CN111675225B - Regulator for synthesis process of silicon-aluminum-phosphorus molecular sieve and use method - Google Patents
Regulator for synthesis process of silicon-aluminum-phosphorus molecular sieve and use method Download PDFInfo
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- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention provides a regulator used in the synthesis process of a silicon-aluminum-phosphorus molecular sieve and a using method thereof. The invention provides a regulator used in the synthesis process of a silicon-aluminum-phosphorus molecular sieve and a use method thereof, which can remedy the poor synthesis reaction effect of the silicon-aluminum-phosphorus molecular sieve and improve the catalytic performance of the silicon-aluminum-phosphorus molecular sieve.
Description
Technical Field
The invention belongs to the technical field of methanol-to-olefin, and particularly relates to a regulator used in a synthesis process of a silicon-aluminum-phosphorus molecular sieve and a use method thereof.
Background
Propylene is one of the most important bulk chemical products in the world and basic chemical raw materials supporting the economic development of China at present, and can be used for preparing various basic organic raw materials, such as propylene oxide, acrolein, allyl alcohol, isopropanol, carbon tetrachloride, butanol and the like. In recent years, the demand for propylene has increased dramatically due to the demand for downstream derivatives, particularly polypropylene. Due to shortage of domestic propylene resources, the demand of domestic markets can not be met, the domestic self-sufficiency rate is greatly reduced, and a large amount of imports are needed. With the strongly competitive environment of the international market, the most advanced international environment-friendly process technology must be adopted for developing propylene and derivatives thereof, so that the large-scale economic scale of low-cost production is achieved, and the development and utilization prospects of propylene in China are wide.
Aiming at the development prospect of propylene in China, a methanol-to-propylene catalyst developed by the Chinese Houtt engineering Co., ltd is mainly a silicon-aluminum-phosphorus molecular sieve, the molecular sieve can enable the conversion rate of methanol to reach 100% or approach 100%, the selectivity of ethylene and propylene to be more than 78%, almost no products with more than 5C exist, and the outstanding hydrothermal stability and the proper pore structure of the silicon-aluminum-phosphorus molecular sieve enable the performance of the silicon-aluminum-phosphorus molecular sieve to be more excellent, so that the silicon-aluminum-phosphorus molecular sieve can be widely applied in the future.
The grain size and structure of the silicon-aluminum-phosphorus molecular sieve influence the catalytic performance of the silicon-aluminum-phosphorus molecular sieve, the optimal grain size is about 1 micron, and the optimal structure is a cube structure. In the process of synthesizing the silicon-aluminum-phosphorus molecular sieve, the conditions of uneven grain growth, uncontrollable grain growth and grain size, various irregular shapes such as a rod shape, an octagon shape, a decagon shape, a sphere shape and the like often occur, so that the catalytic performance is poor. In the prior art, if the reaction time is more than 10-16 hours, but the number of cubic crystal grains is not 99%, the catalytic performance of the synthesized silicon-aluminum-phosphorus molecular sieve becomes worse, and the synthesized silicon-aluminum-phosphorus molecular sieve can become waste or needs to take remedial measures. The problem of adopting the remedial measure is that even if the synthetic raw materials are added, the subsequent crystal grain forming is uncontrollable, and higher waste risk still exists. The silicoaluminophosphate molecular sieve is usually synthesized by using a reaction kettle, the reaction temperature is generally higher, usually 200-250 ℃, when the reaction process needs to be remedied, the reaction kettle is usually cooled to room temperature, and then synthesis raw materials are supplemented, so that the method is time-consuming and labor-consuming, and is not beneficial to the production of the silicoaluminophosphate molecular sieve.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a regulator for a silicon-aluminum-phosphorus molecular sieve synthesis process and a use method thereof, wherein the regulator is used for remedying when the synthesis condition of the silicon-aluminum-phosphorus molecular sieve is not ideal, so that the catalytic performance of the silicon-aluminum-phosphorus molecular sieve is improved.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a regulator used in the synthesis process of a silicon-aluminum-phosphorus molecular sieve comprises a first component, a second component and a third component, wherein the first component comprises sodium carboxymethylcellulose and trimethylolpropane, the second component comprises desalted water and isopropanol, and the third component comprises inert gas and ammonia gas; preferably, the inert gas is nitrogen.
Further, the mass ratio of the sodium carboxymethyl cellulose to the trimethylolpropane in the first component is as follows: 2 to 10:1 to 5.
Further, the second component also comprises butyl acrylate and methyl methacrylate.
Further, the mass ratio of the desalted water to the isopropanol to the butyl acrylate to the methyl methacrylate in the second component is as follows: 100:10 to 25:0 to 8:0 to 20.
Further, the ammonia gas in the third component adjusts the pH value of the silicon-aluminum-phosphorus molecular sieve in the synthesis process to be 5.0-6.9.
Further, the mass ratio of the first component to the second component is as follows: 1 to 20:30 to 80.
Furthermore, in the synthesis process of the silicon-aluminum-phosphorus molecular sieve of the known method, when the reaction time reaches more than 10-16 hours and the number of the cubic crystal grains is less than 99% of the total number, the synthesis raw materials and the regulator are added into the reaction process through an auxiliary feeding device.
The known method for synthesizing the silicon-aluminum-phosphorus molecular sieve comprises the following steps: uniformly mixing silica sol, pseudo-boehmite, phosphoric acid, triethylamine and desalted water according to a proportion, then putting the slurry into a synthesis reaction kettle, and crystallizing for 40-72 h at the pressure of 2.0-2.4 MPa and the temperature of 200-250 ℃ to obtain the silicon-aluminum-phosphorus molecular sieve.
Further, the mass ratio of the synthetic raw materials added in the reaction process to the total mass of the first component and the second component of the regulator is as follows: 3 to 18:1.
furthermore, the auxiliary feeding device comprises a bin, a support and a feeding pipeline, the bin is fixed on the movable support, and the feeding pipeline comprises a main pipeline, an air inlet pipeline, branch pipelines, a receiving pipeline and a liquid inlet pipeline; the main pipeline is arranged below the storage bin, the front end of the main pipeline is communicated with the air inlet pipeline, and the rear end of the main pipeline is provided with a discharge hole; the main pipeline is sequentially communicated with a branch pipeline and a material receiving pipeline from front to back, the other end of the branch pipeline is communicated with the side wall of the storage bin, and the other end of the material receiving pipeline is communicated with the bottom of the storage bin; the liquid inlet pipeline is communicated with the main pipeline and is positioned behind the connection point of the branch pipelines; preferably, the main pipe inclines downwards from front to back, and the inclination angle is less than 60 degrees.
Furthermore, valves or flowmeters are arranged on the material receiving pipeline, the branch pipeline, the air inlet pipeline and the liquid inlet pipeline, or the valves and the flowmeters are arranged at the same time; preferably, the bottom of the storage bin is provided with a level meter for detecting the height of the material in the storage bin, the valve on the branch pipeline is an induction valve, and the level meter is in signal connection with the induction valve.
The regulator used in the synthesis process of the silicon-aluminum-phosphorus molecular sieve and the use method thereof provided by the invention have the following advantages:
1. the regulator can reduce the diffusion rate of substances dissolved in water, and can effectively enhance the thermal stability of the synthesized silicon-aluminum-phosphorus molecular sieve, thereby improving the crystallinity and the particle size distribution of the molecular sieve and remedying the synthesis reaction;
2. the ammonia gas is used for adjusting the pH value to be weak acid or weak acid is neutral, so that the catalytic performance of the silicon-aluminum-phosphorus molecular sieve can be further improved;
3. the auxiliary feeding device is adopted to add the regulator into the reaction process, the regulator does not need to be added after the synthesis reaction kettle is cooled, the time is saved, and the production efficiency is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is an overall configuration diagram of an auxiliary feeding device.
Reference is made to the accompanying drawings in which: 1-a storage bin; 2-a scaffold; 3-a main pipeline; 4-a receiving pipe; 5-branch pipes; 6-an air inlet pipeline; 7-a liquid inlet pipeline; 8-a transverse plate; 9-a valve; 10-pushing hands; 11-a cross-bar; 12-a travelling wheel; 13-a fixed frame; 14-a discharge port.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are all conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
The synthesis process of the silicon-aluminum-phosphorus molecular sieve comprises the following steps: 20Kg of silica sol, 80Kg of pseudo-boehmite, 100Kg of phosphoric acid, 120Kg of triethylamine and 480Kg of desalted water are mixed uniformly, and then the slurry is put into a synthesis reaction kettle and crystallized for 40 to 72 hours under the pressure of 2.0 to 2.4MPa and the temperature of 200 to 250 ℃, so as to obtain the silicon-aluminum-phosphorus molecular sieve. The synthesis of the silicoaluminophosphate molecular sieves in the following examples and comparative examples was carried out in accordance with this procedure.
The auxiliary feeding device comprises a storage bin 1, a support 2 and a feeding pipeline, wherein walking wheels 12 are arranged at the bottom end of the support 2, and the support 2 can move through the walking wheels 12; the support 2 is provided with a cross rod 11, and the support 2 is also provided with a push handle 10 which is convenient to use; the feed bin 1 is a container with an opening at the upper end, the feed bin 1 is fixed on the bracket 2 through a transverse plate 8, and the feed pipeline comprises a main pipeline 3, an air inlet pipeline 6, a branch pipeline 5, a material receiving pipeline 4 and a liquid inlet pipeline 7; the main pipeline 3 is arranged below the storage bin 1, the front end of the main pipeline 3 is communicated with the air inlet pipeline 6, and the rear end of the main pipeline 3 is provided with a discharge hole 14; the main pipeline 3 is sequentially communicated with a branch pipeline 5 and a material receiving pipeline 4 from front to back, the other end of the branch pipeline 5 is communicated with the side wall of the storage bin 1, and the other end of the material receiving pipeline 4 is communicated with the bottom of the storage bin 1; the liquid inlet pipeline 7 is communicated with the main pipeline 3 and is positioned behind the connection point of the branch pipelines 5; preferably, the main pipeline inclines downwards from front to back, and the inclination angle is less than 60 degrees, so that the feeding is facilitated. A plurality of gas inlet pipelines 6 can be arranged according to the types of the introduced gases; because two kinds of gas are introduced in the subsequent embodiment, the auxiliary feeding device used in the embodiment is provided with two gas inlet pipelines 6; the auxiliary feeding device used in the comparative example was provided with an air inlet duct 6; according to different requirements, a plurality of liquid inlet pipelines 7 can be arranged, and the auxiliary feeding device used in the embodiment is provided with two liquid inlet pipelines 7. Valves or flowmeters are arranged on the material receiving pipeline 4, the branch pipeline 5, the air inlet pipeline 6 and the liquid inlet pipeline 7, and preferably, the valves and the flowmeters are arranged at the same time; preferably, the valve on the branch pipeline 5 is an induction valve, a material level meter for detecting the height of the material in the storage bin 1 is arranged at the bottom of the storage bin 1 and is in signal connection with the induction valve, and the induction valve is automatically closed after the material in the storage bin 1 is discharged. During the use, the discharge gate 14 of trunk line 3 is connected with synthetic reation kettle, first component and solid synthetic raw materials add feed bin 1, the inert gas and the ammonia of third component let in trunk line 3 through admission line 6, liquid synthetic raw materials and second component let in trunk line 3 through two inlet lines 7 respectively, liquid and solid matter in promoting trunk line 3 through inert gas flow out from discharge gate 14 and enter into synthetic reation kettle, a part of gas enters into feed bin 1 through lateral conduit 5, accelerate the unloading speed of interior material of feed bin 1. The auxiliary feeding devices and the use modes mentioned in the subsequent embodiments are the same as those described above.
Comparative example one: uniformly mixing silica sol, pseudo-boehmite, phosphoric acid, triethylamine and desalted water according to a proportion, then putting the slurry into a synthesis reaction kettle, and crystallizing for 52 hours at the pressure of 2.2MPa and the temperature of 230 ℃ to obtain the silicon-aluminum-phosphorus molecular sieve.
Comparative example two: uniformly mixing silica sol, pseudo-boehmite, phosphoric acid, triethylamine and desalted water according to a proportion, then putting the slurry into a synthesis reaction kettle, crystallizing for 12 hours at the pressure of 2.2MPa and the temperature of 230 ℃, adding the phosphoric acid and the pseudo-boehmite into the synthesis reaction kettle by adopting an auxiliary feeding device when the number of cubic crystal grains is found to be less than 99% of the total number, pushing the materials into the synthesis reaction kettle by nitrogen, and continuously reacting for 40 hours to obtain the silicon-aluminum-phosphorus molecular sieve.
The first embodiment is as follows:
the first component of the regulator is sodium carboxymethylcellulose and trimethylolpropane, the second component is desalted water, isopropanol, butyl acrylate and methyl methacrylate, and the third component is nitrogen and ammonia; the mass ratio of the first component to the second component is as follows: 14:47; the mass ratio of the sodium carboxymethylcellulose to the trimethylolpropane in the first component is as follows: 8:3; the mass ratio of desalted water, isopropanol, butyl acrylate and methyl methacrylate in the second component is as follows: 100:13:7:19. in the synthesis process of the silicon-aluminum-phosphorus molecular sieve, samples are taken from reaction liquid once every 1-2 hours, after the reaction time lasts for 12 hours, the number of cubic crystal grains accounts for 83% of the total number, an auxiliary feeding device is utilized to add synthesis raw materials and a regulator into a synthesis reaction kettle, the added synthesis raw materials are 50Kg of pseudo-boehmite, 40Kg of phosphoric acid, 2.64Kg of a first component material and 8.86Kg of a second component material are added, 270L of ammonia gas is introduced to adjust the reaction pH of the synthesis reaction kettle to 6.5, the first component material and the second component material are pushed into the synthesis reaction kettle by nitrogen gas, and then the reaction is stopped after the reaction continues for 40 hours in the synthesis reaction kettle.
The second embodiment:
the first component of the regulator is sodium carboxymethylcellulose and trimethylolpropane, the second component is desalted water, isopropanol and butyl acrylate, the third component is nitrogen and ammonia, and the mass ratio of the first component to the second component is as follows: 13:77; the mass ratio of the sodium carboxymethylcellulose to the trimethylolpropane in the first component is as follows: 3:4; the mass ratio of desalted water, isopropanol and butyl acrylate in the second component is as follows: 100:19:8. In the synthesis process of the silicon-aluminum-phosphorus molecular sieve, samples are taken from reaction liquid once every 1-2 hours, after the reaction time lasts for 14 hours, the number of cubic crystal grains accounts for 93 percent of the total number, an auxiliary feeding device is utilized to add synthesis raw materials and a regulator into a synthesis reaction kettle, the added synthesis raw materials are 60Kg of pseudo-boehmite and 20Kg of phosphoric acid, 2.74Kg of a first component material is added, 16.23Kg of a second component material is added, 212L of ammonia gas is introduced to adjust the reaction pH of the synthesis reaction kettle to 6.4, the first component material and the second component material are pushed into the synthesis reaction kettle by nitrogen gas, and then the reaction is stopped after the reaction continues for 41 hours in the synthesis reaction kettle.
Example three:
the first component of the regulator is sodium carboxymethylcellulose and trimethylolpropane, the second component is desalted water, isopropanol, butyl acrylate and methyl methacrylate, the third component is nitrogen and ammonia, and the mass ratio of the first component to the second component is as follows: 18:70; the mass ratio of the sodium carboxymethylcellulose to the trimethylolpropane in the first component is as follows: 4:5; the mass ratio of desalted water, isopropanol, butyl acrylate and methyl methacrylate in the second component is as follows: 100:24:2:15. in the synthesis process of the silicon-aluminum-phosphorus molecular sieve, samples are taken from reaction liquid every 1-2 hours, after the reaction time lasts 13 hours, the number of cubic crystal grains accounts for 80% of the total number, an auxiliary feeding device is utilized to add synthesis raw materials and a regulator into a synthesis reaction kettle, the added synthesis raw materials are 30Kg of pseudo-boehmite, 30Kg of phosphoric acid, 4.7Kg of a first component material and 18.3Kg of a second component material are added, 378L of ammonia is introduced to adjust the reaction PH of the synthesis reaction kettle to 6.6, the first component material and the second component material are pushed into the synthesis reaction kettle by nitrogen, and then the reaction is stopped after the reaction continues for 50 hours in the synthesis reaction kettle.
Example four:
the first component of the regulator is sodium carboxymethylcellulose and trimethylolpropane, the second component is desalted water, isopropanol and methyl methacrylate, the third component is nitrogen and ammonia, and the mass ratio of the first component to the second component is as follows: 4:45, a first step of; the mass ratio of the sodium carboxymethylcellulose to the trimethylolpropane in the first component is as follows: 2:5; the mass ratio of desalted water, isopropanol and methyl methacrylate in the second component is as follows: 100:13:7. in the synthesis process of the silicon-aluminum-phosphorus molecular sieve, samples are taken from reaction liquid once every 1-2 hours, after the reaction time lasts for 15 hours, the number of cubic crystal grains accounts for 88% of the total number, an auxiliary feeding device is utilized to add synthesis raw materials and a regulator into a synthesis reaction kettle, the added synthesis raw materials are 25Kg of pseudo-boehmite and 10Kg of phosphoric acid, 0.57Kg of a first component material is added, 6.41Kg of a second component material is added, 453L of ammonia gas is introduced to adjust the reaction pH of the synthesis reaction kettle to 6.3, the first component material and the second component material are pushed into the synthesis reaction kettle by nitrogen gas, and then the reaction is stopped after the reaction continues for 51 hours in the synthesis reaction kettle.
Example five:
the first component of the regulator is sodium carboxymethylcellulose and trimethylolpropane, the second component is desalted water and isopropanol, the third component is nitrogen and ammonia, and the mass ratio of the first component to the second component is as follows: 18:35; the mass ratio of the sodium carboxymethylcellulose to the trimethylolpropane in the first component is as follows: 7:4; the mass ratio of desalted water to isopropanol in the second component is as follows: 100:23. in the process of synthesizing the silicon-aluminum-phosphorus molecular sieve, samples are taken from reaction liquid once every 1-2 hours, after the reaction time lasts for 11 hours, the number of cubic crystal grains accounts for 92% of the total number, an auxiliary feeding device is utilized to add synthesis raw materials and a regulator into a synthesis reaction kettle, the added synthesis raw materials are 35Kg of pseudo-boehmite, 15Kg of phosphoric acid, 1.7Kg of a first component material and 3.3Kg of a second component material are added, 298L of ammonia gas is introduced to adjust the reaction pH of the synthesis reaction kettle to 6.8, the first component and the second component materials are pushed into the synthesis reaction kettle by nitrogen gas, and then the reaction is stopped after the reaction is continued for 47 hours in the synthesis reaction kettle.
Example six:
the first component of the regulator is sodium carboxymethylcellulose and trimethylolpropane, the second component is desalted water, isopropanol, butyl acrylate and methyl methacrylate, the third component is nitrogen and ammonia, and the mass ratio of the first component to the second component is as follows: 2:67; the mass ratio of the sodium carboxymethylcellulose to the trimethylolpropane in the first component is as follows: 7:2; the mass ratio of desalted water, isopropanol, butyl acrylate and methyl methacrylate in the second component is as follows: 100:24:0.03:0.01. in the synthesis process of the silicon-aluminum-phosphorus molecular sieve, samples are taken from reaction liquid once every 1-2 hours, after the reaction time lasts for 12 hours, the number of cubic crystal grains accounts for 90% of the total number, an auxiliary feeding device is utilized to add synthesis raw materials and a regulator into a synthesis reaction kettle, the added synthesis raw materials are 30Kg of pseudo-boehmite, 30Kg of phosphoric acid, 0.64Kg of a first component material is added, 21.44Kg of a second component material is added, 311L of ammonia gas is introduced to adjust the reaction pH of the synthesis reaction kettle to 6.8, the first component material and the second component material are pushed into the synthesis reaction kettle by nitrogen gas, and then the reaction is stopped after the reaction continues for 53 hours in the synthesis reaction kettle.
The catalytic performance of the silicoaluminophosphate molecular sieves synthesized according to the comparative example I, the comparative example II, the example I, the example II, the example III, the example IV, the example V and the example VI was verified, and the following data were obtained:
| ethylene selectivity% | Selectivity to propylene% | Conversion rate% | |
| Example one | 39.4 | 41.1 | 99.5 |
| Example two | 38.9 | 40.7 | 99.7 |
| EXAMPLE III | 40.2 | 39.9 | 99.3 |
| Example four | 39.9 | 40.2 | 99.6 |
| EXAMPLE five | 39.7 | 41.3 | 99.5 |
| Example six | 39.2 | 41.0 | 99.5 |
| Comparative example 1 | 36.8 | 38.4 | 97.4 |
| Comparative example No. two | 37.0 | 37.8 | 96.2 |
According to the experimental data, in the process of the silicon-aluminum-phosphorus synthesis reaction, when the reaction time reaches more than 10-16 hours, mixed crystals appear in the reaction process, and the ratio of the number of cubic crystal grains is not 99%, the mixed crystals are remedied by adding the regulator, and the silicon-aluminum-phosphorus molecular sieve is obtained after the regulator is added, so that the conversion rate is high, the selectivity is good, and the overall catalytic performance is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A regulator used in the synthesis process of a silicon-aluminum-phosphorus molecular sieve is characterized in that: the composite material comprises a first component, a second component and a third component, wherein the first component comprises sodium carboxymethylcellulose and trimethylolpropane, the second component comprises desalted water, isopropanol, butyl acrylate and methyl methacrylate, and the third component comprises inert gas and ammonia gas;
the mass ratio of the sodium carboxymethylcellulose to the trimethylolpropane in the first component is as follows: 2 to 10:1 to 5;
the mass ratio of desalted water, isopropanol, butyl acrylate and methyl methacrylate in the second component is as follows: 100:10 to 25:0 to 8:0 to 20;
the ammonia in the third component adjusts the pH value of the silicon-aluminum-phosphorus molecular sieve in the synthesis process to be 5.0-6.9;
the mass ratio of the first component to the second component is as follows: 1 to 20:30 to 80.
2. A using method of a regulator used in the synthesis process of a silicon-aluminum-phosphorus molecular sieve is characterized by comprising the following steps: in the process of synthesizing the silicon-aluminum-phosphorus molecular sieve, when the reaction time is more than 10 to 16 hours and the number of the cubic crystal grains is less than 99 percent of the total number, adding a synthesis raw material and the regulator of claim 1 into the reaction process through an auxiliary feeding device.
3. The use method of the regulator for the synthesis process of the silicon-aluminum-phosphorus molecular sieve as claimed in claim 2, characterized in that: the mass ratio of the synthetic raw materials added in the reaction process to the total mass of the first component and the second component of the regulator is as follows: 3 to 18:1.
4. the use method of the regulator for the synthesis process of the silicon-aluminum-phosphorus molecular sieve as claimed in claim 2, characterized in that: the auxiliary feeding device comprises a storage bin (1), a support (2) and a feeding pipeline, wherein the storage bin (1) is fixed on the movable support (2), and the feeding pipeline comprises a main pipeline (3), an air inlet pipeline (6), a branch pipeline (5), a material receiving pipeline (4) and a liquid inlet pipeline (7); the main pipeline (3) is arranged below the storage bin (1), the front end of the main pipeline (3) is communicated with the air inlet pipeline (6), and the rear end of the main pipeline is provided with a discharge hole (14); the main pipeline (3) is sequentially communicated with a branch pipeline (5) and a material receiving pipeline (4) from front to back, the other end of the branch pipeline (5) is communicated with the side wall of the storage bin (1), and the other end of the material receiving pipeline (4) is communicated with the bottom of the storage bin (1); the liquid inlet pipeline (7) is communicated with the main pipeline (3) and is positioned behind the connection point of the branch pipelines (5).
5. The use method of the regulator for the synthesis process of the silicon-aluminum-phosphorus molecular sieve as claimed in claim 4, characterized in that: and valves or flowmeters are arranged on the material receiving pipeline (4), the branch pipeline (5), the air inlet pipeline (6) and the liquid inlet pipeline (7), or the valves and the flowmeters are arranged at the same time.
6. The use method of the regulator for the synthesis process of the silicon-aluminum-phosphorus molecular sieve according to claim 5, is characterized in that: the material level measuring device is characterized in that a material level meter for detecting the height of materials in the material bin (1) is arranged at the bottom of the material bin (1), a valve on the branch pipeline (5) is a sensing valve, and the material level meter is in signal connection with the sensing valve.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170128379A1 (en) * | 2014-06-30 | 2017-05-11 | Rubicon Research Private Limited | Modified release pharmaceutical preparations |
| CN110981458A (en) * | 2019-12-27 | 2020-04-10 | 中国天辰工程有限公司 | Device for containing silicon-aluminum-phosphorus molecular sieve and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170128379A1 (en) * | 2014-06-30 | 2017-05-11 | Rubicon Research Private Limited | Modified release pharmaceutical preparations |
| CN110981458A (en) * | 2019-12-27 | 2020-04-10 | 中国天辰工程有限公司 | Device for containing silicon-aluminum-phosphorus molecular sieve and preparation method thereof |
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