CN110330030B - Production method for producing selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate - Google Patents
Production method for producing selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate Download PDFInfo
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- CN110330030B CN110330030B CN201910698545.7A CN201910698545A CN110330030B CN 110330030 B CN110330030 B CN 110330030B CN 201910698545 A CN201910698545 A CN 201910698545A CN 110330030 B CN110330030 B CN 110330030B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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Abstract
The invention relates to a production method for producing a selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate, belonging to the field of molecular sieve preparation; the method comprises the following steps: adding the mother liquor into a pulping tank, and then adding silica gel, low caustic ratio sodium metaaluminate, a template agent and neutral water; transferring the material into a pressure reaction kettle, stirring and heating to 130-180 ℃, keeping the temperature, and keeping the constant temperature at 0.3-1.0 MPa; keeping the temperature for 15-25 h, and then relieving pressure and cooling; filtering and washing the mixed solution after reaction; drying and roasting the filter cake (the temperature is lower than 600 ℃), and discharging; the low caustic ratio sodium metaaluminate in the step (1) is liquid sodium metaaluminate, and the caustic ratio is 2.0-2.2. The invention reduces the use and loss of sodium oxide in production, reduces pollutant discharge and material waste, and reduces production cost. The causticity ratio of sodium metaaluminate is reduced, thereby reducing the consumption and loss of sodium oxide in production and improving the utilization rate of raw materials.
Description
Technical Field
The invention relates to a production method for producing a selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate, belonging to the field of molecular sieve preparation.
Background
The shape-selective molecular sieve is widely applied to the field of petroleum catalytic cracking in the chemical industry, has very high shape-selective catalytic function, and is one of the common molecular sieves in the petroleum industry;
the raw materials used by the existing company to produce the selective molecular sieve comprise silica gel, sodium metaaluminate and a template agent, the causticity ratio of the used sodium metaaluminate is about 2.5, the content of sodium oxide in the sodium metaaluminate is high, and under the condition of normal production, the content of sodium oxide is high, so that the sodium oxide which enters the subsequent process and can not be recycled is more, and the loss of the sodium oxide is large, thereby causing waste.
Disclosure of Invention
According to the defects of the prior art, the technical problems to be solved by the invention are as follows: the method for producing the selective molecular sieve ZSM-5 by using the low caustic ratio sodium metaaluminate reduces the caustic ratio of the sodium metaaluminate, thereby reducing the consumption and loss of sodium oxide in production and improving the utilization rate of raw materials.
The technical scheme adopted by the invention for solving the technical problems is as follows: provides a production method for producing a selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate, which comprises the following steps:
(1) Adding the mother liquor into a pulping tank, and then adding silica gel, low caustic ratio sodium metaaluminate, a template agent and neutral water;
(2) Transferring the material into a pressure reaction kettle, stirring and heating to 130-180 ℃, keeping the temperature, and keeping the constant temperature at the pressure of 0.3-1.0 MPa;
(3) Keeping the temperature for 15-25 h, and then relieving pressure and cooling;
(4) Filtering and washing the mixed solution after reaction;
(5) Drying and roasting the filter cake (the temperature is lower than 600 ℃), and discharging;
the low caustic ratio sodium metaaluminate in the step (1) is liquid sodium metaaluminate, and the caustic ratio is 2.0-2.2.
The mother liquor is a filtrate obtained by filtering a mixed liquor obtained after raw material reaction in the molecular sieve preparation process of the molecular sieve ZSM-5.
The template agent is organic amine and comprises ethylamine, propylamine, butylamine and quaternary ammonium salt.
The liquid sodium metaaluminate has 130 plus or minus 2.0g/L of sodium oxide, 102 plus or minus 2.0g/L of silicon oxide and 2.0-2.2 of caustic ratio, and has clear and transparent appearance.
The production method of the low-silica-alumina selective molecular sieve ZSM-5 comprises the following steps of: mother liquor: silica gel: sodium metaaluminate: template agent: neutral water =2-3:1:0.3-0.4:0.08-0.15:0.5-1.0.
The selective molecular sieve produced by the scheme replaces a common sodium metaaluminate solution (caustic ratio is 2.5) with a low-causticity ratio sodium metaaluminate solution (caustic ratio is 2.0-2.2), a silicon source still uses solid silica gel, and a template agent is added to realize the synthesis of the molecular sieve;
by optimizing the formula, the reduced alkalinity in the low caustic ratio sodium metaaluminate is supplemented by using the molecular sieve filtration filtrate (mother liquor), so that the proper alkalinity is provided for the system, and the normal operation of the reaction is ensured;
the produced molecular sieve filter filtrate (mother liquor) is completely recycled and used for pulping raw material solid silica gel, and the non-filter filtrate is discharged;
because the causticity ratio of the raw material sodium metaaluminate is reduced, namely the content of sodium oxide in the sodium metaaluminate is reduced, the sodium oxide feeding is reduced by about 16 percent compared with the normal sodium metaaluminate.
The invention has the beneficial effects that:
1. the invention reduces the use and loss of sodium oxide in production, reduces pollutant discharge and material waste, and reduces production cost.
2. The causticity ratio of sodium metaaluminate is reduced, thereby reducing the consumption and loss of sodium oxide in production and improving the utilization rate of raw materials.
Detailed Description
The following further describes embodiments of the present invention:
example 1
A method for producing selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate comprises the following steps:
(1) Adding the mother liquor into a pulping tank, and then adding silica gel, low caustic ratio sodium metaaluminate, a template agent and neutral water;
(2) Transferring the material into a pressure reaction kettle, stirring and heating to 130-140 ℃, keeping the temperature, and keeping the constant temperature at 0.3-0.5 MPa;
(3) Keeping the temperature for 15 hours, and then relieving pressure and reducing temperature;
(4) Filtering and washing the mixed solution after reaction;
(5) Drying and roasting the filter cake (the temperature is not more than 600 ℃), and discharging;
the low caustic ratio sodium metaaluminate in the step (1) is liquid sodium metaaluminate, and the caustic ratio is 2.0.
The template agent is ethylamine.
The liquid sodium metaaluminate has 130 plus or minus 2.0g/L of sodium oxide and 102 plus or minus 2.0g/L of silicon oxide, and is clear and transparent in appearance.
The mass ratio of the feeding amount is as follows: mother liquor: silica gel: sodium metaaluminate: template agent: neutral water =2:1:0.3:0.08:0.5.
the silica gel: the requirement is that the coarse-pore silica gel has a particle size distribution of 0-149 μm or more than 92.0%.
The quality index of the prepared ZSM-5 product is as follows: the ignition loss is less than or equal to 10 percent, the relative crystallinity is more than or equal to 90 percent, and the sodium oxide is less than or equal to0.20 percent, the ratio of silicon to aluminum is 40-50, and the specific surface is more than or equal to 300m 2 /g。
Example 2
A method for producing selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate comprises the following steps:
(1) Adding the mother liquor into a pulping tank, and then adding silica gel, low caustic ratio sodium metaaluminate, a template agent and neutral water;
(2) Transferring the material into a pressure reaction kettle, stirring and heating to 170-180 ℃, keeping the temperature, and keeping the constant temperature at 0.8-1.0 MPa;
(3) Keeping the temperature for 25h, and then relieving pressure and cooling;
(4) Filtering and washing the mixed solution after reaction;
(5) Drying and roasting the filter cake (the temperature is not more than 600 ℃), and discharging;
the low caustic ratio sodium metaaluminate in the step (1) is liquid sodium metaaluminate, and the caustic ratio is 2.2.
The template agent is propylamine.
The liquid sodium metaaluminate has 130 plus or minus 2.0g/L of sodium oxide and 102 plus or minus 2.0g/L of silicon oxide, and is clear and transparent in appearance.
The mass ratio of the feeding amount is as follows: mother liquor: silica gel: sodium metaaluminate: template agent: neutral water =3:1:0.4:0.15:1.0.
the silica gel: the coarse silica gel is required to have a particle size distribution of 0-149 μm or more than 92.0%.
The quality index of the prepared ZSM-5 product is as follows: the ignition loss is less than or equal to 10 percent, the relative crystallinity is more than or equal to 90 percent, the sodium oxide is less than or equal to 0.20 percent, the silicon-aluminum ratio is 40-50, and the specific surface is more than or equal to 300m 2 /g。
Example 3
A method for producing selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate comprises the following steps:
(1) Adding the mother liquor into a pulping tank, and then adding silica gel, low caustic ratio sodium metaaluminate, a template agent and neutral water;
(2) Transferring the material into a pressure reaction kettle, stirring and heating to 150-160 ℃, keeping the temperature, and keeping the constant temperature at 0.5-0.7 MPa;
(3) Keeping the temperature for 20 hours, and then relieving pressure and reducing temperature;
(4) Filtering and washing the mixed solution after reaction;
(5) Drying and roasting the filter cake (the temperature is not more than 600 ℃), and discharging;
the low caustic ratio sodium metaaluminate in the step (1) is liquid sodium metaaluminate, and the caustic ratio is 2.1.
The template agent is butylamine.
The liquid sodium metaaluminate has 130 plus or minus 2.0g/L of sodium oxide and 102 plus or minus 2.0g/L of silicon oxide, and is clear and transparent in appearance.
The mass ratio of the feeding amount is as follows: mother liquor: silica gel: sodium metaaluminate: template agent: neutral water =2.5:1:0.35:0.12:0.7.
the silica gel: the requirement is that the coarse-pore silica gel has a particle size distribution of 0-149 μm or more than 92.0%.
The quality index of the prepared ZSM-5 product is as follows: the ignition loss is less than or equal to 10 percent, the relative crystallinity is more than or equal to 90 percent, the sodium oxide is less than or equal to 0.20 percent, the silicon-aluminum ratio is 40-50, and the specific surface is more than or equal to 300m 2 /g。
Claims (1)
1. A production method for producing selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate is characterized by comprising the following steps:
(1) Adding the mother liquor into a pulping tank, and then adding silica gel, low caustic ratio sodium metaaluminate, a template agent and neutral water;
(2) Transferring the material into a pressure reaction kettle, stirring and heating to 130-180 ℃, keeping the temperature, and keeping the constant temperature at 0.3-1.0 MPa;
(3) Keeping the temperature for 15-25 h, and then relieving pressure and cooling;
(4) Filtering and washing the mixed solution after reaction;
(5) Drying and roasting the filter cake, and discharging;
the low caustic ratio sodium metaaluminate in the step (1) is liquid sodium metaaluminate, and the caustic ratio is 2.0-2.2;
the template agent is organic amine and comprises ethylamine, propylamine, butylamine and quaternary ammonium salt;
the mass ratio of the raw materials in the step (1) is as follows: mother liquor: silica gel: sodium metaaluminate: template agent: neutral water =2-3:1:0.3-0.4:0.08-0.15:0.5-1.0;
the mother liquor is a filtrate obtained by filtering a mixed liquor obtained after raw material reaction in the molecular sieve preparation process of the molecular sieve ZSM-5.
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| EP1817258A1 (en) * | 2004-11-08 | 2007-08-15 | SASOL ITALY S.p.A. | Improved process for the preparation of zms-5 zeolites |
| CN101468807A (en) * | 2007-12-25 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 molecular sieve |
| CN102616807A (en) * | 2012-03-29 | 2012-08-01 | 北京化工大学 | Method for synthesizing Y type molecular sieve |
| CN102826569A (en) * | 2012-08-14 | 2012-12-19 | 华南理工大学 | Preparation method for mesoporous ZSM-5 zeolite molecular sieve |
| CN105000572A (en) * | 2014-12-24 | 2015-10-28 | 北京恩泽福莱科技有限公司 | Synthetic method of small-crystal ZSM-5 molecular sieve |
| CN107720773A (en) * | 2017-10-30 | 2018-02-23 | 中海油天津化工研究设计院有限公司 | A kind of method for efficiently synthesizing the molecular sieves of B Al ZSM 5 |
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- 2019-07-31 CN CN201910698545.7A patent/CN110330030B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1817258A1 (en) * | 2004-11-08 | 2007-08-15 | SASOL ITALY S.p.A. | Improved process for the preparation of zms-5 zeolites |
| CN101468807A (en) * | 2007-12-25 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 molecular sieve |
| CN102616807A (en) * | 2012-03-29 | 2012-08-01 | 北京化工大学 | Method for synthesizing Y type molecular sieve |
| CN102826569A (en) * | 2012-08-14 | 2012-12-19 | 华南理工大学 | Preparation method for mesoporous ZSM-5 zeolite molecular sieve |
| CN105000572A (en) * | 2014-12-24 | 2015-10-28 | 北京恩泽福莱科技有限公司 | Synthetic method of small-crystal ZSM-5 molecular sieve |
| CN107720773A (en) * | 2017-10-30 | 2018-02-23 | 中海油天津化工研究设计院有限公司 | A kind of method for efficiently synthesizing the molecular sieves of B Al ZSM 5 |
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