CN1116099C - Circular catalyst separating process in catalytic reaction of Ti-Si molecular sieve - Google Patents
Circular catalyst separating process in catalytic reaction of Ti-Si molecular sieve Download PDFInfo
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- CN1116099C CN1116099C CN 00113447 CN00113447A CN1116099C CN 1116099 C CN1116099 C CN 1116099C CN 00113447 CN00113447 CN 00113447 CN 00113447 A CN00113447 A CN 00113447A CN 1116099 C CN1116099 C CN 1116099C
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- molecular sieve
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- membrane separator
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Abstract
The present invention relates to a circular catalyst separating method in a catalytic reaction of titanium-silicon molecular sieve, which is characterized in that reactant materials which contain titanium-silicon molecular sieve catalysts is pumped into a membrane separator which has a certain hole diameter, and the membrane face flow rate of the materials in the membrane separator is controlled; purified liquor is obtained from the permeation side of the membrane separator, and trapped liquor is obtained from the outlet of the membrane separator; the trapped liquor is circulated to return to a material tank, and the purified liquor at the permeation side is the material which does not contain catalysts. Nitrogen gas or the trapped liquor is used periodically for carrying out back flushing to a membrane tube, and certain back flushing time interval, back flushing pressure and duration time are controlled.
Description
The present invention relates to the circulation partition method of catalyst in a kind of catalytic reaction of Ti-Si molecular sieve.
HTS is a kind of new catalytic material that development in recent years is got up, the various organic oxidizing reactions that participate in hydrogen peroxide had unique catalytic performance, the selectivity of product height, the reaction condition gentleness, environmental friendliness, but the partial oxidation of the epoxidation of its catalysis of pimelinketone prepared by ammoxidation cyclohexanone oxime, alkene, alkane, the oxidation of alcohols and the hydroxylating of aromatic hydrocarbon ring etc.But the titanium-silicon molecular sieve catalyst particle is little, has only about 0.2 μ m as common TS-1 catalyst average grain diameter, and reclaiming filtration is a difficult problem.The method that Italy ENI company adopts is with spray shaping technology catalyst particle to be made oarse-grained catalyst earlier, the stainless steel perforated baffle is installed in reactor again catalyst is held back separation.To be catalyst wanted make bulky grain through spray shaping earlier before using the shortcoming of this method, the flow process that extended, and catalyst granules do big after; its intensity reduces; under strong agitation, catalyst granules can be slowly broken, might pass the stainless steel baffle plate and cause loss.The method that adopts the sedimentation separation catalyst is also arranged, but the required sedimentation separation equipment of this method is big, and causes easily in the material of catalyst granules after separation and carry secretly, cause catalyst loss.
The circulating and separating method that the purpose of this invention is to provide catalyst in a kind of catalytic reaction of Ti-Si molecular sieve.
The present invention is achieved in that the organic materials that will contain titanium-silicon molecular sieve catalyst adds membrane separator with pump, per-meate side at membrane separator obtains clear liquid, outlet at membrane separator obtains trapped fluid, trapped fluid loops back batch can, the clear liquid of per-meate side is the material that does not contain catalyst, regularly with nitrogen or penetrating fluid the film pipe is recoiled.For average grain diameter is the titanium-silicon molecular sieve catalyst of 0.2 μ m, and the film pore directly is 0.01～1.0 μ m, and preferably the film pore directly is 0.05～0.2 μ m.The crossflow velocity of material in membrane separator is 1～8m/s, is preferably 2～4m/s.The recoil time interval is 1～300 minute, is preferably 10～120 minutes, and recoil pressure is controlled at 0.2～1.0Mpa, is preferably 0.4～0.6Mpa, and the recoil duration is 0.1～10 second, is preferably 0.5～1 second.
The used membrane separator of the present invention can be various organic films or inoranic membrane, generally adopts the inorganic ceramic micro-filtration membrane.
Fig. 1 is the process flow diagram of film device circulation separating titanium silicalite molecular sieve catalyst.
Detailed processing step is shown in Figure of description 1: the material in the batch can 1 is squeezed into membrane separator 6 with pump 3 through valve 4, flowmeter 5 through valve 2, and trapped fluid enters membrane separator 7, loops back batch can 1 through pipeloop 8 then.The penetrating fluid of membrane separator 6 is joined after flowmeter 11 enters clear liquid jar 12 through valve 10 through the valve 9 and the penetrating fluid of film pipe 7.Regularly with nitrogen or penetrating fluid two film pipes are recoiled, nitrogen recoils through the per-meate side that valve 13, gas buffer jar 14, valve 15 and fluid cushion jar 16 enter two film pipes.
Good effect of the present invention is to realize that titanium-silicon molecular sieve catalyst is also recycling with separating fully of material, can guarantee that the continous-stable of reaction carries out.The separating technology of our invention is directly to adopt membrane separation device or combine with other method, the material that will contain titanium-silicon molecular sieve catalyst is squeezed into membrane separation device, the a large amount of trapped fluids that come out from the film pipe circulate, and a small amount of penetrating fluid that infiltrates promptly becomes product.Its characteristics are that circulating filtration combines with the recoil operation, and simple to operation, the cycle is long, and good separating effect does not contain catalyst granules after testing in the penetrating fluid, solved the difficult problem that titanium-silicon molecular sieve catalyst separates effectively.
Embodiment 1. film devices are applied to the isolated by filtration of titanium molecular sieve catalysis ammoxidation of cyclohexanone preparing cyclohexanone oxime reacting middle catalyst.To contain 2kg cyclohexanone oxime, the 4.8kg tert-butyl alcohol, 3.2kg water and 0.25kg average grain diameter is in solution (catalyst concn the is 2.5wt%) batch can 1 of packing into of the TS-1 type titanium-silicon molecular sieve catalyst of 0.2 μ m, keeping temperature of charge is 85 ℃, squeeze into the inorganic ceramic micro-filtration membrane separator 6 that membrane aperture is 0.2 μ m through pump 3, valve 4 and flowmeter 5 then, trapped fluid enters the inorganic ceramic micro-filtration membrane separator 7 that membrane aperture is 0.2 μ m, and then looping back batch can 1, membrane separator 6 and 7 infiltration clear liquid enter clear liquid jar 12 through flowmeter 11.The crossflow velocity of material in membrane separator is controlled to be 2m/s, and controlling diaphragm separator inlet outlet pressure differential is no more than 0.5Mpa.Regularly with nitrogen two film pipes are recoiled, the recoil time interval controls is 1 hour, and the duration of at every turn recoiling is 0.5 second, and recoil pressure is controlled at 0.45Mpa.Nitrogen recoils through the per-meate side that gas buffer jar 14 and fluid cushion jar 16 enter two film pipes.Through detecting penetrating fluid, do not find catalyst granules.
Embodiment 2. film devices are applied to the isolated by filtration of titanium molecular sieve catalysis propylene to prepare epoxy propane reacting middle catalyst.To contain 3.2kg expoxy propane, 6kg methyl alcohol, 0.66kg water and 0.09kg average grain diameter is the solution (catalyst concn is 0.9wt%) of the TS-1 type titanium-silicon molecular sieve catalyst of 0.2 μ m, pack in the batch can 1, keeping temperature of charge is 40 ℃, squeeze into the inorganic ceramic micro-filtration membrane separator 6 that membrane aperture is 0.05 μ m through pump 3, valve 4 and flowmeter 5 then, trapped fluid enters the inorganic ceramic micro-filtration membrane separator 7 that membrane aperture is 0.05 μ m, and then looping back batch can 1, membrane separator 6 and 7 infiltration clear liquid enter clear liquid jar 12 through flowmeter 11.The crossflow velocity of material in membrane separator is controlled to be 3m/s, and controlling diaphragm separator inlet outlet pressure differential is no more than 0.5Mpa.Regularly with nitrogen two film pipes are recoiled, the recoil time interval controls is 30 minutes, and the duration of at every turn recoiling is 1 second, and recoil pressure is controlled at 0.5Mpa.Nitrogen recoils through the per-meate side that gas buffer jar 14 and fluid cushion jar 16 enter two film pipes.Through detecting penetrating fluid, do not find catalyst granules.
Claims (7)
1. the circulating and separating method of catalyst in the catalytic reaction of Ti-Si molecular sieve, it is characterized in that: the reaction mass that will contain titanium-silicon molecular sieve catalyst adds membrane separator with pump, and the crossflow velocity of control material in membrane separator, obtain clear liquid from the per-meate side of membrane separator, the outlet of membrane separator obtains the liquid that dams, the liquid that dams loops back batch can, and the clear liquid of per-meate side is the material that does not contain catalyst, regularly with nitrogen or trapped fluid the film pipe is recoiled.
2. the circulating and separating method of catalyst in a kind of catalytic reaction of Ti-Si molecular sieve according to claim 1, it is characterized in that separating and contain the reaction mass that average grain diameter is the titanium-silicon molecular sieve catalyst of 0.2 μ m, using membrane aperture is the membrane separator of 0.01 μ m～1.0 μ m.
3. the circulating and separating method of catalyst in a kind of catalytic reaction of Ti-Si molecular sieve according to claim 2 is characterized in that the membrane separator aperture is the inorganic ceramic micro-filtration membrane separator of 0.05 μ m～0.2 μ m.
4. the circulating and separating method of catalyst in a kind of catalytic reaction of Ti-Si molecular sieve according to claim 1 is characterized in that the crossflow velocity of material in membrane separator is controlled to be 1m/s～8m/s.
5. the circulating and separating method of catalyst in a kind of catalytic reaction of Ti-Si molecular sieve according to claim 4 is characterized in that the crossflow velocity of material in membrane separator is controlled to be 2m/s～4m/s.
6. the circulating and separating method of catalyst in a kind of catalytic reaction of Ti-Si molecular sieve according to claim 1, the time interval controls that it is characterized in that recoiling is 1 minute～300 minutes, recoil pressure is controlled at 0.2MPa～1.0Mpa, and the recoil duration is 0.1 second～10 seconds.
7. the circulating and separating method of catalyst in a kind of catalytic reaction of Ti-Si molecular sieve according to claim 1, the time interval controls that it is characterized in that recoiling is 10 minutes～120 minutes, recoil pressure is controlled at 0.4MPa～0.6Mpa, and the recoil duration is 0.5 second～1 second.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113447 CN1116099C (en) | 2000-05-22 | 2000-05-22 | Circular catalyst separating process in catalytic reaction of Ti-Si molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113447 CN1116099C (en) | 2000-05-22 | 2000-05-22 | Circular catalyst separating process in catalytic reaction of Ti-Si molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1324684A CN1324684A (en) | 2001-12-05 |
| CN1116099C true CN1116099C (en) | 2003-07-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 00113447 Expired - Lifetime CN1116099C (en) | 2000-05-22 | 2000-05-22 | Circular catalyst separating process in catalytic reaction of Ti-Si molecular sieve |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102070488A (en) * | 2010-12-21 | 2011-05-25 | 湘潭大学 | Method for preparing ketoxime |
| CN103130748B (en) * | 2011-11-29 | 2015-04-29 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
| CN103007755B (en) * | 2012-12-29 | 2015-12-09 | 上海安赐机械设备有限公司 | Be applied to dynamic video disc film device and the technique thereof of ultrafine solids catalyst recovery |
| CN113428871B (en) * | 2021-07-12 | 2022-11-18 | 宁夏美邦寰宇化学有限公司 | Separation and purification method and separation and purification system of titanium-silicon molecular sieve |
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- 2000-05-22 CN CN 00113447 patent/CN1116099C/en not_active Expired - Lifetime
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Owner name: CHINA PETROLEUM + CHEMICAL CORPORATION Free format text: FORMER OWNER: BALIN BRANCH CORP. SINOPEC Effective date: 20090522 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090522 Address after: Chaoyang District, Chaoyangmen, North Street, No. 22, No. Patentee after: Sinopec Corp. Address before: Baling Petrochemical Industries Co No. 1 in Hunan province Yueyang City dongting Avenue Patentee before: Baling Branch, China Petro-Chemical Co., Ltd. |
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Granted publication date: 20030730 |