CN102050803B - Olefin epoxidation method - Google Patents
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Abstract
The invention discloses an olefin epoxidation method. The olefin epoxidation method comprises the step of performing epoxidation on the olefin and hydrogen peroxide in the presence of a catalyst, wherein alcohol serves as a solvent; and the catalyst is a titanium silicon molecular sieve and resin composite catalyst. In the olefin epoxidation method, a fixed bed reaction mode is adopted, so the problem that the titanium silicon catalyst powder and the reaction solution are difficult to separate in a slurry reactor in the past is solved, and reaction efficiency is improved.
Description
Technical field
The invention belongs to a kind of olefin epoxidation method, particularly a kind of fixed bed olefin epoxidation method.
Background technology
Since synthetic first lattice oxygen selective oxidation titanium-silicon molecular sieve catalyst TS-1 of Italian Enichem company's nineteen eighty-three, owing to its excellent oxidation selectivity and gentle reaction conditions become the focus that oxide catalyst is studied, this discovery is regarded as a quantum jump of environment-friendly catalyst exploitation.
Titanium-silicon molecular sieve catalyst has important effect aspect the organic compound selective oxidation, uses the hydrogen peroxide preparing epoxypropane by epoxidation as propylene under the titanium-silicon molecular sieve catalyst effect.In industrial application, titanium-silicon molecular sieve catalyst shows the good type of selecting catalytic performance, general particle diameter is more little, catalyst activity is high more, selectivity is good more, the particle diameter of titanium-silicon molecular sieve catalyst is about 0.1-15.0 μ m in the practical application, yet, so little particle diameter can be given catalyzer and bring great difficulty separating of product, though existing various achievements in research about filtering material are applied to reality, but for separating of titanium-silicon molecular sieve catalyst and product, the resistance that produces when it filters does not also lie in the size in the duct of filtering material, and to occupy and stop up duct, the especially particle diameter of formed filter cake the most unfavorable to filtering less than the catalyst particle of 2 μ m but come from superfine little catalyst particle, cause production efficiency low like this, also have influence on the process of HTS industrial applications.The catalyzer of small particle size when filtering except that stopping up the filter cake duct, part then runs off from the duct of filtration medium, general turnover rate is about 5%～8% of catalyzer input amount, not only cause the unnecessary consumption of catalyzer, and enter and cause further side reaction in the product material, cause the increase of separation costs, influence quality product.
Propylene oxide (PO) is important basic petrochemical materials, it is the third-largest kind that output is only second to polypropylene and vinyl cyanide in the acryloyl derivative, be mainly used in and produce polyethers, propylene glycol, Yi Bingchunan, vinyl carbinol etc., and then produce important source material such as unsaturated polyester resin, urethane, tensio-active agent, be widely used in industries such as chemical industry, light industry, medicine, food, weaving.
Present industrial production PO mainly adopts chlorohydrination, indirect oxidation method (conjugated oxidation) and cumene method.The main drawback of chlorohydrination is to use poisonous chlorine, and equipment corrosion is serious and produce the chlorine-contained wastewater of a large amount of contaminate environment, does not meet the requirement of Green Chemistry and cleaner production, and therefore along with the raising day by day of environmental protection requirement, this technology will finally be eliminated; The indirect oxidation method has overcome the shortcoming that the chlorohydrination three-waste pollution is serious, corrode big and demand chlorine resource, but its disadvantage is arranged also, long as technical process, requirement of explosion proof tight, the investment big, to raw material specification require high, operational condition is strict, the byproduct ratio is big etc., 1 ton of propylene oxide of every production has 2.5 tons of trimethyl carbinols or 1.8 tons of vinylbenzene to generate, this far surpasses the output of major product, and the fluctuation of the market demand of byproduct is big, is subjected to market factor restriction serious so produce.Cumene method process using hydrogen phosphide cumene (CHP) is an oxygenant, and this technology has superiority technically and economically, but its essence is still a kind of conjugated oxidation technology.
Drawback in view of the existence of present industrial preparation PO operational path, the investigator is devoted to always that flow process is simple, by product is few and the green Study on clean process for production of feed of the PO of green non-pollution over nearly more than 20 years, each major company of the world is also in the active development new technology and update prior art up to now, wherein HTS (TS-1) catalysis, hydrogen peroxide direct oxidation technology reaches its maturity, and shows excellent industrial application foreground.
CN1256274A has proposed the technology of titanium molecular sieve catalysis propylene, hydrogen peroxide epoxidation continuous production propylene oxide, catalyzer exists with paste-like in this process, though obtained feed stock conversion and product yield preferably, but because catalyzer is a slurry state, need after the reaction from product, to separate, reuse.This has caused technical process loaded down with trivial details, and is unfavorable for large-scale industrial production, and in this process, catalyzer also will have inevitable loss in addition.The TS-1 catalyzing propone of CN1639143A, hydrogen peroxide epoxidation adopt the reactive mode of autoclave, still do not have well to solve the problem of catalyzer and product separation difficulty.
The median size of HTS powder is less, can't be directly used in the commercial fixed bed reactor, must make by forming process have suitable shape, good mechanical strength and greater activity is arranged and catalyzer optionally.So the shaping of catalyst problem becomes the important problem that can HTS be applied to the commercial fixed bed reaction technology.
Summary of the invention
For overcoming the deficiency that prior art exists, the invention provides a kind of adopt fixed-bed reactor, reaction-ure conversion-age height, olefin epoxidation method that target product selectivity is high.
Olefin epoxidation method of the present invention in the presence of catalyzer, is made solvent with alcohol, and alkene and hydrogen peroxide carry out epoxidation reaction, and wherein the catalyzer that is adopted is HTS and resin compounded catalyzer, and the fixed bed reaction mode is adopted in this reaction.
In described HTS and the resin compounded catalyzer, be benchmark with the weight of catalyzer, the content of HTS is 1%～50%, is preferably 10%～25%, and the content of resin is 50%～99%, is preferably 75%～90%.The character of this catalyzer is as follows: specific surface area is 70～260m
2/ g, pore volume are 0.15～0.50cm
3/ g, intensity is 9～20N.mm
-1
Described resin is the polymkeric substance of vinylbenzene and polyene-based compound, and both weight ratios are 2: 1～5: 1.Described polyene-based compound can be one or more in divinylbenzene, divinyl toluene and the biethenyl-xylene, is preferably divinylbenzene.
In the described olefin epoxidation method, raw material olefin refers generally to propylene.Described alcohol is one or more in methyl alcohol, ethanol, propyl alcohol and the trimethyl carbinol, is preferably methyl alcohol.
The operational condition that described olefin epoxidation process adopted is as follows: 40～80 ℃ of temperature of reaction, pressure 1.0～3.0MPa, alkene and H
2O
2Mol ratio be 1: 1～7: 1, alcohol and H
2O
2Mol ratio be that 20: 1～40: 1, liquid phase volume air speed are 5～15h
-1
HTS that the present invention is used and resin compounded catalyzer adopt following method preparation:
With polymerization single polymerization monomer and perforating agent thorough mixing that HTS powder, preparation resin are used, in the presence of initiator, at 60～150 ℃, preferably 80～90 ℃ were carried out polyreaction 3～10 hours, preferably 4～6 hours, obtained the blocks of solid catalyzer; Obtain the catalyst solid particle through fragmentation then, above-mentioned catalyst solid particle is added in the halohydrocarbon after the swelling, adopt the solvent extraction activation, obtain HTS of the present invention and resin compounded catalyzer.
In the inventive method, the add-on of described perforating agent is 30%～60% of HTS powder and the polymerization single polymerization monomer weight used of preparation resin.
In the polymerization single polymerization monomer that described preparation resin is used, a kind of is polymerization single polymerization monomer vinylbenzene, another kind of polymerization single polymerization monomer polyene-based compound, and both weight ratios are 2: 1～5: 1.
Described polymerization single polymerization monomer polyene-based compound can be one or more in divinylbenzene, divinyl toluene and the biethenyl-xylene.
Described perforating agent can be gasoline, C
5～C
13Normal paraffin, C
4～C
12In the Fatty Alcohol(C12-C14 and C12-C18) one or more, preferably C
5～C
13In the normal paraffin one or more.
Described initiator can be benzoyl peroxide and/or azo two isopropylcarbinols, and add-on is 0.5%～2.5% of HTS powder and the polymerization single polymerization monomer weight used of preparation resin.
Described halohydrocarbon can be C
1～C
4Halohydrocarbon in one or more, wherein preferably 1, one or both in 2-ethylene dichloride and the chloroform, described swelling time are 3～8 hours, preferably 5～6 hours.
Described extraction solvent can be one or more in benzene,toluene,xylene, ethyl acetate, butylacetate, ethanol and the butanols etc.Described extractive reaction temperature is 30～60 ℃, preferably 50～60 ℃; The described extracting time is 2～8 hours, preferably 4～6 hours.
Compared with prior art, the inventive method adopts HTS and resin compounded catalyzer, has following characteristics:
1, can adopt the fixed bed reaction mode behind the shaping of catalyst, the catalyzer and the reaction solution that have solved the Ti-Si catalyst powder are difficult to isolating problem, have improved reaction efficiency.
2, in catalytic reaction process because the diluting effect of a large amount of dispersion agents makes HTS exist with isolated form, so the oxidizing reaction heat effect relaxes, can reduce side reaction and take place, improved reaction preference.
3, behind the shaping of catalyst, do not need high temperature (＞500 ℃) roasting to remove the perforating agent that adds in the moulding process, only need low temperature (＜150 ℃) extracting activation, can avoid causing framework of molecular sieve to cave in or titanium detaches skeleton, fully keep the HTS activity.
4, catalyst backbone is water-fast, helps at H
2O
2React in the reaction atmosphere.
Embodiment
Specific surface area and pore volume are to adopt the low temperature liquid nitrogen determination of adsorption method in the inventive method.Intensity is to adopt QCY-602 type catalyst strength determinator to measure.
The concrete preparation process of the inventive method is as follows:
(1), polymerization
In polymeric kettle, add HTS powder, polymerization single polymerization monomer vinylbenzene, polymerization single polymerization monomer polyene-based compound, perforating agent, after mixing, slowly heat up, add initiator when being preferably in 60～90 ℃, under 60～150 ℃, carry out polyreaction 3～10 hours, and obtained block titanium-silicon molecular sieve catalyst.
(2), solvent extraction activation
Above-mentioned block titanium-silicon molecular sieve catalyst is carried out broken granulation, choose the catalyzer that particle diameter is 1 * 1～5 * 5mm after the screening, add halohydrocarbon and carry out swelling, the volume of catalyzer and halohydrocarbon is 1: 10～1: 1, dissolved expanding 3～8 hours, after pouring out halohydrocarbon, add extraction solvent again and carry out extracting, it is that the volume ratio of extraction solvent and catalyzer is 1: 1～5: 1,30～60 ℃ of extractive reaction temperature, 2～6 hours extracting time, extracting number of times 2～5 times obtains HTS of the present invention and resin compounded catalyzer.This catalyzer can directly be packed into and be carried out epoxidation reaction of olefines in the fixed-bed reactor.
The present invention is described in further detail below in conjunction with embodiment; following examples are not limiting the scope of the invention; those skilled in the art is in conjunction with specification sheets of the present invention and can do suitable expansion in full, and these expansions all should be protection scope of the present invention.
Embodiment 1
In polymeric kettle, add HTS powder 7.5g, polymerization single polymerization monomer vinylbenzene 90g and divinylbenzene 30g, perforating agent liquid wax 60g, after mixing, during warming-in-water to 60 ℃, add initiator benzoyl peroxide 1.5g,, obtain block titanium-silicon molecular sieve catalyst 90 ℃ of following polymeric reaction temperatures 6 hours.Carry out broken granulation then, choose the catalyzer of suitable particle diameter after the screening, add 1,2-ethylene dichloride 250ml carries out swelling, dissolved expanding 5 hours.Pour out 1, behind the 2-ethylene dichloride, add ethyl acetate 200ml again and carry out solvent extraction, 55 ℃ of extractive reaction temperature, 4 hours extracting time, carry out three extractings with quadrat method, obtain HTS and resin compounded catalyst A, its physico-chemical property sees Table 1.
Embodiment 2
In polymeric kettle, add HTS powder 15g, polymerization single polymerization monomer vinylbenzene 90g, divinyl toluene 15g, biethenyl-xylene 25g, perforating agent C
5Fatty Alcohol(C12-C14 and C12-C18) 60g after mixing, during warming-in-water to 80 ℃, adds initiator azo two isopropylcarbinol 2.0g, 100 ℃ of following polymeric reaction temperatures 6 hours, obtains block titanium-silicon molecular sieve catalyst.Carry out broken granulation then, choose the catalyzer of suitable particle diameter after the screening, add 1,2-ethylene dichloride 250ml carries out swelling, dissolved expanding 5 hours.Pour out 1, behind the 2-ethylene dichloride, add dimethylbenzene 200ml again and carry out solvent extraction, 55 ℃ of extractive reaction temperature, 4 hours extracting time, carry out three extractings with quadrat method, obtain HTS and resin compounded catalyst B, its physico-chemical property sees Table 1.
Embodiment 3
The weight of HTS powder among the embodiment 1 is become 30g, and extraction solvent is used chloroform instead, and all the other obtain HTS and resin compounded catalyzer C with embodiment 1, and its physico-chemical property sees Table 1.
Embodiment 4
The weight of HTS powder among the embodiment 1 is become 45g, and all the other obtain HTS and resin compounded catalyzer D with embodiment 1, and its physico-chemical property sees Table 1.
Embodiment 5
The weight of HTS powder among the embodiment 1 is become 60g, and all the other obtain HTS and resin compounded catalyzer E with embodiment 1, and its physico-chemical property sees Table 1.
Embodiment 6
The weight of HTS powder among the embodiment 1 is become 75g, and all the other obtain HTS and resin compounded catalyzer F with embodiment 1, and its physico-chemical property sees Table 1.
The physico-chemical property of table 1 catalyzer
| Catalyzer | Specific surface area, m 2.g -1 | Pore volume, ml.g -1 | Intensity, N.mm -1 |
| A | 80.2 | 0.22 | 17.1 |
| B | 97.4 | 0.18 | 15.0 |
| C | 110.9 | 0.24 | 11.2 |
| D | 141.5 | 0.32 | 10.5 |
| E | 175.6 | 0.41 | 9.7 |
| F | 211.7 | 0.25 | 8.3 |
Embodiment 7～12
(particle diameter 2 * 2mm) the 50ml diameter 20mm that packs in the fixed-bed reactor of long 1200mm, carries out epoxidation reaction of olefines, reaction conditions and the results are shown in Table 2 to get the catalyzer of embodiment 1～6.
Table 2 alkene epoxidation operational condition and reaction result
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Catalyzer | A | B | C | D | E | F |
| Raw material | Propylene | Propylene | Propylene | Propylene | Propylene | Propylene |
| Solvent | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol | Methyl alcohol |
| Operational condition | ||||||
| Temperature of reaction, ℃ | 75 | 45 | 45 | 45 | 60 | 40 |
| Pressure, MPa | 1.0 | 15 | 1.5 | 2.5 | 2.5 | 2.5 |
| Volume space velocity during liquid, h -1 | 15 | 10 | 10 | 12 | 12 | 5 |
| Propylene and H 2O 2Mol ratio | 3 | 3 | 5 | 5 | 2 | 2 |
| Methyl alcohol and H 2O 2Mol ratio | 40 | 30 | 30 | 30 | 20 | 30 |
| Reaction result | ||||||
| H 2O 2Transformation efficiency, % (volume fraction) | 99.9 | 98.3 | 98.9 | 98.6 | 99.1 | 99.7 |
| The selectivity of propylene oxide, % (volume fraction) | 93.1 | 92.6 | 97.2 | 99.0 | 95.4 | 94.1 |
By table 2 as seen, adopt the inventive method, H
2O
2Transformation efficiency reach more than 98%, reach more than 92% based on the propylene oxide selectivity of propylene.
Claims (14)
1. an olefin epoxidation method in the presence of catalyzer, is made solvent with alcohol, and alkene and hydrogen peroxide and alcohol carry out epoxidation reaction, and wherein the catalyzer that is adopted is HTS and resin compounded catalyzer, and the fixed bed reaction mode is adopted in this reaction; In described HTS and the resin compounded catalyzer, be benchmark with the weight of catalyzer, the content of HTS is 1%～50%, and the content of resin is 50%～99%, and character is as follows: specific surface area is 70～260m
2/ g, pore volume are 0.15～0.50cm
3/ g, intensity is 9～20N.mm
-1Used HTS and resin compounded catalyzer adopt following method preparation:
Polymerization single polymerization monomer and perforating agent thorough mixing with HTS powder, preparation resin are used in the presence of initiator, carried out polyreaction 3～10 hours at 60～150 ℃, obtained the blocks of solid catalyzer; Obtain the catalyst solid particle through fragmentation then, above-mentioned catalyst solid particle is added in the halohydrocarbon after the swelling, adopt the solvent extraction activation, obtain HTS and resin compounded catalyzer.
2. in accordance with the method for claim 1, it is characterized in that in described HTS and the resin compounded catalyzer, is benchmark with the weight of catalyzer, and the content of HTS is 10%～25%, and the content of resin is 75%～90%.
3. in accordance with the method for claim 1, it is characterized in that described resin is the polymkeric substance of vinylbenzene and polyene-based compound; Described polyene-based compound is one or more in divinylbenzene, divinyl toluene and the biethenyl-xylene.
4. in accordance with the method for claim 3, it is characterized in that in the described resin that the weight ratio of vinylbenzene and polyene-based compound is 2: 1～5: 1.
5. in accordance with the method for claim 3, it is characterized in that described polyene-based compound is a divinylbenzene.
6. in accordance with the method for claim 1, it is characterized in that in the described olefin epoxidation method that raw material olefin is a propylene; Described alcohol is one or more in methyl alcohol, ethanol, propyl alcohol and the trimethyl carbinol.
7. according to claim 1 or 6 described methods, it is characterized in that described alcohol is methyl alcohol.
8. in accordance with the method for claim 1, it is characterized in that the operational condition that described olefin epoxidation process adopts is as follows: 40～80 ℃ of temperature of reaction, pressure 1.0～3.0MPa, alkene and H
2O
2Mol ratio be 1: 1～7: 1, alcohol and H
2O
2Mol ratio be that 20: 1～40: 1, liquid phase volume air speed are 5～15h
-1
9. in accordance with the method for claim 1, the add-on that it is characterized in that described perforating agent is 30%～60% of the polymerization single polymerization monomer weight used of HTS powder and preparation resin.
10. in accordance with the method for claim 1, it is characterized in that a kind of is polymerization single polymerization monomer vinylbenzene in the polymerization single polymerization monomer that described preparation resin uses, another kind of polymerization single polymerization monomer polyene-based compound, both weight ratios are 2: 1～5: 1; Described polymerization single polymerization monomer polyene-based compound is one or more in divinylbenzene, divinyl toluene and the biethenyl-xylene.
11. in accordance with the method for claim 1, it is characterized in that described perforating agent is gasoline, C
5～C
13Normal paraffin, C
4～C
12In the Fatty Alcohol(C12-C14 and C12-C18) one or more.
12. in accordance with the method for claim 1, it is characterized in that described initiator is benzoyl peroxide and/or azo two isopropylcarbinols, add-on is 0.5%～2.5% of HTS powder and the polymerization single polymerization monomer weight used of preparation resin.
13. in accordance with the method for claim 1, it is characterized in that described halohydrocarbon is C
1～C
4Halohydrocarbon in one or more; Described swelling time is 3～8 hours.
14. in accordance with the method for claim 1, it is characterized in that described extraction solvent is one or more in benzene,toluene,xylene, ethyl acetate, butylacetate, ethanol and the butanols; Described extractive reaction temperature is 30～60 ℃; The described extracting time is 2～8 hours.
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| CN 200910188169 CN102050803B (en) | 2009-10-27 | 2009-10-27 | Olefin epoxidation method |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311363B (en) * | 2010-07-07 | 2014-05-21 | 中国石油化工股份有限公司 | Ammoxidation method for cyclohexanone |
| SG189877A1 (en) * | 2010-10-11 | 2013-06-28 | China Petroleum & Chemical | Epoxidation method for olefin |
| CN102952024B (en) * | 2011-08-24 | 2014-05-28 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethanolamine by using one-step ethylene method |
| CN102952003B (en) * | 2011-08-24 | 2015-04-01 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethylene glycol monomethyl ether by using one-step ethylene method |
| CN103012064B (en) * | 2011-09-28 | 2015-03-18 | 中国石油化工股份有限公司 | Method for preparing propylene glycol from propylene |
| CN103121980B (en) * | 2011-11-18 | 2015-09-09 | 中国石油化工股份有限公司 | The method of epoxidation of propylene |
| CN103801406B (en) * | 2012-11-08 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of HTS and the preparation method of resin compounded catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131152A (en) * | 1994-11-16 | 1996-09-18 | 阿克奥化学技术有限公司 | Improved process for titanium silicalite-catalyzed epoxidation |
| CN101291919A (en) * | 2005-10-20 | 2008-10-22 | 利安德化学技术有限公司 | Direct epoxidation process |
-
2009
- 2009-10-27 CN CN 200910188169 patent/CN102050803B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131152A (en) * | 1994-11-16 | 1996-09-18 | 阿克奥化学技术有限公司 | Improved process for titanium silicalite-catalyzed epoxidation |
| CN101291919A (en) * | 2005-10-20 | 2008-10-22 | 利安德化学技术有限公司 | Direct epoxidation process |
Non-Patent Citations (1)
| Title |
|---|
| Sunyoung Park, et al..Epoxidation of Propylene with Hydrogen Peroxide Over TS-1 Catalyst Synthesized in the Presence of Polystyrene.《Catal Lett》.2008,349-353. * |
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