CN102049305B - Method for preparing titanium silicon molecular sieve catalyst - Google Patents
Method for preparing titanium silicon molecular sieve catalyst Download PDFInfo
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- CN102049305B CN102049305B CN200910188162A CN200910188162A CN102049305B CN 102049305 B CN102049305 B CN 102049305B CN 200910188162 A CN200910188162 A CN 200910188162A CN 200910188162 A CN200910188162 A CN 200910188162A CN 102049305 B CN102049305 B CN 102049305B
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Abstract
The invention discloses a method for preparing a titanium silicon molecular sieve catalyst. The method comprises the following steps of: mixing titanium silicon molecular sieve powder, polymer monomer styrene, a polymer monomer multi-alkenyl compound and a pore-forming agent completely; in the presence of an initiator, performing a polymerization reaction; smashing the obtained blocky solid catalyst; adding the smashed catalyst into halohydrocarbon to swell; and performing extraction by using a solvent to obtain the formed titanium silicon molecular sieve catalyst. The titanium silicon molecular sieve catalyst prepared by the method solves the problem that the titanium silicon catalyst powder and reaction solution are difficult to separate and improves the reaction efficiency. The titanium silicon molecular sieve catalyst is applied to a catalytic reaction of alkene epoxidation of a fixed bed process and has excellent catalytic effect.
Description
Technical field
The invention belongs to a kind of preparation method of titanium-silicon molecular sieve catalyst, be suitable in the catalytic reaction processes such as epoxidation 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, under the titanium-silicon molecular sieve catalyst effect, uses the hydrogen peroxide preparing epoxypropane by epoxidation like propylene.In commercial Application, titanium-silicon molecular sieve catalyst shows the good type of selecting catalytic performance, and general particle diameter is more little; Catalyst activity is high more, and selectivity is good more, and 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 causes the unnecessary consumption of catalyst, and causes further side reaction in the entering 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.
Industry is at present gone up production PO and is mainly adopted 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, so 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 like 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, receives 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.
In view of the drawback that preparation PO process route exists is gone up in industry at present; 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 solution 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 from product, separate after the reaction, reuse.This has caused technological process loaded down with trivial details, and is unfavorable for large-scale commercial production, and in this process, catalyst also will have inevitable loss in addition.The TS-1 catalyzing propone of CN1639143A, hydrogen peroxide solution 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 directly be used for the commercial fixed bed reactor, must process through 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 preparation method who is used for fixing titanium-silicon molecular sieve catalyst bed bioreactor, that activity is good.
The preparation method of titanium-silicon molecular sieve catalyst of the present invention comprises:
HTS powder, polymerization single polymerization monomer styrene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed, and wherein the raw material addition in parts by weight as follows: 5～30 parts of HTS powders, 10～120 parts of polymerization single polymerization monomer styrene; Be preferably 30～90 parts, 15～120 parts of polyene-based compounds are preferably 20～80 parts; 5～60 parts of perforating agents; In the presence of initator, at 60～150 ℃, preferably 80～90 ℃ were carried out polymerisation 3～10 hours; Preferably 4～6 hours, 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 of the present invention.
Described polymerization single polymerization monomer polyene-based compound can be one or more in 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 0.5～1.5 part.
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 applications that the inventive method obtains is in the catalytic reaction process of the alkene epoxidation of fixed-bed process, and catalytic effect is excellent.
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 HTS active.
4, catalyst backbone is water-fast, helps at H
2O
2React in the reaction atmosphere.
The specific embodiment
Specific area is to adopt the low temperature liquid nitrogen determination of adsorption method among the present invention.Intensity is to adopt QCY-602 type catalyst strength analyzer to measure.
The concrete preparation process of the inventive method is following:
(1), polymerization
In polymeric kettle; Add 5～30 parts of HTS powders, 15～120 parts of polymerization single polymerization monomer polyene-based compounds, 5～60 parts in perforating agent liquid wax; After mixing, warming-in-water adds 0.5～1.5 part of 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, pour out halogenated hydrocarbons after; 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 titanium-silicon molecular sieve catalyst of the present invention.This catalyst can directly be packed into and carried out the epoxidised catalytic reaction of alkene in the fixed bed reactors.
Below in conjunction with embodiment the present invention is done further detailed description; Following examples are not the restriction to protection domain of the present invention; Those skilled in the art combines 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 is 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 titanium-silicon molecular sieve catalyst A, its physico-chemical property is seen 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 xylenes 200ml again and carry out solvent extraction, 55 ℃ of extractive reaction temperature, 4 hours extracting time, carry out three extractings with quadrat method, obtain titanium-silicon molecular sieve catalyst B, its physico-chemical property is seen 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 titanium-silicon molecular sieve catalyst C with embodiment 1, and its physico-chemical property is seen table 1.
Embodiment 4
The weight of HTS powder among the embodiment 1 is become 45g, and all the other obtain titanium-silicon molecular sieve catalyst D with embodiment 1, and its physico-chemical property is seen table 1.
Embodiment 5
The weight of HTS powder among the embodiment 1 is become 60g, and all the other obtain titanium-silicon molecular sieve catalyst E with embodiment 1, and its physico-chemical property is seen table 1.
Embodiment 6
The weight of HTS powder among the embodiment 1 is become 75g, and all the other obtain titanium-silicon molecular sieve catalyst F with embodiment 1, and its physico-chemical property is seen table 1.
The physico-chemical property of table 1 catalyst
| Catalyst | Specific area (BET), m 2·g -1 | Intensity, N.mm -1 |
| A | 80.2 | 17.1 |
| B | 97.4 | 15.0 |
| C | 110.9 | 11.2 |
| D | 141.5 | 10.5 |
| E | 175.6 | 9.7 |
| F | 211.7 | 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 (12)
1. the preparation method of a titanium-silicon molecular sieve catalyst comprises:
HTS powder, polymerization single polymerization monomer styrene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed; Wherein the raw material addition in parts by weight as follows: 5～30 parts of HTS powders, 10～120 parts of styrene, 5～100 parts of polymerization single polymerization monomer polyene-based compounds; 5～60 parts of perforating agents; In the presence of initator, carried 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; Described initator is benzoyl peroxide and/or azo two isobutanols, and addition is counted 0.5～1.5 part with weight portion.
2. according to the described method of claim 1, it is characterized in that described polymeric reaction temperature is 80～90 ℃, the reaction time is 4～6 hours.
3. according to the described method of claim 1, it is characterized in that described polymerization single polymerization monomer polyene-based compound is one or more in divinylbenzene, divinyl toluene and the biethenyl-xylene.
4. according to claim 1 or 3 described methods, it is characterized in that 30～90 parts of described polymerization single polymerization monomer styrene, the addition of polymerization single polymerization monomer polyene-based compound is 20～80 parts.
5. according to the described method of claim 1, 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.
6. according to the described method of claim 1, it is characterized in that described perforating agent is C
5～C
13In the n-alkane one or more.
7. according to the described method of claim 1, 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.
8. according to the described method of claim 1, 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.
9. according to the described method of claim 1, it is characterized in that described extraction solvent is one or more in benzene,toluene,xylene, ethyl acetate, butyl acetate, ethanol, the butanols, the volume ratio of described extraction solvent and catalyst is 1: 1～5: 1.
10. according to the described method of claim 1, 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.
11., it is characterized in that described extractive reaction temperature is 50～60 ℃ according to the described method of claim 1; The described extracting time is 4～6 hours, and the extracting number of times is 2～5 times.
12., it is characterized in that the temperature in the described initator adding system is 60～90 ℃ according to the described method of claim 1.
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| CN103041855B (en) * | 2013-01-07 | 2014-09-10 | 上海卓悦化工科技有限公司 | Preparation method of catalysts for dichloro-pyridine oxynitride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346705A (en) * | 2001-09-13 | 2002-05-01 | 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 |
| CN101371989A (en) * | 2007-08-22 | 2009-02-25 | 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346705A (en) * | 2001-09-13 | 2002-05-01 | 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 |
| CN101371989A (en) * | 2007-08-22 | 2009-02-25 | 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 |
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