CN103894226B - Preparation method of granular titanium silicalite molecular sieve catalyst - Google Patents
Preparation method of granular titanium silicalite molecular sieve catalyst Download PDFInfo
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- CN103894226B CN103894226B CN201410066577.2A CN201410066577A CN103894226B CN 103894226 B CN103894226 B CN 103894226B CN 201410066577 A CN201410066577 A CN 201410066577A CN 103894226 B CN103894226 B CN 103894226B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 36
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000010936 titanium Substances 0.000 title abstract description 9
- 229910052719 titanium Inorganic materials 0.000 title abstract description 8
- -1 polyethylene Polymers 0.000 claims abstract description 24
- 239000004698 Polyethylene Substances 0.000 claims abstract description 17
- 229920000573 polyethylene Polymers 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 239000004088 foaming agent Substances 0.000 claims description 14
- 238000005453 pelletization Methods 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 2
- 238000011049 filling Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000640 hydroxylating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000000017 hydrogel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
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- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 229920002379 silicone rubber Polymers 0.000 description 1
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
The invention discloses a granular titanium silicalite molecular sieve catalyst, which comprises the following components in parts by weight: 15 parts of high-pressure polyethylene, 5 parts of low-pressure polyethylene, 60-75 parts of titanium silicalite molecular sieve, 0.5-2 parts of coupling agent and 4-20 parts of pore-forming agent; the invention also provides a preparation method of the granular titanium silicalite molecular sieve catalyst; the invention has the advantages of good activity of the prepared catalyst, convenient filling, difficult loss and small system resistance.
Description
Technical field
The present invention relates to molecular sieve catalyst and preparation method thereof, particularly a kind of preparation method of graininess titanium-silicon molecular sieve catalyst.
Background technology
Zeolite molecular sieve refers to the microporous crystalline body (comprising natural and Prof. Du Yucang) of a class hydrated aluminosilicate, has regular orderly pore passage structure and the feature such as larger pore volume and specific area.As a kind of novel chemical materials, it is widely used in petrochemical industry, fine chemistry industry, petroleum and natural gas processing and refining, gas absorption and is separated, in the numerous areas such as environmental protection, and plays the effect become more and more important.Nineteen eighty-three, namely Taramasso and partner thereof the pure silicon molecular sieve Silicalite-1 skeleton that transition metals Ti induced one first becomes Titanium-Silicalite-1, referred to as TS-1.Because in TS-1 molecular sieve, Ti4+ ion has hexa-coordinate characteristic, therefore the tetrahedral energy of titanyl is higher, there is the electronic defects of structure, has the potential accepting duplet, thus to H
2o
2there is unique adsorption activation performance (even the H of low concentration
2o
2), thus selective oxidation can be carried out to multiple organic compound, therefore, be widely used in the catalyst of oxidation reaction, as the hydroxylating of benzene and phenol, the epoxidation of alkene, the oximate of cyclohexanone, the oxidation etc. of amine and saturated alkane etc., wherein, the report that TS-1 molecular sieve is used for the oxidation of phenol, the epoxidation catalyst of the oximate of cyclohexanone and propylene has industrial applications.
TS-1 molecular sieve catalyst makes reaction have following remarkable advantage: 1. reaction condition is gentle, can carry out under normal pressure, low temperature (20 ~ 100 DEG C); 2. object product yield is oxidized high, selective good; 3. technical process is simple; 4. owing to using low concentration hydrogen peroxide as oxidant, oxidation source is easy to get safely; 5. reduzate is H
2o, reaction system does not introduce impurity, can not cause environmental pollution.Its successful exploitation is considered to the milestone of the zeolite catalysis eighties in 20th century, for hydrocarbon oxidization, the developing green technique studying high selectivity is laid a good foundation.Therefore, carried out a series of linguistic term both at home and abroad and had bibliographical information:
As US Patent No. 4410501 adopts two kinds of hydrothermal methods to synthesize TS-1 first, the method of preparation is for do silicon source with ethyl orthosilicate (TEOS) or silica gel, positive tetraethyl titanate (TEOT) is titanium source, template is tetrapropyl oxyammonia (TPAOH), make synthesis mother liquid according to a certain ratio in 448K, use water heat transfer at autogenous pressures, crystallization time about 10 days.When with Ludox as silicon source time, need in mixture to add H
2o
2, titanium is existed with pertitanic acid ionic species.
And for example China Patent Publication No. patent CN1301599A provides a kind of HTS (TS-1) and preparation method thereof, and the crystal grain of this molecular sieve is hollow-core construction; The radical length of the chamber portion of this hollow crystal grain is 5 ~ 300 nanometers; This sieve sample at 25 DEG C, P/P
0the benzene adsorbance of adsorbing 1 hour under=0.1 condition is at least 70 milligrams/grams; The preparation method of this molecular sieve comprises the TS-1 molecular sieve synthesized first is used acid compound process, then uses organic base process, or directly uses organic base process.
For another example China Patent Publication No. CN102320619A discloses a kind of synthetic method of TS-1 molecular sieve, silicon source, titanium source, template, alkaline mineralizer and water are prepared titanium Silica hydrogel in proportion, adopts direct method or indirect method to introduce appropriate alkali metal salt joining in glue process; Then hydrothermal crystallizing at 160 ~ 180 DEG C; Again after filtration, washing, dry and roasting, obtain TS-1 molecular sieve.
Above prior art has following weak point: the TS-1 HTS of preparation, be the powder product that particle diameter is less, in use, easily be adsorbed on contact surface as reactor wall, tube wall, pump inner chamber, film surface etc., cause the reduction of catalyst valid density, catalytic activity decline, and easily block reactor, increase reactor resistance, reduce reaction efficiency.In addition, powder product is easy with material loss in process of production, and for keeping catalyst valid density, need increase film filter, equipment investment is large.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provide a kind of prepare good catalyst activity, convenient filling, not easily run off, the preparation method of graininess titanium-silicon molecular sieve catalyst that SR is little.
In order to solve above technical problem, present invention employs following technical scheme: a kind of preparation method of graininess titanium-silicon molecular sieve catalyst, comprises the following steps:
A () by weight, by polyethylene from high pressure process 15 parts, low-pressure polyethylene 5 parts, HTS 60-75 part, coupling agent 0.5-2 part, pore-foaming agent 4-20 part adds high-speed mixer and carries out blended, described blending temperature is 90-120 DEG C, the blended time is 10-60min, high-speed mixer rotating speed is 800-1500r/min, obtain mixed material, described coupling agent is preferably the one in aluminate coupling agent, titanate coupling agent, boric acid ester coupler, aluminium titanium composite coupler, and described pore-foaming agent is preferably the one in oleic acid, brominated paraffin, white oil;
B mixed material that step (a) obtains by () adds double screw extruder and carries out extruding pelletization, in described extruding pelletization process, twin-screw extruder barrel temperature is a district 170-190 DEG C, two district 180-195 DEG C, three district 190-200 DEG C, four district 190-200 DEG C, five district 190-200 DEG C, six district 180-190 DEG C, seven district 165-185 DEG C, head temperature is 170-190 DEG C, obtains granulation material;
C granulation material that step (b) obtains by () soaks 10-30h in a solvent at 40-80 DEG C, immersion terminates rear washing, dry, obtain graininess titanium-silicon molecular sieve catalyst, described solvent is preferably the one in butyl acetate, butyl acetate, o-dichlorohenzene, acetone, ethanol, dimethyl ether.
The present invention uses HTS as inorganic filler, with polyethylene, and pore-foaming agent, coupling agents etc. mix in high-speed mixer, then use the granulation of twin-screw granulating extruder, granular product Solvent Extract methods pore-foaming agent, generates the graininess titanium-silicon molecular sieve catalyst with microcellular structure.Graininess titanium-silicon molecular sieve catalyst of the present invention, has microcellular structure, can improve the contact area of reaction, compared with ultra-fine titanium-silicon molecular sieve catalyst, graininess titanium-silicon molecular sieve catalyst there will not be with material loss phenomenon, so need not take film filter, reduces equipment investment.Graininess titanium-silicon molecular sieve catalyst of the present invention can be used for fixed bed continuous prodution, or catalytic distillation technology, has bed resistance and falls little, convenient filling, do not need the advantages such as complicated reactor internal components.Be particularly useful for reactive distillation and counter-current reactor field, can be used for producing hydroquinones technique, caprolactam oximate technique etc.
Compared with prior art, the present invention has following beneficial effect:
1, compared with ultra-fine titanium-silicon molecular sieve catalyst, convenient filling during use, and there will not be with material loss phenomenon, therefore need not film filter be set, reduces equipment investment;
2, good catalyst activity, graininess titanium-silicon molecular sieve catalyst of the present invention, has microcellular structure, can improve the contact area of reaction, and catalytic activity is good;
3, for fixed bed continuous prodution or catalytic distillation technology, little, convenient filling falls in bed resistance.
Detailed description of the invention
Below in conjunction with specific embodiment, illustrate the present invention further, but these embodiments are only for explaining the present invention, instead of for limiting the scope of the invention.
In embodiment, raw materials used and equipment all can commercially availablely obtain, part material and specification of equipment demonstration of the type as follows:
Polyethylene from high pressure process (LDPE): model 1810D, Petrochina Lanzhou Petrochemical Company;
Low-pressure polyethylene (HDPE): model B160C, Beijing Beiqing Lianke Nano P&R Co., Ltd.;
HTS: model JTS-1, Juhua Group Co..
Twin-screw granulating extruder: model SHJ-36, Nanjing Cheng Meng chemical machinery Co., Ltd;
High-speed mixer: model GHJ-36, Shanghai Plastic machinery plant.
Embodiment 1
Step (1) raw material is blended:
Pulp furnish is as follows:
Using polyethylene from high pressure process (LDPE), low-pressure polyethylene (HDPE), HTS, the brominated paraffin as pore-foaming agent, aluminium titanium composite coupler (model HY-133, Hangzhou Jesse blocks Chemical Co., Ltd. and produces), adding high-speed mixer by proportioning carries out blended, blending temperature 100 DEG C, the blended time is 10min, high-speed mixer rotating speed is 1000r/min, obtains mixed material.
Step (2) extruding pelletization:
The mixed material that above-mentioned steps (1) obtains is added twin-screw granulating extruder and carries out extruding pelletization, in extruding pelletization process, twin-screw granulating extruder barrel temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 195 DEG C, districts, four 200 DEG C, districts, five 200 DEG C, districts, six 185 DEG C, districts, seven 170 DEG C, districts, head temperature is 175 DEG C, obtains granulation material;
Step (3) extracts pore-foaming agent:
The acetone granulation material that step (2) obtains being used as solvent soaks 20h, soaking temperature controls at 50 DEG C, soaks after terminating and cleans 2 times by solvent acetone again, finally dry, obtain the graininess titanium-silicon molecular sieve catalyst product with microcellular structure, product designation K-1.
Embodiment 2
Step (1) raw material is blended:
Pulp furnish is as follows:
Using polyethylene from high pressure process (LDPE), low-pressure polyethylene (HDPE), HTS, the brominated paraffin as pore-foaming agent, aluminate coupling agent (model JCL-60, Guangzhou is polymerized to million industry organosilicon materials Co., Ltds and produces), adding high-speed mixer by proportioning carries out blended, blending temperature 90 DEG C, the blended time is 40min, high-speed mixer rotating speed is 800r/min, obtains mixed material.
Step (2) extruding pelletization:
The mixed material that step (1) obtains is added twin-screw granulating extruder and carries out extruding pelletization, in described extruding pelletization process, twin-screw granulating extruder barrel temperature is 170 DEG C, a district, two 180 DEG C, districts, three 200 DEG C, districts, four 195 DEG C, districts, five 195 DEG C, districts, six 180 DEG C, districts, seven 165 DEG C, districts, head temperature is 170 DEG C, obtains granulation material;
Step (3) extracts pore-foaming agent:
The acetone granulation material that step (2) obtains being used as solvent soaks 10h, soaking temperature controls at 80 DEG C, soaks after terminating and cleans 2 times by solvent acetone again, finally dry, obtain the graininess titanium-silicon molecular sieve catalyst product with microcellular structure, product designation K-2.
Embodiment 3
Step (1) raw material is blended:
Pulp furnish is as follows:
Using polyethylene from high pressure process (LDPE), low-pressure polyethylene (HDPE), HTS, the brominated paraffin as pore-foaming agent, titanate coupling agent (model TMC-981, green chemical industry auxiliary reagent factory of Tianzhang City produces), adding high-speed mixer by proportioning carries out blended, blending temperature 120 DEG C, the blended time is 20min, high-speed mixer rotating speed is 1200r/min, obtains mixed material.
Step (2) extruding pelletization:
Mixed material step (a) obtained adds twin-screw granulating extruder and carries out extruding pelletization, in described extruding pelletization process, twin-screw granulating extruder barrel temperature is 190 DEG C, a district, two 195 DEG C, districts, three 190 DEG C, districts, four 190 DEG C, districts, five 190 DEG C, districts, six 190 DEG C, districts, seven 185 DEG C, districts, head temperature is 190 DEG C, obtains granulation material;
Step (3) extracts pore-foaming agent:
The acetone granulation material that step (2) obtains being used as solvent soaks 30h, soaking temperature controls at 40 DEG C, soaks after terminating and cleans 2 times by solvent acetone again, finally dry, obtain the graininess titanium-silicon molecular sieve catalyst product with microcellular structure, product designation K-3.
Embodiment 4
Step (1) raw material is blended:
Pulp furnish is as follows:
Using polyethylene from high pressure process (LDPE), low-pressure polyethylene (HDPE), HTS, the brominated paraffin as pore-foaming agent, boric acid ester coupler (model JCL-50, Guangzhou is polymerized to million industry organosilicon materials Co., Ltds and produces), adding high-speed mixer by proportioning carries out blended, blending temperature 110 DEG C, the blended time is 60min, high-speed mixer rotating speed is 1500r/min, obtains mixed material.
Step (2) is with embodiment 1;
Step (3) extracts pore-foaming agent:
The butyl acetate granulation material that step (2) obtains being used as solvent soaks 15h, soaking temperature controls at 60 DEG C, soaks after terminating and cleans 2 times with solvent butyl acetate again, finally dry, obtain the graininess titanium-silicon molecular sieve catalyst product with microcellular structure, product designation K-4.
Embodiment 5
Dimethyl ether selected by solvent in step (3), and other condition, with embodiment 2, obtains the graininess titanium-silicon molecular sieve catalyst product with microcellular structure, product designation K-5.
Embodiment 6
Ethanol selected by solvent in step (3), and other condition, with embodiment 3, obtains the graininess titanium-silicon molecular sieve catalyst product with microcellular structure, product designation K-6.
By catalysis of phenol hydroxylating, performance test is carried out to the graininess titanium-silicon molecular sieve catalyst product with microcellular structure that HTS (JTS-1, Juhua Group Co.) and embodiment 1 ~ 6 obtain:
Carry out in the 50ml two-neck bottle of benzene hydroxylation reaction in water bath with thermostatic control, and be furnished with the reflux condensing tube of a silicon rubber cap and a rubber seal.Be weighed into a certain amount of TS-1 catalyst and benzene (marking containing in dichloro-benzenes) in above-mentioned two-neck bottle after, stir, after temperature constant, inject diluted hydrogen peroxide (H
2o
2), start reaction and timing, after reaction terminates, filtering recovering catalyst, dry also weighs, and product analysis carries out on GLC capillary gas chromatograph, detects the conversion ratio of phenol, response parameter as table 1, phenol conversion as table 2, wherein:
The phenol amount of the phenol amount/input of conversion ratio (the phenol)=consumption of phenol
The catalytic amount of catalyst attrition=(catalytic amount-recovery catalytic amount of input)/input
Table 1: phenol hydroxylation response parameter
| Reactant species | Quality (g) |
| Phenol | 200 |
| Acetone | 160 |
| Catalyst | 10 |
| Hydrogen peroxide (30%) | 78 |
| Reaction temperature DEG C | 80 |
| Reaction time h | 6 |
Table 2: the result of the catalyst prod catalysis of phenol hydroxylating that embodiment 1 ~ 6 is obtained
| Numbering | Phenol conversion % | Catalyst attrition % |
| K-1 | 21.7 | 0 |
| K-2 | 25.3 | 0 |
| K-3 | 23.5 | 0 |
| K-4 | 23.2 | 0 |
| K-5 | 25.1 | 0 |
| K-6 | 22.8 | 0 |
| HTS | 19.63 | 5.3 |
Claims (1)
1. a preparation method for graininess titanium-silicon molecular sieve catalyst, is characterized in that comprising the following steps:
A () by weight, by polyethylene from high pressure process 15 parts, low-pressure polyethylene 5 parts, HTS 60-75 part, coupling agent 0.5-2 part, pore-foaming agent 4-20 part adds high-speed mixer and carries out blended, described blending temperature is 90-120 DEG C, the blended time is 10-60min, high-speed mixer rotating speed is 800-1500r/min, obtain mixed material, described coupling agent is the one in aluminate coupling agent, titanate coupling agent, boric acid ester coupler, aluminium titanium composite coupler, and described pore-foaming agent is the one in oleic acid, brominated paraffin, white oil;
B mixed material that step (a) obtains by () adds double screw extruder and carries out extruding pelletization, in described extruding pelletization process, twin-screw extruder barrel temperature is a district 170-190 DEG C, two district 180-195 DEG C, three district 190-200 DEG C, four district 190-200 DEG C, five district 190-200 DEG C, six district 180-190 DEG C, seven district 165-185 DEG C, head temperature is 170-190 DEG C, obtains granulation material;
C granulation material that step (b) obtains by () soaks 10-30h in a solvent at 40-80 DEG C, immersion terminates rear washing, dry, obtain graininess titanium-silicon molecular sieve catalyst, described solvent is the one in butyl acetate, butyl acetate, o-dichlorohenzene, acetone, ethanol, dimethyl ether.
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