CN115025809B - Modified hzsm-5 molecular sieve composition for continuously synthesizing tertiary amine catalyst for polyurethane and preparation method thereof - Google Patents
Modified hzsm-5 molecular sieve composition for continuously synthesizing tertiary amine catalyst for polyurethane and preparation method thereof Download PDFInfo
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- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- 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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- 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
- C07C213/08—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 not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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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
- B01J2229/18—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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- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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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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- 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 catalysts, relates to the field of B01J, and particularly relates to a modified hzsm-5 molecular sieve composition for continuously synthesizing a tertiary amine catalyst for polyurethane and a preparation method thereof. The composition comprises the following raw materials in parts by weight: 50 to 60 parts of modified hzsm-5 molecular sieve, 35 to 45 parts of pseudo-boehmite, 9 to 14 parts of extrusion aid and 6~8 parts of adhesive. The modified hzsm-5 molecular sieve is obtained by firstly treating with a nitrate solution and then modifying with a phosphoric acid solution. According to the invention, lanthanum nitrate and the hzsm-5 molecular sieve soaked by zinc nitrate solution are used, so that the condition of generating dimethylamino ethoxyethylamine by the reaction can be reduced, and the yield equivalent to that under a pressurized condition can be obtained by the reaction under normal pressure; secondly, the hzsm-5 molecular sieve is treated by using a phosphoric acid solution, so that the use amount of the hzsm-5 molecular sieve as a catalyst can be reduced on the premise of ensuring the yield of reaction products, thereby reducing the use amount of nitrate substances and heavy metals in the nitrate substances, and further reducing the production cost.
Description
Technical Field
The invention relates to the technical field of catalysts, relates to the field of B01J, and particularly relates to a modified hzsm-5 molecular sieve composition for continuously synthesizing a tertiary amine catalyst for polyurethane and a preparation method thereof.
Background
BDMAEE is colorless liquid, is dissolved in water, is one of important amine catalysts in the polyurethane industry, and has extremely high catalytic activity and selectivity on foaming reaction; the 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 the soft slab foam formulation, BDMAEE can improve foam processing from low to high density grades and can fill to high resilience grades. BDMAEE is also a highly effective catalyst for high resilience molded foams due to its unique functional properties.
CN103450035A discloses a preparation method of BDMAEE, which adopts dimethylamino ethoxy ethanol and a process for synthesizing BDMAEE through two steps of ammonolysis and condensation reduction. The first step needs to react under the pressure of 10MPa and the high temperature of 180 ℃, and the second step needs to use Pd/C as a catalyst, the pressure of 2.5MPa and the reaction temperature of 100 ℃ for reaction. The first step needs to be carried out at high temperature and high pressure, has high requirements on equipment and harsh process conditions, and is not beneficial to industrialization.
Based on the situation, the invention provides a modified hzsm-5 molecular sieve composition for continuously synthesizing a tertiary amine catalyst for polyurethane and a preparation method thereof, and the modified hzsm-5 molecular sieve composition can effectively solve the problems.
Disclosure of Invention
The invention aims to provide a modified hzsm-5 molecular sieve composition for continuously synthesizing a tertiary amine catalyst for polyurethane and a preparation method thereof.
In order to achieve the aim, the invention provides a modified hzsm-5 molecular sieve composition for continuously synthesizing a tertiary amine catalyst for polyurethane, which comprises the following raw materials in parts by weight: 50 to 60 parts of modified hzsm-5 molecular sieve, 35 to 45 parts of pseudo-boehmite, 9 to 14 parts of extrusion aid and 6~8 parts of adhesive.
Preferably, the modified hzsm-5 molecular sieve is obtained by firstly treating with a nitrate solution and then modifying with a phosphoric acid solution.
Preferably, the nitrate solution is a combination of a lanthanum nitrate solution and a zinc nitrate solution.
Preferably, the lanthanum nitrate solution is 6~8% by mass.
Preferably, the dosage of the lanthanum nitrate solution is 0.5 to 1.0ml of lanthanum nitrate solution per 1g of hzsm-5 molecular sieve.
Preferably, the mass fraction of the zinc nitrate solution is 4~6% zinc nitrate solution.
Preferably, the dosage of the lanthanum nitrate solution is 0.2 to 0.5ml of the lanthanum nitrate solution per 1g of hzsm-5 molecular sieve.
Preferably, the concentration of the phosphoric acid solution is 0.6 to 0.8mol/L, and the dosage of the phosphoric acid solution is 1.5 to 2.0ml of the phosphoric acid solution for every 1g of hzsm-5 molecular sieve.
Preferably, the extrusion aid is selected from one or a combination of more than two of starch, sesbania powder, hydroxyethyl methyl cellulose, methyl cellulose and polyethylene glycol.
Preferably, the adhesive is a nitric acid solution with the mass fraction of 3%, and the dosage of the nitric acid solution is 0.12 to 0.16ml per 1g of hzsm-5 molecular sieve.
The solvents in the nitric acid solution, the phosphoric acid solution, the lanthanum nitrate solution and the zinc nitrate solution used in the invention are all deionized water.
The invention also provides a preparation method of the modified hzsm-5 molecular sieve composition for continuously synthesizing the tertiary amine catalyst for polyurethane, which comprises the following steps:
(1) Mixing a lanthanum nitrate solution and a zinc nitrate solution, then adding the hzsm-5 molecular sieve into the mixed nitrate solution, ultrasonically vibrating for 2-3h, and drying for 2-3h at the temperature of 110 +/-5 ℃ to obtain a hzsm-5 molecular sieve precursor;
(2) Dropwise adding a phosphoric acid solution into the precursor, continuously stirring in the process, carrying out ultrasonic vibration for 1.5-2h after dropwise adding, drying for 5-6 h at 80 +/-5 ℃, and then roasting for 8-10h at 600-650 ℃ to obtain a modified hzsm-5 molecular sieve;
(3) And (3) uniformly mixing the modified hzsm-5 molecular sieve obtained in the step (2) with pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 10 to 12h, and then roasting at 600 to 650 ℃ for 8 to 10h to obtain the modified hzsm-5 molecular sieve.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, lanthanum nitrate and the hzsm-5 molecular sieve soaked by zinc nitrate solution are used, so that the reaction condition of dimethylamino ethoxyethanol and liquid ammonia to generate dimethylamino ethoxyethylamine can be reduced, and the yield equivalent to that under a pressurized condition can be obtained when the reaction is carried out under normal pressure; secondly, the hzsm-5 molecular sieve is treated by using a phosphoric acid solution, so that the use amount of the hzsm-5 molecular sieve as a catalyst can be reduced on the premise of ensuring the yield of reaction products, thereby reducing the use amount of nitrate substances and heavy metals in the nitrate substances, and further reducing the production cost.
2. The preparation method is convenient to operate, easy for large-scale production and stable in quality.
3. The raw materials of the invention are sufficient in China and proper in price, so that the large-scale production of the invention is not limited by too high cost.
Detailed Description
Example 1
The amounts of the respective raw materials are shown in Table 1.
(1) Mixing a lanthanum nitrate solution and a zinc nitrate solution, then adding an hzsm-5 molecular sieve into the mixed nitrate solution, ultrasonically vibrating for 2h, and drying for 2h at the temperature of 110 +/-5 ℃ to obtain an hzsm-5 molecular sieve precursor;
(2) Dropwise adding a phosphoric acid solution into the precursor, continuously stirring in the process, performing ultrasonic vibration for 1.5h after dropwise adding, drying for 5h at the temperature of 80 +/-5 ℃, and then roasting for 10h at the temperature of 600 ℃ to obtain the modified hzsm-5 molecular sieve;
(3) And (3) uniformly mixing the modified hzsm-5 molecular sieve obtained in the step (2) with pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 10 hours, and then roasting at 600 ℃ for 10 hours to obtain the modified hzsm-5 molecular sieve.
Example 2
The amounts of the respective raw materials are shown in Table 1.
(1) Mixing a lanthanum nitrate solution and a zinc nitrate solution, then adding an hzsm-5 molecular sieve into the mixed nitrate solution, ultrasonically vibrating for 3h, and drying for 3h at the temperature of 110 +/-5 ℃ to obtain an hzsm-5 molecular sieve precursor;
(2) Dropwise adding a phosphoric acid solution into the precursor, continuously stirring in the process, performing ultrasonic vibration for 2 hours after dropwise adding, drying for 6 hours at the temperature of 80 +/-5 ℃, and then roasting for 8 hours at the temperature of 650 ℃ to obtain the modified hzsm-5 molecular sieve;
(3) And (3) uniformly mixing the modified hzsm-5 molecular sieve obtained in the step (2) with pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 10 hours, and then roasting at 650 ℃ for 8 hours to obtain the modified hzsm-5 molecular sieve.
Example 3
The amounts of the respective raw materials are shown in table 1.
(1) Mixing a lanthanum nitrate solution and a zinc nitrate solution, then adding an hzsm-5 molecular sieve into the mixed nitrate solution, ultrasonically vibrating for 3h, and drying for 3h at the temperature of 110 +/-5 ℃ to obtain an hzsm-5 molecular sieve precursor;
(2) Dropwise adding a phosphoric acid solution into the precursor, continuously stirring in the process, performing ultrasonic vibration for 2 hours after dropwise adding, drying for 6 hours at the temperature of 80 +/-5 ℃, and then roasting for 10 hours at the temperature of 650 ℃ to obtain the modified hzsm-5 molecular sieve;
(3) And (3) uniformly mixing the modified hzsm-5 molecular sieve obtained in the step (2) with pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 12h, and then roasting at 650 ℃ for 10h to obtain the modified hzsm-5 molecular sieve.
Comparative example 1
The amounts of the respective raw materials are shown in table 1.
(1) Mixing a lanthanum nitrate solution and a zinc nitrate solution, then adding an hzsm-5 molecular sieve into the mixed nitrate solution, ultrasonically vibrating for 3h, and drying for 3h at the temperature of 110 +/-5 ℃ to obtain an hzsm-5 molecular sieve precursor;
(2) Then roasting for 10 hours at 650 ℃ to obtain a modified hzsm-5 molecular sieve;
(3) And (3) uniformly mixing the modified hzsm-5 molecular sieve obtained in the step (2) with pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 12h, and then roasting at 650 ℃ for 10h to obtain the modified hzsm-5 molecular sieve.
Comparative example 2
The amounts of the respective raw materials are shown in Table 1.
(1) Mixing a lanthanum nitrate solution and a zinc nitrate solution, then adding the hzsm-5 molecular sieve into the mixed nitrate solution, ultrasonically vibrating for 3 hours, and drying for 3 hours at the temperature of 110 +/-5 ℃ to obtain a hzsm-5 molecular sieve precursor;
(2) Then roasting for 10h at 650 ℃ to obtain the modified hzsm-5 molecular sieve;
(3) And (3) uniformly mixing the modified hzsm-5 molecular sieve obtained in the step (2) with pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 12 hours, and then roasting at 650 ℃ for 10 hours to obtain the modified hzsm-5 molecular sieve.
Comparative example 3
The amounts of the respective raw materials are shown in table 1.
Uniformly mixing the hzsm-5 molecular sieve and the pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 12h, and then roasting at 650 ℃ for 10h to obtain the finished product.
TABLE 1
| Species of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| hzsm-5 molecular sieve | 50 | 55 | 60 | 60 | 60 | 60 |
| 0.8mol/L phosphoric acid solution | 100ml | 110ml | 120ml | / | / | / |
| 8% lanthanum nitrate solution | 25 ml | 38 ml | 54ml | 54ml | 54ml | / |
| 6% Zinc nitrate solution | 10 ml | 22 ml | 30 ml | 30 ml | 30 ml | / |
| Pseudo-boehmite | 35 | 40 | 45 | 45 | 45 | 45 |
| Hydroxyethyl methyl cellulose | 5 | 6 | 8 | 8 | 8 | 8 |
| Sesbania powder | 4 | 5 | 6 | 6 | 6 | 6 |
| 3% nitric acid solution | 6 ml | 8ml | 10 ml | 7 | 7 | 7 |
EXAMPLE 4 preparation of bis-dimethylaminoethyl ether
266g of dimethylaminoethoxyethanol, followed by 140L of water, and then example 1~3 and comparative example 1~3 as catalysts (ground and sieved through a 40 mesh screen before use) were charged into the reactor, with a 25g throw for comparative example 1 and a 5g throw for comparative examples 2, 3 and 1~3. Example 1~3 and comparative examples 1 and 2 were heated to 50 ℃ in a nitrogen atmosphere, followed by addition of 170g of anhydrous liquid ammonia, and then heated to 180 ℃ for reaction for 9 hours; comparative example 3 temperature in the nitrogen protective atmosphere to 50 degrees, then add anhydrous liquid ammonia 170g, while introducing hydrogen to maintain the pressure of 10Mpa, then temperature to 180 degrees for reaction 9h. After the reaction is finished, reducing the temperature to normal temperature, then discharging, filtering, rectifying the filtrate at 90-95 ℃ under the pressure of 25mmhg to obtain the dimethylamino ethoxyethylamine, sampling, measuring the purity, weighing, and meanwhile calculating the yield of the dimethylamino ethoxyethylamine.
TABLE 2
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Dimethylamino ethoxyethanol g | 266 | 266 | 266 | 266 | 266 | 266 |
| Anhydrous liquid ammonia g | 170 | 170 | 170 | 170 | 170 | 170 |
| Catalyst g | 5 | 5 | 5 | 25 | 5 | 5 |
| Purity of the product% | 98.7 | 98.8 | 99.1 | 98.6 | 98.2 | 98.5 |
| Product weight g | 286.9 | 280.3 | 282.1 | 292.6 | 207.1 | 233.7 |
| The product yield is% | 65.8 | 64.3 | 64.7 | 67.1 | 47.5 | 53.6 |
The foregoing description of specific exemplary embodiments of the invention has been presented for the 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 certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and 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 (5)
1. A modified hzsm-5 molecular sieve composition for continuously synthesizing a tertiary amine catalyst for polyurethane is characterized by comprising the following raw materials in parts by weight: 50 to 60 parts of modified hzsm-5 molecular sieve, 35 to 45 parts of pseudo-boehmite, 9 to 14 parts of extrusion aid and 6~8 parts of adhesive;
the modified hzsm-5 molecular sieve is obtained by firstly treating with a nitrate solution and then modifying with a phosphoric acid solution;
the nitrate solution is a combination of a lanthanum nitrate solution and a zinc nitrate solution;
the lanthanum nitrate solution is 6~8% by mass; the dosage of the lanthanum nitrate solution is 0.5 to 1.0ml of lanthanum nitrate solution used for every 1g of hzsm-5 molecular sieve;
the mass fraction of the zinc nitrate solution is 4~6 percent of the zinc nitrate solution; the dosage of the lanthanum nitrate solution is 0.2 to 0.5ml of lanthanum nitrate solution for every 1g of hzsm-5 molecular sieve;
the concentration of the phosphoric acid solution is 0.6 to 0.8mol/L, and the dosage of the phosphoric acid solution is 1.5 to 2.0ml of phosphoric acid solution used for every 1g of hzsm-5 molecular sieve;
the preparation method of the modified hzsm-5 molecular sieve composition comprises the following steps:
(1) Mixing a lanthanum nitrate solution and a zinc nitrate solution, then adding a hzsm-5 molecular sieve into the mixed nitrate solution, ultrasonically vibrating for 2 to 3 hours, and drying for 2 to 3 hours at the temperature of 110 +/-5 ℃ to obtain a hzsm-5 molecular sieve precursor;
(2) Dropwise adding a phosphoric acid solution into the precursor, continuously stirring in the process, carrying out ultrasonic vibration for 1.5-2h after dropwise adding, drying for 5-6 h at 80 +/-5 ℃, and then roasting for 8-10h at 600-650 ℃ to obtain a modified hzsm-5 molecular sieve;
(3) And (3) uniformly mixing the modified hzsm-5 molecular sieve obtained in the step (2) with pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 10 to 12h, and then roasting at 600 to 650 ℃ for 8 to 10h to obtain the modified hzsm-5 molecular sieve.
2. The composition as claimed in claim 1, wherein the extrusion aid is selected from one or more of starch, sesbania powder, hydroxyethyl methylcellulose, and polyethylene glycol.
3. The composition as claimed in claim 1, wherein the binder is a 3% nitric acid solution, and the amount of the nitric acid solution is 0.12 to 0.16ml per 1g of hzsm-5 molecular sieve.
4. A process for the preparation of the modified hzsm-5 molecular sieve composition of claim 1 for use in the continuous synthesis of polyurethane with a tertiary amine catalyst, said process comprising the steps of:
(1) Mixing a lanthanum nitrate solution and a zinc nitrate solution, then adding the hzsm-5 molecular sieve into the mixed nitrate solution, ultrasonically vibrating for 2-3h, and drying for 2-3h at the temperature of 110 +/-5 ℃ to obtain a hzsm-5 molecular sieve precursor;
(2) Dropwise adding a phosphoric acid solution into the precursor, continuously stirring in the process, carrying out ultrasonic vibration for 1.5-2h after dropwise adding, drying for 5-6 h at 80 +/-5 ℃, and then roasting for 8-10h at 600-650 ℃ to obtain a modified hzsm-5 molecular sieve;
(3) And (3) uniformly mixing the modified hzsm-5 molecular sieve obtained in the step (2) with pseudo-boehmite, then adding an extrusion aid and an adhesive, fully rolling and forming, drying at 100 +/-5 ℃ for 10 to 12h, and then roasting at 600 to 650 ℃ for 8 to 10h to obtain the modified hzsm-5 molecular sieve.
5. The use of the modified hzsm-5 molecular sieve composition of claim 1 as a catalyst in the reaction of dimethylaminoethoxyethanol and liquid ammonia as raw materials to produce dimethylaminoethoxyethylamine.
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| CN114225958A (en) * | 2021-12-31 | 2022-03-25 | 山东京博石油化工有限公司 | Catalytic cracking catalyst for producing more propylene and preparation method thereof |
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| WO2017052854A1 (en) * | 2015-09-25 | 2017-03-30 | Exxonmobil Upstream Research Company | Aromatization of non-aromatic hydrocarbon |
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