CN111437877B - Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst and preparation method and application thereof - Google Patents
Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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- CN111437877B CN111437877B CN202010320800.7A CN202010320800A CN111437877B CN 111437877 B CN111437877 B CN 111437877B CN 202010320800 A CN202010320800 A CN 202010320800A CN 111437877 B CN111437877 B CN 111437877B
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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
- B01J29/70—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
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Abstract
The invention relates to a Cu/Zr double-metal framework type high-silicon beta molecular sieve catalyst, a preparation method and application thereof, wherein cheap coal-based ethanol is used as a raw material, and the reaction temperature is 320-400 ℃, the reaction pressure is 0.5-1MPa and the weight space velocity is 1-3h under the action of the Cu/Zr double-metal framework type high-silicon beta molecular sieve catalyst ‑1 Under the condition, the ethanol is dehydrogenated to prepare acetaldehyde and the ethanol acetaldehyde is prepared to butadiene through a relay catalytic reaction in a fixed bed reactor, so that the ethanol is prepared to butadiene through a one-step method. The molar selectivity of the butadiene product is more than 95 percent, the conversion rate of ethanol is more than 90 percent, and the problems of longer process flow, low conversion rate and selectivity and the like in the conventional production process for preparing butadiene from ethanol and acetaldehyde are solved.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst, and a preparation method and application thereof.
Background
Butadiene is an important basic organic chemical product, colorless gas and has special odor. Slightly soluble in water, soluble in ethanol, methanol, and easily soluble in acetone, diethyl ether, chloroform, etc. Is a raw material for producing synthetic rubber, synthetic resin, nylon, and the like. The preparation method mainly comprises the dehydrogenation of butane and butylene or the separation of four carbon fractions. It is anesthetic, especially irritating to mucosa, and easily liquefies.
Butadiene is the main raw material for producing synthetic rubber (styrene butadiene rubber, nitrile butadiene rubber, chloroprene rubber). With the development of styrene plastics, styrene and butadiene are copolymerized to produce various resins (such as ABS resin, SBS resin, BS resin and MBS resin) with wide application, so that butadiene gradually takes an important position in resin production. In addition, butadiene has been used to produce ethylidene norbornene (a third monomer of ethylene-propylene rubber), 1, 4-butanediol (engineering plastics), adiponitrile (a monomer of nylon 66), sulfolane, anthraquinone, tetrahydrofuran, and the like. And thus is also an important basic chemical raw material. Butadiene also has many uses in the production of fine chemicals.
The industrial production of butadiene mainly comprises a C4 extraction process using naphtha as a raw material, butadiene preparation by butylene dehydrogenation, butylene preparation by butane dehydrogenation and butadiene preparation by ethanol method. In 1928, the soviet union realizes the industrialization of preparing butadiene by using ethanol in one step, and the method is influenced by the impact of petroleum revolution and ethanol raw materials, so that the route is shelved due to the lack of economy. Along with the continuous fluctuation of the international oil price in recent years, particularly the great reduction of the ethanol price brought by the ethanol preparation from coal, the economy of the butadiene preparation from ethanol is greatly improved, and the butadiene preparation from ethanol is paid attention again to the industrial industry.
At present, the method mainly adopts a one-step method for preparing butadiene by using ethanol, a two-step method for preparing butadiene by using ethanol and acetaldehyde through dehydrogenation of ethanol. The one-step method has the problems of low product selectivity (about 40 percent), high cost, complex product and the like, and is basically not applicable. The two-step method has the problems of complex process, high cost, more byproducts and the like, and has certain disadvantage of industrial economy at present.
Research shows that Cu/Ag is a good catalyst for ethanol dehydrogenation, but Cu/Ag is easy to agglomerate and reunite, so that the activity is quickly deactivated, and the regeneration is not easy. The condensation of ethanol and acetaldehyde to prepare butadiene mainly takes Zr-Zn as an L acid-alkali center. The shape selection and the catalytic effect of butadiene can be realized in the high-alkalinity high-silicon beta molecular sieve. Therefore, if the Cu/Zr metal can be accurately encapsulated in the high-silicon beta molecular sieve, and the aluminum content in the conventional high-silicon beta molecular sieve is reduced to obtain the high-dispersion limited-domain type high-silicon beta molecular sieve containing the Cu/Zr metal, the key point for realizing the reaction for preparing the butadiene with high selectivity by the ethanol one-step method is realized.
Disclosure of Invention
The invention aims to solve the technical problems of low product selectivity, quick catalyst inactivation, more byproducts, difficult separation, longer process and the like in the traditional one-step or two-step method for preparing butadiene by ethanol. By utilizing the molecular sieve modification strategy, a citrulline Cu/Zr bimetallic complex is designed and synthesized, the complex solution and a conventional silicon-aluminum high-silicon beta molecular sieve are subjected to circulating ion exchange, the Al atom in the framework of the conventional high-silicon beta molecular sieve and the Cu and Zr in the complex solution realize monatomic exchange under a large circulation ratio due to stronger coordination capacity of the Al and citrulline, and the Al is replaced by the Cu and Zr in an atomic form and then enters the framework of the molecular sieve, so that the bimetallic framework type high-silicon beta molecular sieve catalyst is prepared, and the Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst is skillfully obtained while the load and monatomic confinement of the copper and zirconium metal atoms on the upper framework of the high-silicon beta molecular sieve are realized.
Ethanol is subjected to ethanol dehydrogenation and ethanol acetaldehyde-butadiene relay catalytic reaction under the action of a Cu/Zr double-metal framework type high-silicon beta molecular sieve catalyst, and butadiene is prepared by a one-step method.
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide 1-5 parts, zirconium oxide 2-8 parts, and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
Preferably, the catalyst comprises 2 parts of cuprous oxide, 6 parts of zirconium oxide and the balance of high-silicon beta molecular sieve according to 100 parts by weight.
A preparation method of a Cu/Zr double-metal framework type high-silicon beta molecular sieve catalyst comprises the following steps:
(1) Grinding a high-silicon beta molecular sieve with the Si/Al ratio of 100 for later use;
(2) Adding cuprous oxide and zirconium oxide into a citrulline aqueous solution, and regulating the pH value of the solution by using dilute hydrochloric acid to adjust the isoelectric point of citrulline to obtain a citrulline bimetallic complex solution;
(3) And (3) adding the high-silicon beta molecular sieve with the Si/Al ratio of 100, which is ground in the step (1), into the citrulline bimetallic complex solution in the step (2), soaking at room temperature for 12-24h, heating, purifying for 12-24h, filtering, washing with distilled water for 3-5 times, and drying to obtain the Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst.
Preferably, the mesh number of the grinding in the step (1) is 80-100 meshes.
Preferably, the temperature of the heating in step (3) is 70-90 ℃.
Preferably, the drying in step (3) is carried out at a temperature of 120-150 ℃ for a time of 4-8h.
A process for preparing butadiene directly by catalyzing alcohol includes such steps as loading alcohol in fixed-bed reactor, filling the bed layer of Cu/Zr bimetal skeleton type high-silicon beta-molecular sieve catalyst, reacting at 320-400 deg.C and 0.5-1MPa for 1-3 hr -1 Passing through the bed layer under the condition to obtain butadiene.
The invention has the advantages that:
1) The raw material cost is low, the one-step preparation method is adopted, the process route is simple and efficient, and the economic advantages are obvious: the method takes cheap coal-based ethanol as a raw material, adopts a fixed bed reactor to realize the dehydrogenation of ethanol and the relay catalytic reaction of acetaldehyde and ethanol by gas phase high selectivity under the action of a bimetallic framework type high-silicon beta molecular sieve catalyst, and realizes the preparation of high-selectivity butadiene in a pore channel of the high-silicon beta catalyst;
2) The technical route is advanced, no three wastes are discharged, no greenhouse gas is discharged, and the process is zero in pollution;
3) Simple separation and purification and high product selectivity: ethanol is adopted as a raw material, and due to the unique active metal packaging confinement effect of metal on a molecular sieve framework and the spatial pore channel shape-selecting effect of the molecular sieve, few byproducts are generated, the composition of reactants is simple, and the cost of a separation and purification process is low;
4) The service life of the catalyst is greatly prolonged, and the copper atoms which are easy to inactivate and coalesce are embedded into the molecular sieve framework, so that the limitation and dispersion of atomic levels are realized, and compared with the service life of a conventional copper catalyst for ethanol dehydrogenation for dozens of hours, the service life of the catalyst reaches more than 2000 hours.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 8 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst comprises the following steps: weighing the following raw materials in proportion:
(1) Grinding a high-silicon beta molecular sieve with the Si/Al ratio of 100, wherein the ground mesh number is 80 meshes for later use;
(2) Adding cuprous oxide and zirconium oxide into a citrulline aqueous solution, and regulating the pH value of the solution by using dilute hydrochloric acid to adjust the isoelectric point of citrulline to obtain a citrulline bimetallic complex solution;
(3) And (3) adding the high-silicon beta molecular sieve with the Si/Al ratio of 100 ground in the step (1) into the citrulline bimetallic complex solution in the step (2), soaking at room temperature for 24h, heating at 90 ℃, purifying for 24h, filtering, washing for 3-5 times by using distilled water, and drying at 150 ℃ for 4h to obtain the Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst.
The catalyst was numbered YCSY-01.
Example 2
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 6 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-02.
Example 3
A Cu/Zr bimetal framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide 5 parts, zirconium oxide 2 parts and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-03.
Example 4
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 8 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-04.
Example 5
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 6 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-05.
Example 6
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 6 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-06.
Example 7
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 8 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-07.
Example 8
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 2 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-08.
Example 9
A Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 2 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-09.
Example 10
A Cu/Zr bimetal framework type high-silicon beta molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 2 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100.
The preparation method of the catalyst is the same as that of example 1;
the catalyst was numbered YCSY-010.
Use of the catalysts prepared in examples 1 to 10:
the preparation method of the butadiene by using ethanol as a raw material comprises the following steps: filling a bed layer formed by a Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst in a fixed bed reactor, and reacting at the temperature of 320-400 ℃, the reaction pressure of 0.5-1Mpa and the weight space velocity of 1-3h -1 Passing through the bed under conditions to obtain butadiene.
The reaction conditions and the results of the catalysts of the examples in the preparation of butadiene are shown in Table 1.
TABLE 1
As can be seen from Table 1, under the action of the Cu/Zr double-metal framework type high-silicon beta molecular sieve catalyst, the selectivity of butadiene is greater than 95%, and the conversion rate of ethanol is greater than 90%.
Claims (6)
1. A Cu/Zr bimetal framework type high-silicon beta molecular sieve catalyst is characterized in that: the catalyst comprises, by weight, 100 parts of cuprous oxide 1-5 parts, zirconium oxide 2-8 parts, and the balance of a high-silicon beta molecular sieve with a Si/Al ratio of 100;
the preparation method of the Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst comprises the following steps:
(1) Grinding a high-silicon beta molecular sieve with the Si/Al ratio of 100 for later use;
(2) Adding cuprous oxide and zirconium oxide into a citrulline aqueous solution, and regulating the pH value of the solution by using dilute hydrochloric acid to adjust the isoelectric point of citrulline to obtain a citrulline bimetallic complex solution;
(3) And (3) adding the high-silicon beta molecular sieve with the Si/Al ratio of 100, which is ground in the step (1), into the citrulline bimetallic complex solution in the step (2), soaking at room temperature for 12-24h, heating, purifying for 12-24h, filtering, washing with distilled water for 3-5 times, and drying to obtain the Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst.
2. The Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst according to claim 1, characterized in that: the catalyst comprises, by weight, 100 parts of cuprous oxide, 6 parts of zirconium oxide and the balance of a high-silicon beta molecular sieve.
3. The Cu/Zr bi-metal framework type high-silicon beta molecular sieve catalyst according to claim 1, characterized in that: the mesh number of the grinding in the step (1) is 80-100 meshes.
4. The Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst according to claim 1, characterized in that: the heating temperature in the step (3) is 70-90 ℃.
5. The Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst according to claim 1, characterized in that: the drying temperature in the step (3) is 120-150 ℃, and the drying time is 4-8h.
6. A method for directly preparing butadiene by catalyzing ethanol is characterized by comprising the following steps: in a fixed bed reactor, ethanol is used as a raw material, a bed layer formed by the Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst as claimed in claim 1 or 2 is filled, the reaction temperature is 320-400 ℃, the reaction pressure is 0.5-1Mpa, and the weight space velocity is 1-3h -1 Under the condition, butadiene is obtained through a Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst bed layer.
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