CN102049304A - Titanium-silicon molecular sieve and resin composite catalyst and preparation method thereof - Google Patents
Titanium-silicon molecular sieve and resin composite catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN102049304A CN102049304A CN2009101881617A CN200910188161A CN102049304A CN 102049304 A CN102049304 A CN 102049304A CN 2009101881617 A CN2009101881617 A CN 2009101881617A CN 200910188161 A CN200910188161 A CN 200910188161A CN 102049304 A CN102049304 A CN 102049304A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- accordance
- resin
- hts
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Epoxy Compounds (AREA)
Abstract
The invention discloses a titanium-silicon molecular sieve and resin composite catalyst and a preparation method thereof. The catalyst mainly comprises a titanium-silicon molecular sieve and resin. The preparation method comprises the following steps of: fully mixing titanium-silicon molecular sieve powder, a polymeric monomer and a porogen, performing polymerization reaction in the presence of an initiator to obtain a blocky solid catalyst, crushing, adding into halogenated hydrocarbon for swelling, and performing solvent extraction to obtain a formed catalyst. The catalyst prepared by the method solves the problem that titanium-silicon catalyst powder and reaction liquid are difficult to separate, improves reaction efficiency, is applied to the catalytic reaction process of olefin epoxidation in a fixed bed process, and has good catalytic effect.
Description
Technical field
The invention belongs to a kind of HTS and resin compounded Catalysts and its preparation method, be suitable in the fixed bed catalyst process of epoxidation etc. of alkene.
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 condition become the focus that oxidation 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 commercial 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 catalyst 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 catalyst of small particle diameter when filtering except that stopping up the filter cake duct, part then runs off from the duct of filter medium, general turnover rate is about 5%～8% of catalyst input amount, not only cause the unnecessary consumption of catalyst, and enter and cause further side reaction in the product material, cause the increase of separation costs, influence product quality.
Expoxy propane (PO) is important basic petrochemical materials, it is the third-largest kind that output is only second to polypropylene and acrylonitrile in the acryloyl derivative, be mainly used in and produce polyethers, propane diols, isopropanolamine, allyl alcohol etc., and then produce important source material such as unsaturated polyester resin, polyurethane, surfactant, 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 major defect of chlorohydrination is to use poisonous chlorine, and equipment corrosion is serious and produce the chlorine-contained wastewater of a large amount of contaminated 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 technological process, requirement of explosion proof tight, the investment big, to raw material specification require high, operating condition is strict, the byproduct ratio is big etc., 1 ton of expoxy propane of every production has 2.5 tons of tert-butyl alcohols or 1.8 tons of styrene 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 oxidant, 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 process route, the researcher is devoted to always that flow process is simple, accessory substance 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 that titanium molecular sieve catalysis propylene, hydrogen peroxide epoxidation are produced expoxy propane continuously, catalyst exists with paste-like in this process, though obtained feed stock conversion and product yield preferably, but because catalyst is a slurry state, need after the reaction from product, to separate, reuse.This has caused technological process loaded down with trivial details, and is unfavorable for large-scale industrial production, and in this process, catalyst 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 the separation difficulty of catalyst and product.
The average grain diameter of HTS powder is less, can't be directly used in the commercial fixed bed reactor, must make by processing and forming have suitable shape, good mechanical strength and greater activity is arranged and catalyst 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 be used for fixing bed bioreactor, active good HTS and resin compounded Catalysts and its preparation method.
HTS of the present invention and resin compounded catalyst are benchmark with the weight of catalyst, and 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 catalyst is as follows: specific area is 70～260m
2/ g, pore volume are 0.15～0.50cm
3/ g, intensity is 9～20N.mm
-1Described resin is the polymer of styrene 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.
HTS of the present invention and resin compounded Preparation of catalysts method comprise:
Polymerization single polymerization monomer and perforating agent that HTS powder, preparation resin are used fully mix, and in the presence of initator, at 60～150 ℃, preferably 80～90 ℃ were carried out polymerisation 3～10 hours, preferably 4～6 hours, obtained the blocks of solid catalyst; Obtain the catalyst solid particle through fragmentation then, above-mentioned catalyst solid particle is added in the halogenated hydrocarbons after the swelling, adopt solvent extraction, obtain HTS of the present invention and resin compounded catalyst.
In the inventive method, the addition 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 styrene, 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 styrene, divinylbenzene, divinyl toluene, the biethenyl-xylene.
Described perforating agent can be gasoline, C
5～C
13N-alkane, C
4～C
12In the fatty alcohol one or more, preferably C
5～C
13In the n-alkane one or more.
Described initator can be benzoyl peroxide and/or azo two isobutanols, and addition is 0.5%～2.5% of HTS powder and the polymerization single polymerization monomer weight used of preparation resin.
Described halogenated hydrocarbons can be C
1～C
4Halogenated hydrocarbons, wherein preferably 1, one or both in 2-dichloroethanes 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, butyl acetate, ethanol, 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.
The catalyst that the inventive method obtains is applied in the catalytic reaction process of alkene epoxidation of fixed-bed process, the catalytic effect excellence.
Compared with prior art, catalyst of the present invention has following characteristics:
1, can adopt the fixed bed reaction mode behind the shaping of catalyst, solve the catalyst and the problem that reactant liquor is difficult to separate of Ti-Si catalyst powder, improve reaction efficiency.
2, in catalytic reaction process because the diluting effect of a large amount of dispersants makes HTS exist with the form of isolating, so the oxidation reaction fuel factor relaxes, can reduce side reaction and take place, improved reaction selectivity.
3, behind the shaping of catalyst, do not need high temperature (＞500 ℃) roasting to remove the perforating agent that adds in the forming 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.
The specific embodiment
Specific 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 analyzer 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 styrene, polymerization single polymerization monomer polyene-based compound, perforating agent, after mixing, warming-in-water, add initator when being preferably in 60～90 ℃, under 60～150 ℃, carry out polymerisation 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 catalyst that particle diameter is 1 * 1～5 * 5mm after the screening, add halogenated hydrocarbons and carry out swelling, the volume of catalyst and halogenated hydrocarbons is 1: 10～1: 1, dissolved expanding 3～8 hours, after pouring out halogenated hydrocarbons, add extraction solvent again and carry out extracting, it is that the volume ratio of extraction solvent and catalyst 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 catalyst.This catalyst can directly be packed into and be carried out the epoxidised catalytic reaction of alkene in the fixed bed reactors.
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 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 styrene 90g and divinylbenzene 30g, perforating agent liquid wax 60g, after mixing, during warming-in-water to 60 ℃, add initator 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 catalyst of suitable particle diameter after the screening, add 1,2-dichloroethanes 250ml carries out swelling, dissolved expanding 5 hours.Pour out 1, behind the 2-dichloroethanes, 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 styrene 90g, divinyl toluene 15g, biethenyl-xylene 25g, perforating agent C
5Fatty alcohol 60g after mixing, during warming-in-water to 80 ℃, adds initator azo two isobutanol 2.0g, 100 ℃ of following polymeric reaction temperatures 6 hours, obtains block titanium-silicon molecular sieve catalyst.Carry out broken granulation then, choose the catalyst of suitable particle diameter after the screening, add 1,2-dichloroethanes 250ml carries out swelling, dissolved expanding 5 hours.Pour out 1, behind the 2-dichloroethanes, 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 catalyst 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 catalyst 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 catalyst 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 catalyst F with embodiment 1, and its physico-chemical property sees Table 1.
The physico-chemical property of table 1 catalyst
| Catalyst | Specific 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
(particle diameter 2 * 2mm) the 50ml diameter 20mm that packs in the fixed bed reactors of long 1200mm, carries out propylene ring oxidation reaction, at 50 ℃ of reaction temperatures, pressure 2.5MPa, propylene and H to get the catalyst B of embodiment 2
2O
2Mol ratio be 5: 1, methyl alcohol and H
2O
2Mol ratio be that 30: 1, reactant liquor phase volume air speed are 10h
-1Condition under, H
2O
2Conversion ratio can reach 99.5%, the selectivity of expoxy propane＞99.5%.
Claims (17)
1. HTS and resin compounded catalyst are benchmark with the weight of catalyst, and the content of HTS is 1%～50%, and the content of resin is 50%～99%; The character of this catalyst is as follows: specific area is 70～260m
2/ g, pore volume are 0.15～0.50cm
3/ g, intensity is 9～20N.mm
-1
2. according to the described catalyst of claim 1, it is characterized in that the weight with catalyst is benchmark, the content of HTS is 10%～25%, and the content of resin is 75%～90%.
3. according to the described catalyst of claim 1, it is characterized in that described resin is the polymer of styrene and polyene-based compound, the polyene-based compound is one or more in divinylbenzene, divinyl toluene and the biethenyl-xylene.
4. according to the described catalyst of claim 3, it is characterized in that described polyene-based compound is a divinylbenzene.
5. according to the described catalyst of claim 3, it is characterized in that in the described resin that the weight ratio of styrene and polyene-based compound is 2: 1～5: 1.
6. arbitrary described HTS of claim 1～5 and resin compounded Preparation of catalysts method comprise:
Polymerization single polymerization monomer and perforating agent that HTS powder, preparation resin are used fully mix, and in the presence of initator, carry out polymerisation 3～10 hours at 60～150 ℃, obtain the blocks of solid catalyst; Obtain the catalyst solid particle through fragmentation then, above-mentioned catalyst solid particle is added in the halogenated hydrocarbons after the swelling, adopt solvent extraction, obtain titanium-silicon molecular sieve catalyst.
7. in accordance with the method for claim 6, the addition 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.
8. in accordance with the method for claim 6, it is characterized in that described polymeric reaction temperature is 80～90 ℃, the reaction time is 4～6 hours.
9. in accordance with the method for claim 6, it is characterized in that described perforating agent is gasoline, C
5～C
13N-alkane, C
4～C
12In the fatty alcohol one or more.
10. in accordance with the method for claim 6, it is characterized in that described perforating agent is C
5～C
13In the n-alkane one or more.
11. in accordance with the method for claim 6, it is characterized in that described initator is benzoyl peroxide and/or azo two isobutanols, addition is 0.5%～2.5% of HTS powder and the polymerization single polymerization monomer weight used of preparation resin.
12. in accordance with the method for claim 6, it is characterized in that described halogenated hydrocarbons is C
1～C
4Halogenated hydrocarbons, the volume of described catalyst and halogenated hydrocarbons is 1: 10～1: 1, described swelling time is 3～8 hours.
13. in accordance with the method for claim 6, it is characterized in that described halogenated hydrocarbons is 1, one or both in 2-dichloroethanes and the chloroform, the volume of described catalyst and halogenated hydrocarbons are 1: 10～1: 1, and described swelling time is 5～6 hours.
14. in accordance with the method for claim 6, it is characterized in that described extraction solvent is one or more in benzene,toluene,xylene, ethyl acetate, butyl acetate, ethanol, the butanols etc., the volume ratio of described extraction solvent and catalyst is 1: 1～5: 1.
15. in accordance with the method for claim 6, it is characterized in that described extractive reaction temperature is 30～60 ℃; The described extracting time is 2～8 hours, and the extracting number of times is 2～5 times.
16. in accordance with the method for claim 6, it is characterized in that described extractive reaction temperature is 50～60 ℃; The described extracting time is 4～6 hours, and the extracting number of times is 2～5 times.
17. in accordance with the method for claim 6, it is characterized in that the temperature in the described initator adding system is 60～90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910188161A CN102049304B (en) | 2009-10-27 | 2009-10-27 | Titanium-silicon molecular sieve and resin composite catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910188161A CN102049304B (en) | 2009-10-27 | 2009-10-27 | Titanium-silicon molecular sieve and resin composite catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102049304A true CN102049304A (en) | 2011-05-11 |
| CN102049304B CN102049304B (en) | 2012-09-12 |
Family
ID=43954298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910188161A Active CN102049304B (en) | 2009-10-27 | 2009-10-27 | Titanium-silicon molecular sieve and resin composite catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102049304B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012003708A1 (en) * | 2010-07-07 | 2012-01-12 | 中国石油化工股份有限公司 | Composite catalyst of ti-si molecular sieve and resin, preparation method and application thereof |
| CN103801405A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method for titanium silicon molecular sieve catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095464C (en) * | 1998-12-09 | 2002-12-04 | 中国石油化工集团公司 | Technological process of oxidizing propylene with hydrogen peroxide solution to produce epoxy propane continuously |
| CN1114495C (en) * | 2001-09-13 | 2003-07-16 | 大连理工大学 | Process for preparing composite catalyst and its application |
| US6958405B2 (en) * | 2004-03-09 | 2005-10-25 | Arco Chemical Technology, L.P. | Polymer-encapsulated titanium zeolites for oxidation reactions |
| CN101371989B (en) * | 2007-08-22 | 2010-09-22 | 中国石油化工股份有限公司 | Titanium silicon molecular sieve catalyst as well as preparation method and use thereof |
-
2009
- 2009-10-27 CN CN200910188161A patent/CN102049304B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012003708A1 (en) * | 2010-07-07 | 2012-01-12 | 中国石油化工股份有限公司 | Composite catalyst of ti-si molecular sieve and resin, preparation method and application thereof |
| CN103801405A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method for titanium silicon molecular sieve catalyst |
| CN103801405B (en) * | 2012-11-08 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of preparation method of titanium-silicon molecular sieve catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102049304B (en) | 2012-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102050803B (en) | Olefin epoxidation method | |
| CN105503811B (en) | The method for preparing ethylene carbonate | |
| CN103121987B (en) | Method for preparing alkylene carbonate | |
| CN103122045B (en) | Nano composite quaternary phosphonium salt resin | |
| CN102451763B (en) | Titanium-silicon molecular sieve compound catalyst and preparation method thereof | |
| WO2012003708A1 (en) | Composite catalyst of ti-si molecular sieve and resin, preparation method and application thereof | |
| CN103864549B (en) | Method for preparing diphenyl ketone compound | |
| CN102755910B (en) | Titanium silicon molecular sieve and resin composite modified catalyst and preparation method thereof | |
| CN102049304B (en) | Titanium-silicon molecular sieve and resin composite catalyst and preparation method thereof | |
| CN102757407B (en) | Allyl chloride epoxidation method for preparing epichlorohydrin | |
| CN105440007B (en) | The method of synthesizing ethylene carbonate | |
| CN102049305B (en) | Method for preparing titanium silicon molecular sieve catalyst | |
| CN103028440A (en) | Macroporous resin catalyst for preparing alkyl carbonate | |
| CN102757406B (en) | Styrene epoxidation method for preparing styrene oxide | |
| CN102452900B (en) | Method for preparing ethylene glycol from ethylene | |
| CN105111044A (en) | Method for synthesizing isopentenol from butenol | |
| CN103012079A (en) | Method for synthesizing ethylene glycol allyl ether under catalysis of solid base catalyst | |
| CN102451757B (en) | Method for preparing propylene glycol monomethyl ether by using propylene | |
| CN105085187B (en) | The method of preparing ethyl glycol by hydrolysis of ethylene carbonate | |
| CN105503529B (en) | Method for preparing ethyl glycol by hydrolysis of ethylene carbonate | |
| CN105503528B (en) | The method that ethylene carbonate ester hydrolysis produces ethylene glycol | |
| CN103801405B (en) | A kind of preparation method of titanium-silicon molecular sieve catalyst | |
| CN106565481A (en) | Method for preparing diphenyl carbonate | |
| CN109225349B (en) | Preparation method of catalyst for preparing isobutene by cracking methyl tert-butyl ether | |
| CN108057458A (en) | It is a kind of for catalyst of synthesizing methyl tertbutyl ether and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |