CN113134387B - Inner framework metal high-silicon beta molecular sieve catalyst and preparation method and application thereof - Google Patents
Inner framework metal high-silicon beta molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention discloses an inner framework metal high-silicon beta molecular sieve catalyst which comprises the following raw materials in parts by weight 100 parts: 1-8 parts of copper, 1-5 parts of zinc, 0.1-2 parts of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve. Meanwhile, a preparation method of the catalyst and an application of the catalyst in preparation of butanediamine are disclosed, and the preparation method comprises the following steps: (1) Grinding the silicon-aluminum type boron-beta molecular sieve, and sieving by a sieve of 80-100 meshes; (2) Mixing the amino acid complex solutions of copper, zinc and lanthanum according to the weight parts of the raw materials in the catalyst to obtain an amino acid metal complex solution, adding a ground and sieved silicon-aluminum type boron-beta molecular sieve for grinding, performing ion lattice exchange, filtering, washing and drying. The catalyst provided by the invention realizes the loading and the single atom confinement of metal atoms on the inner framework of the beta molecular sieve, and when the catalyst is used for preparing butanediamine, the by-products are few, and the product selectivity is high.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to an inner framework metal high-silicon beta molecular sieve catalyst, and a preparation method and application thereof.
Background
1, 4-butanediamine, also called putrescine, of formula H 2 N(CH 2 ) 4 NH 2 Colorless flaky crystal, odorous, easily soluble in water and ethanol and slightly soluble in ether. The relative density is 0.877, the melting point is 27 to 28 ℃, and the boiling point is 158 to 159 ℃. Used as chemical intermediates and as main raw materials for polyamide synthetic materials.
Butanediamine is mainly used for synthesizing a novel polyamide material, namely nylon 46, and polyamide 46 is firstly industrially developed in 1984 by DSM company in the Netherlands. The synthesis of polyamide 46 was studied by dupont as early as the 30's 20 th century and a low molecular weight polyamide 46 was produced. In 1979, the solid phase polycondensation process was successfully used for the synthesis of polyamide 46, producing high molecular weight polyamide 46. However, until DSM showed that 1, 4-butanediamine was produced from acrylonitrile and hydrogen cyanide, the synthesis of polyamide 46 was not advanced to commercial production. By 1990, DSM corporation established an industrial production plant producing 2 million tons per year. Production of polyamide 46 is mainly controlled by DSM company, but by cooperating with DSM, JSR company, imperial company and youth card company in japan also have the ability to develop and produce polyamide 46.
At present, butanediamine is prepared mainly through the addition reaction of acrylonitrile and cyanohydric acid in the presence of potassium oxide to obtain butanedinitrile, and the subsequent hydrogenation in the presence of ammonia. The method uses the virulent acrylonitrile and the hydrocyanic acid as raw materials, and has the advantages of high raw material cost, high toxicity, longer reaction flow and lower product yield. Chinese patent CN101735067A discloses a method for preparing 1, 4-butanediamine by refluxing 1, 4-dibromobutylamine as a raw material through potassium phthalimide to prepare phthalimide butane and then performing methanaminating, and the method also has the defects of long process flow, expensive raw materials and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an inner framework metal high-silicon beta molecular sieve catalyst, a preparation method and an application thereof.
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 1-8 parts of copper, 1-5 parts of zinc, 0.1-2 parts of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve.
The boron content of the silicon-aluminum type boron-containing beta molecular sieve is 8-10wt%.
The silicon-aluminum type boron-beta molecular sieve has a silicon-aluminum ratio of 100.
The preparation method of the internal framework metal high-silicon beta molecular sieve catalyst comprises the following steps:
(1) Grinding the silicon-aluminum type boron-beta molecular sieve, and sieving with a 80-100-mesh sieve;
(2) Mixing the amino acid complex solutions of copper, zinc and lanthanum according to the weight parts of the raw materials in the catalyst to obtain an amino acid metal complex solution, adding a silicon-aluminum type boron-beta molecular sieve which is ground and sieved for grinding, carrying out ion lattice exchange, filtering, washing and drying.
Preferably, the amino acid complexes of copper, zinc and lanthanum are respectively copper aspartate, zinc cysteine and lanthanum glycinate.
The ion lattice exchange is specifically as follows: soaking at room temperature for 24-48h, heating to 85-95 deg.C, and standing at room temperature for 24-48 h.
The washing is 3-5 times by adopting distilled water with equal volume.
The drying is drying for 3-5h at 140-160 ℃.
The application of the catalyst in preparing butanediamine is provided.
The application is as follows: filling the catalyst in a fixed bed reactor, carrying out a hydrogenation reaction at 300-400 ℃ under 0.5-1MPa, using butadiene as a raw material and at a weight space velocity of 1-3h -1 Passing said catalyst while passing ammonia, butadiene: ammonia gas molar ratio 1: (4-10), carrying out hydroamination on butadiene to generate butanediamine, and collecting a product.
The invention has the advantages that:
(1) According to the invention, a molecular sieve modification strategy is utilized to carry out ion lattice exchange on the silicon-aluminum type boron-containing beta molecular sieve, active metal is introduced into an inner framework of the silicon-aluminum type boron-containing beta molecular sieve to prepare the boron-containing beta molecular sieve catalyst with the embedded metal in the inner framework, and the load and the single atom confinement of metal atoms of copper, zinc and lanthanum on the inner framework of the beta molecular sieve are realized;
(2) The service life of the catalyst is greatly prolonged, and because the copper atoms which are easy to deactivate and coalesce are inlaid into the framework of the molecular sieve, the limitation and dispersion of atomic levels are realized, the service life of the catalyst is long, and the manufacturing cost is low;
(3) The method has the advantages that the cheap butadiene is used as a raw material, the butadiene is subjected to hydroamination to prepare butanediamine by adopting a fixed bed reactor in a gas phase high-selectivity one-step method under the action of a boron-beta molecular sieve catalyst embedded in an inner framework, the raw material cost is low, the process route is simple and efficient, and the economic advantage is obvious;
(4) When preparing butanediamine, the technical route is advanced, no three wastes are discharged, no highly toxic raw materials are used, the reaction condition is mild, and the equipment investment is small;
(5) When preparing butanediamine, the by-products are few, the composition of reactants is simple, the separation and purification process is simple, and the product selectivity is high due to the unique active metal encapsulation confinement effect of metal in a molecular sieve framework and the spatial pore channel shape selection effect of the molecular sieve.
Detailed Description
Example 1
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 8 parts of copper, 5 parts of zinc, 2 parts of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst comprises the following steps:
(1) Grinding the silicon-aluminum type boron-beta molecular sieve, and sieving with a 80-100-mesh sieve;
(2) Mixing solutions of copper aspartate, zinc cysteine and lanthanum glycinate according to the weight parts of the raw materials in the catalyst to obtain an amino acid metal complex solution, adding a ground and sieved silicon-aluminum type boron-beta molecular sieve for grinding, performing ion lattice exchange filtration, washing for 3 times by using distilled water with equal volume, and drying at 150 ℃ for 4 hours; wherein the ion lattice exchange is: soaking at room temperature for 24 hr, heating to 90 deg.C, and standing at room temperature for 24 hr.
Example 2
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 6 parts of copper, 5 parts of zinc, 1 part of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst comprises the following steps:
(1) Grinding the silicon-aluminum type boron-beta molecular sieve, and sieving with a 80-100-mesh sieve;
(2) Mixing solutions of copper aspartate, zinc cysteine and lanthanum glycinate according to the weight parts of the raw materials in the catalyst to obtain an amino acid metal complex solution, adding a ground and sieved silicon-aluminum type boron-beta molecular sieve for grinding, performing ion lattice exchange filtration, washing for 5 times by using distilled water with equal volume, and drying for 5 hours at 140 ℃; wherein the ion lattice exchange is: dipping for 48h at room temperature, heating to 95 ℃, and standing for 24h at room temperature.
Example 3
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 1 part of copper, 5 parts of zinc, 2 parts of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the internal framework metal high-silicon beta molecular sieve catalyst comprises the following steps:
(1) Grinding the silicon-aluminum type boron-beta molecular sieve, and sieving by a sieve of 80-100 meshes;
(2) Mixing solutions of copper aspartate, zinc cysteine and lanthanum glycinate according to the weight parts of the raw materials in the catalyst to obtain an amino acid metal complex solution, adding a ground and sieved silicon-aluminum type boron-beta molecular sieve for grinding, performing ion lattice exchange filtration, washing for 5 times by using distilled water with equal volume, and drying at 160 ℃ for 3 hours; wherein the ion lattice is exchanged for: soaking at room temperature for 24 hr, heating to 95 deg.C, and standing at room temperature for 48 hr.
Example 4
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 2 parts of copper, 2 parts of zinc, 0.1 part of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 10wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst is the same as that of the example 1.
Example 5
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 4 parts of copper, 4 parts of zinc, 0.2 part of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst is the same as that of the example 1.
Example 6
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 8 parts of copper, 1 part of zinc, 0.5 part of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst is the same as that of the example 1.
Example 7
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 7 parts of copper, 3 parts of zinc, 0.3 part of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst is the same as that of the example 1.
Example 8
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 1 part of copper, 2 parts of zinc, 2 parts of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst is the same as that of the example 1.
Example 9
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 8 parts of copper, 3 parts of zinc, 0.3 part of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst is the same as that of the example 1.
Example 10
An inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 3 parts of copper, 2 parts of zinc, 1.2 parts of lanthanum and the balance of silicon-aluminum type boron-beta molecular sieve; wherein the boron content of the silicon-aluminum type boron-beta molecular sieve is 8wt%, and the silicon-aluminum ratio is 100.
The preparation method of the inner framework metal high-silicon beta molecular sieve catalyst is the same as that of the example 1.
Application of
The application of the catalyst in preparing butanediamine is as follows: filling the catalyst in a fixed bed reactor, carrying out a hydrogenation reaction at 300-400 ℃ under 0.5-1MPa, using butadiene as a raw material and at a weight space velocity of 1-3h -1 Passing said catalyst while passing ammonia, butadiene: ammonia gas molar ratio 1: (4-10), carrying out hydroammonation on butadiene to generate butanediamine, and collecting the product. The reaction conditions and the reaction results are shown in Table 1.
TABLE 1 reaction conditions and results
Claims (6)
1. The application of the inner framework metal high-silicon beta molecular sieve catalyst in the preparation of butanediamine is characterized in that: the application is as follows: filling the catalyst in a fixed bed reactor, carrying out a hydrogenation reaction at 300-400 ℃ under 0.5-1MPa with butadiene as a raw material at a weight space velocity of 1-3h -1 Passing said catalyst while passing ammonia, butadiene: ammonia gas molar ratio 1: (4-10), collecting the product to obtain butanediamine;
the inner framework metal high-silicon beta molecular sieve catalyst comprises the following raw materials in parts by weight, based on 100 parts by weight: 1-8 parts of copper, 1-5 parts of zinc, 0.1-2 parts of lanthanum and the balance of silicon-aluminum boron-containing beta molecular sieve;
the inner framework metal high-silicon beta molecular sieve catalyst is prepared by the following method:
(1) Grinding the silicon-aluminum type boron-beta molecular sieve, and sieving by a sieve of 80-100 meshes;
(2) Mixing amino acid complex solutions of copper, zinc and lanthanum according to the weight parts of the raw materials in the catalyst to obtain an amino acid metal complex solution, adding a silicon-aluminum type boron-beta molecular sieve which is ground and sieved for grinding, performing ion lattice exchange, filtering, washing and drying;
the amino acid complexes of copper, zinc and lanthanum are respectively copper aspartate, zinc cysteine and lanthanum glycinate.
2. The use of the internal framework metal high silicon beta molecular sieve catalyst of claim 1 in the preparation of butanediamine, wherein: the boron content of the silicon-aluminum type boron-beta molecular sieve is 8-10wt%.
3. The use of the internal framework metal high silicon beta molecular sieve catalyst of claim 1 in the preparation of butanediamine, wherein: the silicon-aluminum ratio of the silicon-aluminum type boron-beta molecular sieve is 100-300.
4. The use of the internal framework metal high silicon beta molecular sieve catalyst according to claim 1 in the preparation of butanediamine, wherein: the ion lattice exchange is specifically as follows: soaking at room temperature for 24-48h, heating to 85-95 deg.C, and standing at room temperature for 24-48 h.
5. The use of the internal framework metal high silicon beta molecular sieve catalyst of claim 1 in the preparation of butanediamine, wherein: the washing is 3-5 times by adopting distilled water with equal volume.
6. The use of the internal framework metal high silicon beta molecular sieve catalyst according to claim 1 in the preparation of butanediamine, wherein: the drying is drying for 3-5h at 140-160 ℃.
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