CN115041226B - Composition based on zsm-48 molecular sieve and preparation method thereof - Google Patents
Composition based on zsm-48 molecular sieve and preparation method thereof Download PDFInfo
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- CN115041226B CN115041226B CN202210760164.9A CN202210760164A CN115041226B CN 115041226 B CN115041226 B CN 115041226B CN 202210760164 A CN202210760164 A CN 202210760164A CN 115041226 B CN115041226 B CN 115041226B
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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
- B01J29/04—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
- B01J29/74—Noble metals
- B01J29/7461—MRE-type, e.g. ZSM-48
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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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
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- 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 discloses a composition based on a zsm-48 molecular sieve and a preparation method thereof. The composition comprises the following raw materials in parts by weight: 40 to 50 parts of ZSM-48 molecular sieve, 50 to 60 parts of copper nitrate solution, 20 to 30 parts of pseudo-boehmite, 8 to 12 parts of extrusion aid, 2 to 4 parts of adhesive and 80 to 100 parts of hexachloroplatinic acid solution. According to the invention, the copper nitrate solution modified ZSM-48 molecular sieve is used for effectively promoting the reaction of dimethylamine and diethylene glycol to generate dimethylaminoethoxy ethanol; the addition of the nano-scale copper oxide is beneficial to the reaction of dimethylamine and dimethylaminoethoxy ethanol to generate dimethylaminoethyl ether, and simultaneously reduces the generation of by-products of tetramethyl ethylenediamine and dimethylethanolamine; further modification is carried out by hexachloroplatinic acid solution, thereby effectively promoting the dimethylamine to react with dimethylaminoethoxy ethanol preferentially and reducing the generation of byproduct methylmorpholine.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a composition based on a zsm-48 molecular sieve and a preparation method thereof.
Background
The ZSM-48 molecular sieve is a high-silicon zeolite, belongs to an orthorhombic structure, has 10-membered pore openings, has no through staggered linear pore canal, is connected by 5-membered rings, and has the pore diameter of about 0.6 nm. ZSM-48 molecular sieves are widely used in isomerisation reactions of straight paraffins due to their steric shape-selective effect. .
BDMAEE is a colorless liquid, dissolved in water. The structural formula of the catalyst is shown as S-1, and one of important amine catalysts in the polyurethane industry has extremely high catalytic activity and selectivity for foaming reaction; the foaming catalyst is suitable for all soft foams. Its strong catalyst effect on the foaming reaction can be balanced with a strong gel catalyst. In the application of flexible slab foam formulations, BDMAEE can improve foam processing from low to high density grades and can fill to high rebound grades. BDMAEE is also a highly efficient catalyst for high resilience molded foams due to its unique functional properties.
The main method for synthesizing BDMAEE at present is to firstly synthesize dimethylaminoethoxy ethanol by taking dimethylamine and diethylene glycol as raw materials, and then further react the dimethylaminoethoxy ethanol with dimethylamine to obtain BDMAEE. The method is carried out in two steps, the operation is more complicated, and other byproducts are easy to generate, thereby influencing the yield of BDMAEE.
Based on the above situation, the invention provides a composition based on a zsm-48 molecular sieve, a preparation method and a method for continuously synthesizing a tertiary amine catalyst for polyurethane, which can effectively solve the problems.
Disclosure of Invention
The invention aims to provide a composition based on a zsm-48 molecular sieve, a preparation method and a method for continuously synthesizing a tertiary amine catalyst for polyurethane.
In order to achieve the above purpose, the invention provides a composition based on zsm-48 molecular sieve, which comprises the following raw materials in parts by weight: 40 to 50 parts of ZSM-48 molecular sieve, 50 to 60 parts of copper nitrate solution, 20 to 30 parts of pseudo-boehmite, 8 to 12 parts of extrusion aid, 2 to 4 parts of adhesive and 80 to 100 parts of hexachloroplatinic acid solution.
Preferably, the concentration of the copper nitrate solution is 0.1-0.3 g of copper nitrate per milliliter of the aqueous solution.
Preferably, the hexachloroplatinic acid solution has a concentration of 1.5 to 2.0mg of hexachloroplatinic acid per milliliter of aqueous solution.
Preferably, the composition further comprises 15 to 35 parts of copper oxide.
Preferably, the copper oxide is nanoscale copper oxide.
Preferably, the extrusion aid is selected from one or more than two of starch, sesbania powder, hydroxyethyl methylcellulose, methylcellulose and polyethylene glycol.
Preferably, the binder is an acid solution containing one or a combination of two or more of nitric acid, citric acid, oxalic acid and tartaric acid.
Preferably, the composition comprises the following raw materials in parts by weight: 40 to 50 parts of ZSM-48 molecular sieve, 50 to 60 parts of copper nitrate solution, 20 to 30 parts of pseudo-boehmite, 15 to 35 parts of copper oxide, 4 to 6 parts of hydroxyethyl methylcellulose, 4 to 6 parts of sesbania powder, 2 to 4 parts of 0.1 percent citric acid-0.1 percent nitric acid solution and 80 to 100 parts of hexachloroplatinic acid solution.
Preferably, the composition comprises the following raw materials in parts by weight: 50 parts of ZSM-48 molecular sieve, 60 parts of copper nitrate solution, 30 parts of pseudo-boehmite, 35 parts of copper oxide, 6 parts of hydroxyethyl methylcellulose, 6 parts of sesbania powder, 4 parts of 0.1% citric acid-0.1% nitric acid solution and 100 parts of hexachloroplatinic acid solution.
The invention also provides a preparation method of the composition taking the modified ZSM-48 molecular sieve as a carrier, which comprises the following steps:
(1) Adding ZSM-48 molecular sieve into copper nitrate solution (0.1-0.3 g of copper nitrate is contained in each milliliter of aqueous solution), soaking for 12-13 hours at room temperature, filtering, collecting solid particles, drying for 2-3 hours at 150 ℃, and roasting for 8-10 hours at 600-650 ℃ to obtain a precursor;
(2) Uniformly mixing the precursor obtained in the step (1) with pseudo-boehmite and nano copper oxide, adding an extrusion aid and an adhesive, fully rolling and forming, and roasting at 600-650 ℃ for 8-10 h to obtain a carrier;
(3) Adding the carrier obtained in the step (3) into hexachloroplatinic acid solution (1.5-2.0 mg hexachloroplatinic acid is contained in each milliliter of aqueous solution), dipping for 4-6 h at 90-95 ℃, drying for 10-12 h in a 100 ℃ oven, and roasting for 5-6 h at 550-600 ℃ to obtain the carrier.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the copper nitrate solution modified ZSM-48 molecular sieve is used for effectively promoting the reaction of dimethylamine and diethylene glycol to generate dimethylaminoethoxy ethanol; the addition of the nano-scale copper oxide is beneficial to the reaction of dimethylamine and dimethylaminoethoxy ethanol to generate dimethylaminoethyl ether, and simultaneously reduces the generation of by-products of tetramethyl ethylenediamine and dimethylethanolamine; further modification is carried out by hexachloroplatinic acid solution, thereby effectively promoting the dimethylamine to react with dimethylaminoethoxy ethanol preferentially and reducing the generation of byproduct methylmorpholine.
2. The preparation method disclosed by the invention is convenient to operate, easy to produce on a large scale and stable in quality.
3. The raw materials of the invention are abundant in China and have proper price, so that the large-scale production of the invention has no high cost limit.
Detailed Description
Examples
Example 1
The amounts of the raw materials are shown in Table 1.
(1) Adding ZSM-48 molecular sieve into copper nitrate solution (0.1 g of copper nitrate is contained in each milliliter of aqueous solution), soaking for 13 hours at room temperature, filtering, collecting solid particles, drying for 2 hours at 150 ℃, and roasting for 10 hours at 600 ℃ to obtain a precursor;
(2) Uniformly mixing the precursor obtained in the step (1) with pseudo-boehmite and nano copper oxide, adding an extrusion aid and an adhesive, fully rolling and forming, and roasting at 600 ℃ for 10 hours to obtain a carrier;
(3) Adding the carrier obtained in the step (3) into hexachloroplatinic acid solution (1.5 mg hexachloroplatinic acid is contained in each milliliter of aqueous solution), soaking for 6 hours at 90 ℃, drying for 10 hours in a 100 ℃ oven, and roasting for 6 hours at 550 ℃ to obtain the carrier.
Example 2
The amounts of the raw materials are shown in Table 1.
(1) Adding ZSM-48 molecular sieve into copper nitrate solution (0.3 g of copper nitrate is contained in each milliliter of aqueous solution), soaking for 12 hours at room temperature, filtering, collecting solid particles, drying for 3 hours at 150 ℃, and roasting for 8 hours at 650 ℃ to obtain a precursor;
(2) Uniformly mixing the precursor obtained in the step (1) with pseudo-boehmite and nano copper oxide, adding an extrusion aid and an adhesive, fully rolling and forming, and roasting at 650 ℃ for 8 hours to obtain a carrier;
(3) Adding the carrier obtained in the step (3) into hexachloroplatinic acid solution (2.0 mg hexachloroplatinic acid is contained in each milliliter of aqueous solution), soaking for 4 hours at 95 ℃, drying for 12 hours in a 100 ℃ oven, and roasting for 5 hours at 600 ℃ to obtain the carrier.
Example 3
The amounts of the raw materials are shown in Table 1.
(1) Adding ZSM-48 molecular sieve into copper nitrate solution (0.3 g of copper nitrate is contained in each milliliter of aqueous solution), soaking for 13 hours at room temperature, filtering, collecting solid particles, drying for 3 hours at 150 ℃, and roasting for 10 hours at 650 ℃ to obtain a precursor;
(2) Uniformly mixing the precursor obtained in the step (1) with pseudo-boehmite and nano copper oxide, adding an extrusion aid and an adhesive, fully rolling and forming, and roasting at 650 ℃ for 10 hours to obtain a carrier;
(3) Adding the carrier obtained in the step (3) into hexachloroplatinic acid solution (2.0 mg hexachloroplatinic acid is contained in each milliliter of aqueous solution), soaking for 6 hours at 95 ℃, drying for 12 hours in a 100 ℃ oven, and roasting for 6 hours at 600 ℃ to obtain the carrier.
Comparative example 1
The amounts of the raw materials are shown in Table 1.
(1) Uniformly mixing a ZSM-48 molecular sieve with pseudo-boehmite and nano copper oxide, adding an extrusion aid and an adhesive, fully rolling and forming, and roasting at 650 ℃ for 10 hours to obtain a carrier;
(2) And (3) adding the carrier obtained in the step (2) into hexachloroplatinic acid solution (2.0 mg of hexachloroplatinic acid is contained in each milliliter of aqueous solution), soaking for 6 hours at 95 ℃, drying for 12 hours in a 100 ℃ oven, and roasting for 6 hours at 600 ℃ to obtain the carrier.
Comparative example 2
The amounts of the raw materials are shown in Table 1.
(1) Adding ZSM-48 molecular sieve into copper nitrate solution (0.3 g of copper nitrate is contained in each milliliter of aqueous solution), soaking for 13 hours at room temperature, filtering, collecting solid particles, drying for 3 hours at 150 ℃, and roasting for 10 hours at 650 ℃ to obtain a precursor;
(2) Uniformly mixing the precursor obtained in the step (1) with pseudo-boehmite, adding an extrusion aid and an adhesive, fully rolling and forming, and roasting at 650 ℃ for 10 hours to obtain a carrier;
(3) Adding the carrier obtained in the step (3) into hexachloroplatinic acid solution (2.0 mg hexachloroplatinic acid is contained in each milliliter of aqueous solution), soaking for 6 hours at 95 ℃, drying for 12 hours in a 100 ℃ oven, and roasting for 6 hours at 600 ℃ to obtain the carrier.
Comparative example 3
The amounts of the raw materials are shown in Table 1.
(1) Adding ZSM-48 molecular sieve into copper nitrate solution (0.3 g of copper nitrate is contained in each milliliter of aqueous solution), soaking for 13 hours at room temperature, filtering, collecting solid particles, drying for 3 hours at 150 ℃, and roasting for 10 hours at 650 ℃ to obtain a precursor;
(2) Adding the precursor obtained in the step (1) into hexachloroplatinic acid solution (2.0 mg hexachloroplatinic acid is contained in each milliliter of aqueous solution), soaking for 6 hours at 95 ℃, drying for 12 hours in a 100 ℃ oven, and roasting for 6 hours at 600 ℃ to obtain a carrier;
(3) Uniformly mixing the carrier obtained in the step (2) with pseudo-boehmite and nano-copper oxide, adding an extrusion aid and an adhesive, fully rolling, forming, and roasting at 650 ℃ for 10 hours to obtain the nano-copper oxide.
TABLE 1
Example 4 Performance evaluation test
The catalysts prepared in examples 1 to 3 and comparative examples 1 to 3 were crushed and sieved, 20ml of the catalyst having a particle size of 20 to 30 mesh was placed in a tubular trickle bed reactor having a diameter of 60mm, hydrogen was introduced, and the catalyst was reduced at 200℃for 5 hours, 300℃for 5 hours, 380℃for 5 hours, the hydrogen pressure was controlled at 5atm, and the hydrogen flow rate was 50ml/min. Then the molar ratio is 3.5:1, respectively introducing dimethylamine and diethylene glycol, controlling the adding speed of the diethylene glycol to be 0.1ml/min, the hydrogen pressure to be 15atm, the hydrogen flow rate to be 200ml/min and the reaction temperature to be 220 ℃.
The reaction products were checked for product content by gas chromatography normalization, and the results of the respective content checks of the reaction products except water are shown in Table 2.
TABLE 2 reaction results
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (2)
1. A composition for reacting dimethylamine with diethylene glycol to produce dimethylaminoethyl ether, the composition comprising the following raw materials in parts by weight: 40-50 parts of ZSM-48 molecular sieve, 50-60 parts of copper nitrate solution, 20-30 parts of pseudo-boehmite, 15-35 parts of nano copper oxide, 4-6 parts of hydroxyethyl methylcellulose, 4-6 parts of sesbania powder, 2-4 parts of 0.1% citric acid-0.1% nitric acid solution and 80-100 parts of hexachloroplatinic acid solution; the composition is prepared by the following steps: (1) Adding ZSM-48 molecular sieve into copper nitrate solution containing 0.1-0.3 g of copper nitrate per milliliter of aqueous solution, soaking for 12-13 hours at room temperature, filtering, collecting solid particles, drying for 2-3 hours at 150 ℃, and roasting for 8-10 hours at 600-650 ℃ to obtain a precursor; (2) Uniformly mixing the precursor obtained in the step (1) with pseudo-boehmite and nano copper oxide, adding an extrusion aid and an adhesive, fully rolling and forming, and roasting at 600-650 ℃ for 8-10 h to obtain a carrier; (3) Adding the carrier obtained in the step (3) into hexachloroplatinic acid solution containing 1.5-2.0 mg hexachloroplatinic acid per milliliter of aqueous solution, soaking for 4-6 h at 90-95 ℃, drying for 10-12 h in a drying oven at 100 ℃, and roasting for 5-6 h at 550-600 ℃ to obtain the carrier.
2. Composition according to claim 1, characterized in that it comprises the following raw materials in parts by weight: 50 parts of ZSM-48 molecular sieve, 60 parts of copper nitrate solution, 30 parts of pseudo-boehmite, 35 parts of nano-copper oxide, 6 parts of hydroxyethyl methylcellulose, 6 parts of sesbania powder, 4 parts of 0.1% citric acid-0.1% nitric acid solution and 100 parts of hexachloroplatinic acid solution.
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| CN105582956B (en) * | 2014-10-21 | 2018-07-31 | 中国石油化工股份有限公司 | The method of hydrogenation catalyst and its preparation method and application and hydrogenation reaction |
| CN105837457B (en) * | 2016-03-30 | 2019-04-16 | 河北华茂伟业科技有限公司 | The method that applied metal catalyst synthesizes bis- (dimethylaminoethyl) ethers |
| CN106881144B (en) * | 2017-03-25 | 2021-04-09 | 河北华茂伟业科技有限公司 | Metal catalyst and method for catalytically synthesizing dimethylamino ethoxyethanol by using same |
| CN110841689B (en) * | 2018-08-20 | 2021-12-17 | 中国石油化工股份有限公司 | Combined catalyst and method for producing high-quality naphtha |
| CN113649064B (en) * | 2021-07-22 | 2022-12-13 | 中国石油大学(北京) | Zeolite molecular sieve supported metal catalyst and synthesis method and application thereof |
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