular sieve catalysis epoxidation reaction.
Take by weighing the conventional former powder of HTS (TS-1) of 0.5g and the methyl alcohol of 60g and the mixed solution (wherein the mol ratio of methyl alcohol and hydrogen peroxide is 20: 1) of hydrogen peroxide respectively, place the stainless steel autoclave reactor after Passivation Treatment.Air in the logical nitrogen replacement reactor, and guarantee that entire reaction system stopping property is intact, switch to propylene feed then.System pressure maintains 0.8MPa, and temperature of reaction is controlled to be 30 ℃.Behind the reaction 30min, place ice-water bath with termination reaction reactor rapidly.When treating that temperature in the kettle is reduced to below 15 ℃, open the still sampling, get supernatant liquor after the centrifugation and analyze its reaction product composition.Analytical results is: the transformation efficiency of hydrogen peroxide is 92.6%, and the selectivity of propylene oxide is 71.3%.
Comparative Examples 2
The explanation of this Comparative Examples is to carry out the process of epoxidation reaction behind the metal salt solution pre-processing titanium si molecular sieves.
The sodium sulfate of 2.0g is dissolved in the deionized water of 200mL, and the TS-1 molecular sieve of adding 5g. then under 40 ℃, magnetic agitation 5h, filtration washing, dry 2h in 120 ℃ of baking ovens again, with the mode of dried sample with temperature programming, 3h rises to 550 ℃ gradually by room temperature, roasting 5h in this temperature, air atmosphere makes the pretreated TS-1 sieve sample of modification then.According to comparative example's 1 described method, investigate the performance of its catalytic epoxidation of propone.The reaction product analytical results is: the transformation efficiency of hydrogen peroxide is 85.2%, and the selectivity of propylene oxide is 81.3%.
Embodiment 1
Take by weighing the methyl alcohol of former powder of 0.5g new titanium-silicone molecular sieve (HTS) and 60g and the mixed solution of hydrogen peroxide (wherein the mol ratio of methyl alcohol and hydrogen peroxide is 20: 1) respectively, place the stainless steel autoclave reactor after Passivation Treatment.Air in the logical nitrogen replacement reactor, and guarantee that entire reaction system stopping property is intact, switch to propylene feed then.System pressure maintains 0.8MPa, and temperature of reaction is controlled to be 30 ℃.Behind the reaction 0.5h, place ice-water bath with termination reaction reactor rapidly.When treating that temperature in the kettle is reduced to below 15 ℃, open the still sampling, get supernatant liquor after the centrifugation and analyze its reaction product composition.Analytical results is: the transformation efficiency of hydrogen peroxide is 98.6%, and the selectivity of propylene oxide is 75.3%.
Embodiment 2
Take by weighing the methyl alcohol of former powder of 1.0g new titanium-silicone molecular sieve (HTS) and 60g and the mixed solution of hydrogen peroxide (wherein the mol ratio of methyl alcohol and hydrogen peroxide is 40: 1), place the stainless steel autoclave reactor after Passivation Treatment.Air in the logical nitrogen replacement reactor, and guarantee that entire reaction system stopping property is intact, switch to propylene feed then.System pressure maintains 0.8MPa, and temperature of reaction is controlled to be 20 ℃.Behind the reaction 0.3h, place ice-water bath with termination reaction reactor rapidly.When treating that temperature in the kettle is reduced to below 15 ℃, open the still sampling, get supernatant liquor after the centrifugation and analyze its reaction product composition.Analytical results is: the transformation efficiency of hydrogen peroxide is 98.2%, and the selectivity of propylene oxide is 85.1%.
Comparative Examples 3
In this Comparative Examples explanation fixed-bed reactor, with the process of conventional TS-1 titanium molecular sieve catalysis epoxidation reaction.
(massfraction of HTS is 70% in the catalyzer to take by weighing conventional HTS (TS-1) catalyzer of 3.0g extruded moulding, with the silicon sol is binding agent), and add certain quartz sand and dilute, place the isothermal reaction district of fixed-bed tube reactor then, guarantee that entire reaction system stopping property is intact.System pressure maintains 0.6MPa, and temperature of reaction is controlled to be 30 ℃.Propylene and liquid phase feed (containing internal standard substance, hydrogen peroxide in methanol) adopt and the mode of the following charging of stream enters reaction zone, and its mass space velocity is 15h
-1, the mol ratio of propylene and hydrogen peroxide is 2: 1, the mol ratio of methyl alcohol and hydrogen peroxide is 20: 1.After question response is stablized 1 hour, the sampling analysis reaction product.The utilization ratio that obtains hydrogen peroxide is 95.6%, and the selectivity of propylene oxide is 71.3%.
Embodiment 3
According to Comparative Examples 3 described evaluation methods, under identical experiment condition, investigated the catalytic performance of moulding HTS molecular sieve catalyst (massfraction of HTS molecular sieve is 70%, is binding agent with the silicon sol).After question response is stablized 1 hour, the sampling analysis reaction product.The utilization ratio that obtains hydrogen peroxide is 96.6%, and the selectivity of propylene oxide is 72.5%.
Comparative Examples 4
The explanation of this Comparative Examples is in fixed-bed reactor, to carry out the process of epoxidation reaction behind the metal salt solution pre-processing titanium si molecular sieves.
With Comparative Examples 2 described method modifications pretreated TS-1 sample extruded mouldings (massfraction of TS-1 molecular sieve is 70% in the catalyzer).Take by weighing 3.0g modification TS-1 catalyzer, and add certain quartz sand and dilute, place the isothermal reaction district of fixed-bed tube reactor then, guarantee that entire reaction system stopping property is intact.System pressure maintains 0.6MPa, and temperature of reaction is controlled to be 30 ℃.Propylene and liquid phase feed (containing internal standard substance, hydrogen peroxide in methanol) adopt and the mode of the following charging of stream enters reaction zone, and its mass space velocity is 15h
-1, the mol ratio of propylene and hydrogen peroxide is 2: 1, the mol ratio of methyl alcohol and hydrogen peroxide is 20: 1.Behind the stable reaction 1h, the effective rate of utilization of hydrogen peroxide is 90%, and the selectivity of propylene oxide is 98.6%, and still along with the prolongation in reaction times, the selectivity of propylene oxide is tending towards descending; After 30h was carried out in reaction, the selectivity of propylene oxide reduced to 78.2%, and the utilization ratio of hydrogen peroxide rises to 95%.
Embodiment 4
According to Comparative Examples 4 described evaluation methods, under identical experiment condition, investigated the catalytic stability of moulding HTS molecular sieve catalyst (massfraction of HTS molecular sieve is 70%, is binding agent with the silicon sol).After the stable reaction 1 hour, the effective rate of utilization of hydrogen peroxide is 95.5%, and the selectivity of propylene oxide is 75.5%; After 30h is carried out in reaction, the sampling analysis reaction product, the utilization ratio that obtains hydrogen peroxide is 98.6%, the selectivity of propylene oxide is 75.3%.
Embodiment 5
(massfraction of HTS is 70% in the catalyzer to take by weighing conventional HTS (HTS) catalyzer of 3.0g extruded moulding, with the silicon sol is binding agent), and add certain quartz sand and dilute, place the isothermal reaction district of fixed-bed tube reactor then, guarantee that entire reaction system stopping property is intact.System pressure maintains 0.6MPa, and temperature of reaction is controlled to be 30 ℃.Propylene and liquid phase feed (containing internal standard substance, hydrogen peroxide in methanol) adopt and the mode of the following charging of stream enters reaction zone, and its mass space velocity is 25h
-1, the mol ratio of propylene and hydrogen peroxide is 2: 1, the mol ratio of methyl alcohol and hydrogen peroxide is 20: 1.Initial period after the stable reaction, the effective rate of utilization of hydrogen peroxide are 98.5%, and the selectivity of propylene oxide is 79.5%; After 30h is carried out in reaction, the sampling analysis reaction product, the utilization ratio that obtains hydrogen peroxide is 99.5%, the selectivity of propylene oxide is 80.3%.
Claims (9)
1. method for preparing propylene oxide, be in the presence of solvent, to be oxygenant with the hydrogen peroxide, preparing epoxypropane by epoxidation of propene, it is characterized in that in this method, the activity of such catalysts constituent element is a kind of HTS of the MFI of having structure, its crystal grain is hollow structure, and the radical length of the cavity part of this hollow crystal grain is 5～300nm, and this sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under the condition of adsorption time 1h is 70mg/g at least, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of molecular sieve and the desorption isotherm.
2. according to the method for claim 1, it is characterized in that said solvent is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol or acetone.
3. according to the method for claim 1, it is characterized in that said solvent is a methyl alcohol.
4. according to the method for claim 1, it is characterized in that being reflected at intermittently on tank reactor or the slurry bed reactor and carrying out, said catalyzer is the former powder of HTS.
5. according to the method for claim 4, it is characterized in that reaction conditions is to contain 0.001～0.01g molecular sieve in every milliliter of reaction solution, the mol ratio of solvent and hydrogen peroxide is 10～50, and temperature is at 20～35 ℃, pressure is 0.4～2.0MPa, reaction times 10～30min.
6. according to the method for claim 1, it is characterized in that being reflected in the fixed-bed reactor and carry out, said catalyzer is the HTS of moulding, by the former powder of HTS with obtain after tackiness agent mixes.
7. according to the method for claim 6, it is characterized in that said tackiness agent is silicon sol and/or aluminium colloidal sol.
8. according to the method for claim 7, said tackiness agent is a silicon sol.
9. according to the method for claim 6, it is characterized in that the fixed bed reaction condition is that the mol ratio of propylene and hydrogen peroxide is 1.0～4.0, the mol ratio of solvent and propylene is 20～100, total liquid feeding volume space velocity is at 1.0～30.0h
-1, pressure is 0.4～2.0MPa, temperature is 20～60 ℃.
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| CN1132699C (en) * | 1999-12-24 | 2003-12-31 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
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Correction item: Patentee|Address|Co-patentee Correct: Sinopec Corp.|100029 Beijing City, Chaoyang District Hui Street No. 6|SINOPEC Research Institute of Petroleum Processin False: SINOPEC Research Institute of Petroleum Processin|100083 No. 18, Haidian District, Beijing, Xueyuan Road Number: 03 Volume: 27 |
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Correction item: Patentee|Address|Co-patentee Correct: Sinopec Corp.|100029 Beijing City, Chaoyang District Hui Street No. 6|SINOPEC Research Institute of Petroleum Processin False: SINOPEC Research Institute of Petroleum Processin|100083 No. 18, Haidian District, Beijing, Xueyuan Road Number: 03 Page: The title page Volume: 27 |
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Free format text: CORRECT: PATENTEE; ADDRESS; CO-PATENTEE; FROM: SINOPEC CORP. RESEARCH INSTITUTE OF PETROLEUM PROCESSING;100083 NO. 18, XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING TO: CHINA PETROCHEMICAL CO., LTD.;100029 NO. 6-A, HUIXIN EAST STREET, CHAOYANG DISTRICT, BEIJING; SINOPEC CORP. RESEARCH INSTITUTE OF PETROLEUM PROCESSING |