CN115805089B - Methylamine shape-selective catalyst and preparation method thereof - Google Patents
Methylamine shape-selective catalyst and preparation method thereof Download PDFInfo
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- CN115805089B CN115805089B CN202310060564.3A CN202310060564A CN115805089B CN 115805089 B CN115805089 B CN 115805089B CN 202310060564 A CN202310060564 A CN 202310060564A CN 115805089 B CN115805089 B CN 115805089B
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- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to the technical field of catalyst preparation, and particularly discloses a methylamine shape-selective catalyst and a preparation method thereof. The methylamine shape-selective catalyst raw material comprises the following components in percentage by mass: 4-6% of silicon source, 27-30% of soluble aluminum salt, 0.2-1.0% of soluble transition metal salt, 2-4% of organic phosphorus compound, 10-15% of silicon kneading agent and the balance of water; wherein the silicon source is a mixture of silicon dioxide and sodium silicate, and the aluminum source is a mixture of aluminum chloride and aluminum nitrate. The radial crushing strength of the methylamine shape-selective catalyst prepared by reasonable proportioning and specific selection of the raw materials reaches 100N/cm 2 The wear resistance reaches 95%/h, and the methanol conversion rate and the total amine selectivity can be further improved, and the selectivity of dimethyl ether impurities can be further reduced.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a methylamine shape-selective catalyst and a preparation method thereof.
Background
The three methylamine products of methylamine which are important chemical raw materials respectively have corresponding application, and the market demand is unbalanced. For the last two years, the market of N-methylpyrrolidone (NMP), another product of monomethylamine downstream, has been continuously growing, NMP can be used as a solvent for positive electrode materials in the field of lithium ion batteries, can be used as a cleaning agent for semiconductors and integrated circuits in the electronic industry, and can also be used in the aspect of PVC tail gas recovery in the field of environmental protection. At present, due to the rapid growth of the chip industry and the electric automobile industry, monomethylamine as one of the NMP synthesis raw materials will come to a rapid growth period. Therefore, improvement of the production efficiency of monomethylamine is urgent.
However, the current industrial production process of methylamine controls dimethylamine as a main product, and the catalyst is mainly dimethylamine catalyst. In view of the current market changes, it is necessary to develop a monomethylamine shape-selective catalyst, adjust the product structure to cope with the market demand of methylamine, and increase the economic benefit of enterprises. In recent years, the monomethylamine shape-selective catalyst is mainly a zeolite catalyst, but the zeolite catalyst has the problems of easy abrasion, short service life, low conversion rate to raw materials, high content of dimethyl ether impurities and the like. Therefore, it is of great importance to provide a methylamine shape-selective catalyst with high strength, high conversion rate of raw materials and low content of dimethyl ether impurities.
Disclosure of Invention
In view of the above, the invention provides a methylamine shape-selective catalyst and a preparation method thereof, which improves the conversion rate of methanol and the selectivity of monomethylamine by adding a specific content of silicon source and soluble aluminum salt; modifying by using soluble transition metal salt and organic phosphorus compound, reducing pore canal and catalyst structure of catalyst, and restricting conversion of dimethylamine and trimethylamine; the specific silicon-based kneading agent improves the strength and abrasion resistance of the catalyst.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the methylamine shape-selective catalyst comprises the following raw materials in percentage by mass: 4-6% of silicon source, 27-30% of soluble aluminum salt, 0.2-1.0% of soluble transition metal salt, 2-4% of organic phosphorus compound, 10-15% of silicon kneading agent and the balance of water; wherein the silicon source is a mixture of silicon dioxide and sodium silicate, and the soluble aluminum salt is a mixture of aluminum chloride and aluminum nitrate.
Compared with the prior art, the methylamine shape-selective catalyst provided by the invention has the advantages that silicon dioxide and sodium silicate are used as silicon sources, aluminum chloride and aluminum nitrate are used as soluble aluminum salts, the specific contents of the silicon sources and the soluble aluminum salts are limited, the specific surface area and the micropore diameter of the prepared catalyst can be improved, and finally the conversion rate of methanol and the selectivity of monomethylamine are improved; the addition of the soluble transition metal salt and the organic phosphorus compound enables the surface of the pore canal of the catalyst to form a coating, thereby reducing the pore canal and the catalyst structure of the catalyst, restricting the conversion of dimethylamine and trimethylamine and improving the selectivity of monomethylamine; the specific silicon-based kneading agent ensures that the prepared methylamine shape-selective catalyst has uniform pore size and improves the strength of the methylamine shape-selective catalystAnd wear resistance; the radial crushing strength of the prepared catalyst reaches 100N/cm by reasonable proportion and specific selection of the raw materials 2 The wear resistance reaches 95%/h, and the methanol conversion rate and the total amine selectivity can be further improved, and the selectivity of dimethyl ether impurities can be further reduced.
Preferably, the silicon source is a mixture of silicon dioxide and sodium silicate in a mass ratio of 1:0.8-2.6.
Preferably, the soluble aluminum salt is a mixture of aluminum chloride and aluminum nitrate in a mass ratio of 1:0.5-1.5.
The preferred silicon source and soluble aluminum salt can increase the specific surface area and pore size of the catalyst, further increasing the conversion of methanol and the selectivity of monomethylamine.
Preferably, the soluble transition metal salt is at least one of cobalt nitrate, ammonium molybdate or copper oxalate.
The preferable soluble transition metal salt forms a coating on the surface of the pore canal of the catalyst, further reduces the pore canal and the catalyst structure of the catalyst, and improves the selectivity of the monomethylamine.
Preferably, the organic phosphorus compound is at least one of trimethyl phosphate or triethyl phosphate.
The catalyst is modified by the preferable organic phosphorus compound, which is favorable for forming a specific coating, further improves the selectivity of monomethylamine and reduces the selectivity of dimethyl ether impurities.
Preferably, the silicon-based kneading agent is silicon carbide.
Further preferably, the silicon carbide has a particle size of 300 to 1000 mesh.
The invention also provides a preparation method of the methylamine shape-selective catalyst, which comprises the following steps:
step a, weighing all raw materials according to a designed proportion, and uniformly mixing a weighed silicon source, soluble aluminum salt and water to obtain a mixed salt solution; under the condition of microwave heating, adding the weighed soluble transition metal salt and the organophosphorus compound into the mixed salt solution, carrying out microwave heating reaction, then adding the weighed silicon kneading agent, uniformly mixing, and roasting to obtain the primary methylamine shape-selective catalyst;
and b, adding the primary methylamine shape-selective catalyst into an alkali solution with the pH of 7-12, heating for reaction, separating solid from liquid, washing and drying to obtain the methylamine shape-selective catalyst.
Preferably, in the step a, the microwave heating power is 500-800W, and the microwave heating reaction time is 90-120 min.
The catalyst performance is greatly improved under the optimized microwave condition, and the formed catalyst has high hardness, difficult coking and long service life.
Preferably, in the step b, the alkali solution is at least one of sodium hydroxide solution, potassium hydroxide solution or ammonia water.
Preferably, in the step a, the roasting temperature is 650-900 ℃ and the roasting time is 10-20 h.
The preferred calcination temperature facilitates catalyst formation and also improves catalyst attrition resistance and crush resistance.
Preferably, in the step b, the temperature of the heating reaction is reflux temperature, and the time of the heating reaction is 13-16 h.
The preparation method of the methylamine shape-selective catalyst provided by the invention is simple to operate, and the catalyst has high strength, good wear resistance and long service life; and the conversion rate of the methanol raw material is high, the monomethylamine selectivity is high, and the selectivity of dimethyl ether impurities can be obviously reduced.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
Example 1
The embodiment provides a methylamine shape-selective catalyst, which comprises the following raw materials in percentage by mass:
6% of a silicon source, 30% of soluble aluminum salt, 0.2% of cobalt nitrate, 4% of triethyl phosphate, 10% of silicon carbide and 49.8% of water;
wherein the silicon source is a mixture of silicon dioxide and sodium silicate in a mass ratio of 1:0.8, the soluble aluminum salt is a mixture of aluminum chloride and aluminum nitrate in a mass ratio of 1:1.5, and the particle size of the silicon carbide is 300 meshes;
the invention also provides a preparation method of the methylamine shape-selective catalyst, which comprises the following steps:
step a, weighing all raw materials according to a designed proportion, and uniformly mixing a weighed silicon source, soluble aluminum salt and water to obtain a mixed salt solution; setting the microwave power to be 500W, adding the weighed cobalt nitrate and the weighed triethyl phosphate into the mixed salt solution under the microwave heating condition, heating for 120min by microwaves, then adding the weighed silicon carbide, uniformly mixing, and roasting for 10h at 650 ℃ to obtain a primary methylamine shape-selective catalyst;
and b, adding the primary methylamine shape-selective catalyst into sodium hydroxide with the pH of 12, refluxing for 13h, performing solid-liquid separation, washing with clear water, and drying to obtain the methylamine shape-selective catalyst.
Example 2
The embodiment provides a methylamine shape-selective catalyst, which comprises the following raw materials in percentage by mass:
4% of a silicon source, 27% of soluble aluminum salt, 1% of ammonium molybdate, 2% of trimethyl phosphate, 15% of silicon carbide and 51% of water;
wherein the silicon source is a mixture of silicon dioxide and sodium silicate in a mass ratio of 1:2.6, the soluble aluminum salt is a mixture of aluminum chloride and aluminum nitrate in a mass ratio of 1:0.5, and the particle size of the silicon carbide is 1000 meshes;
the invention also provides a preparation method of the methylamine shape-selective catalyst, which comprises the following steps:
step a, weighing all raw materials according to a designed proportion, and uniformly mixing a weighed silicon source, soluble aluminum salt and water to obtain a mixed salt solution; setting the microwave power to be 800W, adding the weighed ammonium molybdate and trimethyl phosphate into the mixed salt solution under the microwave heating condition, heating for 90min by microwave, then adding the weighed silicon carbide, uniformly mixing, and roasting for 20h at 900 ℃ to obtain a primary methylamine shape-selective catalyst;
and b, adding the primary methylamine shape-selective catalyst into potassium hydroxide with the pH of 7, refluxing for 16 hours, separating solid from liquid, washing with clear water, and drying to obtain the methylamine shape-selective catalyst.
Example 3
The embodiment provides a methylamine shape-selective catalyst, which comprises the following raw materials in percentage by mass:
5% of a silicon source, 28% of soluble aluminum salt, 0.5% of copper oxalate, 3% of triethyl phosphate, 13% of silicon carbide and 50.5% of water;
the silicon source is a mixture of silicon dioxide and sodium silicate in a mass ratio of 1:2, the soluble aluminum salt is a mixture of aluminum chloride and aluminum nitrate in a mass ratio of 1:1, and the particle size of the silicon carbide is 300 meshes;
the invention also provides a preparation method of the methylamine shape-selective catalyst, which comprises the following steps:
step a, weighing all raw materials according to a designed proportion, and uniformly mixing a weighed silicon source, soluble aluminum salt and water to obtain a mixed salt solution; setting the microwave power to be 600W, adding the weighed copper oxalate and the weighed triethyl phosphate into the mixed salt solution under the microwave heating condition, heating for 100min by microwaves, then adding the weighed silicon carbide, uniformly mixing, and roasting for 15h at 800 ℃ to obtain a primary methylamine shape-selective catalyst;
and b, adding the primary methylamine shape-selective catalyst into sodium hydroxide with the pH of 10, refluxing for 15 hours, separating solid from liquid, washing with clear water, and drying to obtain the methylamine shape-selective catalyst.
Comparative example 1
This comparative example provides a methylamine shape-selective catalyst, which is prepared in exactly the same way as example 1, except that the silica of example 1 is replaced by an equivalent amount of dichlorosilane;
other raw materials were the same as in example 1.
Comparative example 2
This comparative example provides a methylamine shape-selective catalyst, which is prepared in exactly the same way as example 1, except that the aluminium nitrate of example 1 is replaced by an equivalent amount of aluminium carbonate;
other raw materials were the same as in example 1.
Comparative example 3
This comparative example provides a methylamine shape-selective catalyst, which is prepared in exactly the same manner as example 1, except that the cobalt nitrate of example 1 is replaced with an equivalent amount of dibasic calcium phosphate;
other raw materials were the same as in example 1.
Comparative example 4
This comparative example provides a methylamine shape-selective catalyst, which is prepared in exactly the same way as example 1, except that the triethyl phosphate in example 1 is replaced with an equivalent amount of triethylaluminum;
other raw materials were the same as in example 1.
Comparative example 5
This comparative example provides a methylamine shape-selective catalyst, which is prepared in exactly the same way as example 1, except that the silicon carbide in example 1 is replaced by an equivalent amount of alumina sol;
other raw materials were the same as in example 1.
Comparative example 6
This comparative example provides a methylamine shape-selective catalyst, all prepared in exactly the same way as example 1, except that the silicon source is 7% and the water is 48.8%;
other raw materials were the same as in example 1.
Application example
Specific surface and pore size analysis
The catalysts prepared in examples 1 to 3 and comparative examples 1 to 6 were detected by ASAP2020 PLUS fast surface area and pore size analyzer, respectively, and the detection results are shown in Table 1.
TABLE 1 detection results
As can be seen from Table 1, the methylamine shape-selective catalysts prepared in examples 1-3 of the invention have excellent specific surface area, and the pore diameter of the prepared catalyst is smaller than 6.0nm, thereby further improving the selectivity of monomethylamine.
Performance analysis
The catalysts prepared in examples 1 to 3 and comparative examples 1 to 6 were added in a small-sized column reactor in a bag-type packing manner, respectively, and the N/C ratio was set to 2.5/1, and the volume space velocity was set to 1.5 to 3.5m 3 Catalyst m 3 And/h, the pressure is 1.5-1.6MPa, the set temperature is 375 ℃, and the feeding proportion is NH 3 ：69.65wt%、CH 3 OH：18.96-23.7wt%、CH 3 NH 2 ：0.5-1.8wt%、(CH 3 ) 3 N:2.74-4.85wt% and reacting for 5h. The average grain radial crushing strength detection method is HG/T2782-2011, the wear resistance detection method is Q/TSH 3490 909-2006, and specific detection indexes and detection results are shown in Table 2.
TABLE 2 detection results
| Detecting items | Methanol conversion/% | Total amine Selectivity/% | Monomethylamine selectivity/% | Dimethylamine Selectivity/% | Trimethylamine selectivity/% | Dimethyl ether impurity selectivity/% | Average grain radial crush strength/N/cm 2 | Abrasion resistance/%/h |
| Example 1 | 99.8 | 99.5 | 64.6 | 23.8 | 11.6 | 0.5 | 100 | 95 |
| Example 2 | 99.6 | 99.0 | 64.3 | 22.5 | 13.2 | 1.0 | 100 | 95 |
| Example 3 | 99.9 | 99.1 | 65.1 | 21.8 | 13.1 | 0.9 | 100 | 95 |
| Comparative example 1 | 97.6 | 92.8 | 46.2 | 48.2 | 5.6 | 7.2 | 50 | 92 |
| Comparative example 2 | 98.3 | 94.1 | 43.1 | 33.4 | 23.5 | 5.9 | 50 | 92 |
| Comparative example 3 | 97.7 | 93.2 | 30.3 | 60.1 | 9.6 | 6.8 | 100 | 94 |
| Comparative example 4 | 98.1 | 93.5 | 43.4 | 47.3 | 9.3 | 6.5 | 100 | 95 |
| Comparative example 5 | 99.1 | 98.7 | 58.6 | 19.4 | 22.0 | 1.3 | 50 | 93 |
| Comparative example 6 | 97.7 | 96.1 | 57.6 | 35.1 | 7.3 | 3.9 | 50 | 92 |
As shown in Table 2, the methyl amine shape-selective catalyst provided by the invention has the advantages that the methanol conversion rate can reach 99.9%, the total amine selectivity is high, the prepared monomethylamine has high content, the dimethyl ether selectivity is low, the wear resistance and the compression resistance are excellent, and the service life is long.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (6)
1. A method for preparing a methylamine shape-selective catalyst, which is characterized by comprising the following steps:
step a, weighing all raw materials according to a designed proportion, and uniformly mixing a weighed silicon source, soluble aluminum salt and water to obtain a mixed salt solution; under the condition of microwave heating, adding the weighed soluble transition metal salt and the organophosphorus compound into the mixed salt solution, carrying out microwave heating reaction, then adding the weighed silicon kneading agent, uniformly mixing, and roasting to obtain the primary methylamine shape-selective catalyst;
step b, adding the primary methylamine shape-selective catalyst into a solution with pH of 7-12, heating for reaction, separating solid from liquid, washing and drying to obtain the methylamine shape-selective catalyst;
the methylamine shape-selective catalyst comprises the following raw materials in percentage by mass: 4-6% of silicon source, 27-30% of soluble aluminum salt, 0.2-1.0% of soluble transition metal salt, 2-4% of organic phosphorus compound, 10-15% of silicon kneading agent and the balance of water; wherein the silicon source is a mixture of silicon dioxide and sodium silicate, and the soluble aluminum salt is a mixture of aluminum chloride and aluminum nitrate;
wherein the soluble transition metal salt is at least one of cobalt nitrate, ammonium molybdate or copper oxalate; the organic phosphorus compound is at least one of trimethyl phosphate or triethyl phosphate; the silicon-based kneading agent is silicon carbide.
2. The method for preparing the methylamine shape-selective catalyst as claimed in claim 1, wherein the silicon source is a mixture of silicon dioxide and sodium silicate in a mass ratio of 1:0.8-2.6.
3. The method for preparing the methylamine shape-selective catalyst as claimed in claim 1, wherein the soluble aluminium salt is a mixture of aluminium chloride and aluminium nitrate in a mass ratio of 1:0.5-1.5.
4. The method for preparing a methylamine shape-selective catalyst as claimed in claim 1, wherein the silicon carbide has a particle size of 300-1000 mesh.
5. The method for preparing the methylamine shape-selective catalyst as claimed in claim 1, wherein in the step a, the power of microwave heating is 500-800W, and the time of microwave heating reaction is 90-120 min.
6. The method for preparing a methylamine shape-selective catalyst as claimed in claim 1, wherein in step b, the solution is at least one of sodium hydroxide solution, potassium hydroxide solution or ammonia water; and/or
In the step a, the roasting temperature is 650-900 ℃ and the roasting time is 10-20 h; and/or
In the step b, the temperature of the heating reaction is reflux temperature, and the heating reaction time is 13-16 h.
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| CN1177801C (en) * | 2000-09-29 | 2004-12-01 | 中国石油化工股份有限公司 | Methylamine catalyst and preparation process thereof |
| JP4758645B2 (en) * | 2002-06-27 | 2011-08-31 | 三菱レイヨン株式会社 | Method for producing dimethylamine |
| JP5114411B2 (en) * | 2005-09-29 | 2013-01-09 | ビーエーエスエフ ソシエタス・ヨーロピア | Molded product containing aluminosilicate and aluminum oxide and continuous production of methylamine |
| DE102005059711A1 (en) * | 2005-12-12 | 2007-06-14 | Basf Ag | Shaped body containing a microporous material and at least one silicon-containing binder, process for its preparation and its use as a catalyst, in particular in a process for the continuous synthesis of methylamines |
| CN114425337B (en) * | 2020-10-10 | 2024-01-30 | 中国石油化工股份有限公司 | Methanol amination catalyst and application thereof |
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