CN102173434A - Method for removing template in industrial production process of MCM-41 molecular sieves - Google Patents
Method for removing template in industrial production process of MCM-41 molecular sieves Download PDFInfo
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- CN102173434A CN102173434A CN 201010613129 CN201010613129A CN102173434A CN 102173434 A CN102173434 A CN 102173434A CN 201010613129 CN201010613129 CN 201010613129 CN 201010613129 A CN201010613129 A CN 201010613129A CN 102173434 A CN102173434 A CN 102173434A
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Abstract
The invention discloses a novel safe and environmental-protection method for removing an organic template in an industrial production process of MCM-41 molecular sieves. In the method, a programmed heating method is used for removing the template in a closed roasting furnace, the decomposition temperature of the template is controlled so that the template is decomposed at low temperature without spontaneous combustion, and meanwhile, the decomposed gas is introduced into a waste gas treatment device through a specific device so as to be purified. The whole treatment process is safe and controllable, does not pollute the environment, and thus, meets the requirement for environmental protection in the current chemical industry production.
Description
Technical field
The present invention relates to a kind of method of MCM-41 mesoporous molecular sieve removed template method, the safe green environmental protection removal methods of template in a kind of MCM-41 industrial production of saying so more specifically.
Background technology
The MCM-41 molecular sieve is a kind of novel mesoporous molecular sieve, has high-specific surface area (〉=800m
2/ g), big loading capacity (〉=0.8cm
3/G) and the characteristics such as pore size of homogeneous, more help the rapid diffusion of organic molecule than common zeolite and other poromerics, this makes it to select shaped reaction for heavy oil organic molecule in the macromole especially petrochemical process unrivaled favourable space is provided.This molecular sieve analog has sizable potential value in the absorption of catalytic fields such as residual oil catalytic cracking, heavy-oil hydrogenation, lube oil hydrogenation, alkylation, olefinic polymerization and gas, sepn process.But the heavy industrialization of MCM-41 molecular sieve is subjected to the restriction of various factors always, wherein the calcination process link in its preparation process wayward and be exactly one of important restraining factors to the severe contamination of environment.
The MCM-41 molecular sieve has multiple preparation method, but all needs the existence of organic formwork agent in the preparation process, and all inevitably will carry out removing of template in last treating processes, just can obtain duct available zeolite product.Template used dose of long chain alkane quaternary amines cationic surfactant that is the dodecyl trimethyl-ammonium halide to octadecyl trimethyl-ammonium halide one class substantially of MCM-41 molecular sieve.The most frequently used and the simple effective method of removed template method promptly is a roasting method, this method is easier to when handling in the laboratory realize, but in industrial production, there are serious problems, at first the high-temperature roasting meeting causes template to decompose the violent burning in back, make difficult control of temperature, treatment capacity large-scale combustion situation more is serious more, the difficult more control of temperature, not only can cause part destroyed specific surface area in product duct to descend, and can dangerous generation.In addition, remove in the process of template in roasting, template is decomposed, and generates small molecules organic amine, hydrogen bromide and low-carbon (LC) hydro carbons, if oxidation takes place, also can generate materials such as nitrogen protoxide, environment there is serious pollution, must be supporting with the waste gas absorbing and purifying device, it is handled, and can not allow it directly enter atmosphere, cause environmental pollution.
Summary of the invention
The objective of the invention is to, the method of MCM-41 molecular sieve removed template method in a kind of industrial production is provided, and this method adopts temperature programming, the decomposition of control template agent and it is burnt, and supporting with emission-control equipment behind stoving oven, make the treating processes environmentally safe.The MCM-41 zeolite product aperture homogeneous that uses this method to handle, specific surface area is big, the treating processes safety and environmental protection.
The present invention is as follows about the method for MCM-41 molecular sieve removed template method:
1, in being furnished with the closed high-temperature roasting stove of air inlet duct and vent, adopt the method for temperature programming to carry out removing of MCM-41 molecular sieve template.Behind venting hole, add blower unit and emission-control equipment, the waste gas of discharging is introduced in the exhaust gas processing pool carried out purifying treatment.The inlet mouth place is equipped with nitrogen gas generating device, generally takes closing condition, only when device fails or unusual, when in the stove combustion phenomena taking place, charges into nitrogen in stove, stops burning.
2, roasting process adopts the temperature programming method, the slow decomposition of control template agent and not burning.
(1) at first handles certain hour, molecular sieve is thoroughly dried at 110 ℃-120 ℃.
(2) slowly be warming up to template used dose of decomposition temperature and between the decomposition gas spontaneous ignition temperature, handle certain hour, the template overwhelming majority is decomposed overflow.
(3) be warming up to 450-550 ℃, the roasting certain hour makes residual a small amount of template decompose effusion fully, obtains finished product mesopore MCM-41 molecular sieve.
Mode below by example is carried out more specific description to the present invention, but the present invention is not limited thereto.
The specific surface of sample and pore volume use BELSORP-mini to carry out N in example
2Determining adsorption.
Embodiment
Embodiment 1
The contained template of handled MCM-41 is a cetyl trimethylammonium bromide, its temperature-programmed calcination condition is as follows: at first the stoving oven temperature is set at 120 ℃, oven dry 8h, its water that go up to adsorb of Ex-all, slowly be warming up to 200 ℃, 2 ℃/min of temperature rise rate at 200 ℃ of insulation 8h, and opens induced draft fan, waste gas is entered in the treatment unit that the weakly alkaline absorption liquid is housed, temperature is risen to 500 ℃ at last, 2 ℃/min of heat-up rate, insulation 4h.Its physical adsorption data see Table 1.
Embodiment 2
The contained template of handled MCM-41 is a Dodecyl trimethyl ammonium chloride, its temperature-programmed calcination condition is as follows: at first the stoving oven temperature is set at 110 ℃, oven dry 8h, its water that go up to adsorb of Ex-all, slowly be warming up to 160 ℃, 2 ℃/min of temperature rise rate at 160 ℃ of insulation 8h, and opens induced draft fan, waste gas is entered in the treatment unit that the weakly alkaline absorption liquid is housed, temperature is risen to 500 ℃ at last, 2 ℃/min of heat-up rate, insulation 4h.Its physical adsorption data see Table 1.
Comparative Examples 1
The contained template of handled MCM-41 is a cetyl trimethylammonium bromide, directly maturing temperature is set at 500 ℃, roasting 8h.Its physical adsorption data see Table 1.
The physical adsorption data of table 1MCM-41
| Embodiment | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Mean pore size (nm) |
| Embodiment 1 | 1025 | 0.9 | 3.3 |
| Embodiment 2 | 1215 | 1.1 | 2.5 |
| Comparative Examples 1 | 831 | 0.7 | 3.5 |
Claims (6)
1. the method for a MCM-41 molecular sieve removed template method, its feature is as follows:
In the closed high-temperature roasting stove that is equipped with air inlet duct and vent, adopt the method for temperature programming to carry out removing of MCM-41 molecular sieve template.Behind venting hole, add blower unit and emission-control equipment, the waste gas of discharging is introduced in the exhaust gas processing pool that the weakly alkaline absorption liquid is housed carried out purifying treatment.The inlet mouth place is equipped with nitrogen gas generating device, generally takes closing condition, only when device fails or unusual, when in the stove combustion phenomena taking place, charges into nitrogen in stove, stops burning.
2. treatment process according to claim 1, its temperature programming process is as follows: at first at 110-120 ℃ of oven dry 8h, the water that adsorbs in the Ex-all molecular sieve, be warming up to 160-200 ℃ then, insulation 8h, make the template low-temperature decomposition in the molecular sieve, be warming up to 450-550 ℃ of roasting 4h at last, residual template in the Ex-all molecular sieve pore passage.
3. treatment process according to claim 1, it is characterized in that template is decomposed in the temperature programming process during, start blower unit, decomposition gas is imported carries out purifying treatment in the exhaust gas processing pool, solve the pollution problem of waste gas to environment.
4. treatment process according to claim 1 is characterized in that described weakly alkaline absorption liquid is an aqueous sodium carbonate.
5. treatment process according to claim 1, the concentration that it is characterized in that the weakly alkaline absorption liquid is 0.01-0.05mol/L.
6. as temperature programming process as described in the claim 2, it is characterized in that template low-temperature decomposition temperature is 160-200 ℃.
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| CN 201010613129 CN102173434A (en) | 2010-12-30 | 2010-12-30 | Method for removing template in industrial production process of MCM-41 molecular sieves |
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| CN 201010613129 CN102173434A (en) | 2010-12-30 | 2010-12-30 | Method for removing template in industrial production process of MCM-41 molecular sieves |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217649A (en) * | 2015-10-26 | 2016-01-06 | 中国科学院广州能源研究所 | A kind of two steps in low temperature removes the method for organic formwork agent and realizes the device of the method |
| CN106145142A (en) * | 2015-04-13 | 2016-11-23 | 中国石油化工股份有限公司 | Removing molecular sieve organic formwork agent method |
| CN109465024A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using MTW type structure molecular screen as the isomerization catalyst preparation method of carrier |
| CN109465031A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using AFO type structure molecular screen as the isomerization catalyst preparation method of carrier |
| CN109467103A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | A method of removing Molecular Sieves as Template agent |
Citations (3)
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|---|---|---|---|---|
| US20080193734A1 (en) * | 2004-03-16 | 2008-08-14 | Wesley Whitnall | Hybrid Porous Organic-Metal Oxide Materials |
| CN101456562A (en) * | 2009-01-06 | 2009-06-17 | 北京科技大学 | Method for preparing mesoporous titanium silicate molecular sieve |
| CN101613113A (en) * | 2009-05-31 | 2009-12-30 | 华东理工大学 | A kind of method of nanometer hierarchical pore MFI molecular sieve one-step synthesis |
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2010
- 2010-12-30 CN CN 201010613129 patent/CN102173434A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080193734A1 (en) * | 2004-03-16 | 2008-08-14 | Wesley Whitnall | Hybrid Porous Organic-Metal Oxide Materials |
| CN101456562A (en) * | 2009-01-06 | 2009-06-17 | 北京科技大学 | Method for preparing mesoporous titanium silicate molecular sieve |
| CN101613113A (en) * | 2009-05-31 | 2009-12-30 | 华东理工大学 | A kind of method of nanometer hierarchical pore MFI molecular sieve one-step synthesis |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145142A (en) * | 2015-04-13 | 2016-11-23 | 中国石油化工股份有限公司 | Removing molecular sieve organic formwork agent method |
| CN106145142B (en) * | 2015-04-13 | 2019-04-12 | 中国石油化工股份有限公司 | Remove molecular sieve organic formwork agent method |
| CN105217649A (en) * | 2015-10-26 | 2016-01-06 | 中国科学院广州能源研究所 | A kind of two steps in low temperature removes the method for organic formwork agent and realizes the device of the method |
| CN109465024A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using MTW type structure molecular screen as the isomerization catalyst preparation method of carrier |
| CN109465031A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using AFO type structure molecular screen as the isomerization catalyst preparation method of carrier |
| CN109467103A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | A method of removing Molecular Sieves as Template agent |
| CN109465031B (en) * | 2017-09-07 | 2021-07-20 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst taking AFO type structure molecular sieve as carrier |
| CN109465024B (en) * | 2017-09-07 | 2021-09-07 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst with MTW type structure molecular sieve as carrier |
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