CN111437877A - Cu/Zr double-metal-framework type high-silicon β molecular sieve catalyst and preparation method and application thereof - Google Patents
Cu/Zr double-metal-framework type high-silicon β molecular sieve catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111437877A CN111437877A CN202010320800.7A CN202010320800A CN111437877A CN 111437877 A CN111437877 A CN 111437877A CN 202010320800 A CN202010320800 A CN 202010320800A CN 111437877 A CN111437877 A CN 111437877A
- Authority
- CN
- China
- Prior art keywords
- silicon
- molecular sieve
- type high
- framework type
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a Cu/Zr double-metal framework type high-silicon β molecular sieve catalyst and 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 a Cu/Zr double-metal framework type high-silicon β molecular sieve catalyst‑1Under 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 low selectivity existing in the prior production process for preparing butadiene from ethanol and acetaldehyde are solvedAnd the like.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a Cu/Zr double-metal framework type high-silicon β 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 irritant to mucosa, and easy to liquefy.
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 realized the industrialization of preparing butadiene by ethanol in one step, and the process is influenced by the impact of petroleum revolution and ethanol raw materials, so the process 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 the one-step method for preparing butadiene by adopting ethanol, the method mainly adopts the former Soviet Union to prepare butadiene, the method adopts two steps of ethanol dehydrogenation to prepare acetaldehyde and ethanol-acetaldehyde condensation to prepare butadiene. 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 the activity is rapidly inactivated and is not easy to regenerate due to the fact that Cu/Ag is easy to aggregate and agglomerate, butadiene prepared by condensation of ethanol and aldehyde mainly takes Zr-Zn as the L acid-base center, and the shape selection and catalytic effect of butadiene can be realized in the high-alkaline high-silicon β molecular sieve.
Disclosure of Invention
The invention aims to solve the technical problems of low product selectivity, quick catalyst deactivation, more byproducts, difficult separation, longer flow and the like of butadiene prepared by a traditional ethanol one-step method or two-step method by utilizing the molecular sieve modification strategy, and designs and synthesizes a citrulline Cu/Zr bimetallic complex, wherein the complex solution is subjected to circulating ion exchange with a conventional silicon-aluminum high-silicon β molecular sieve, and because Al and citrulline have stronger coordination capacity, under a large circulation ratio, Al atoms in a framework of the conventional high-silicon β molecular sieve and Cu and Zr in the complex solution realize monatomic exchange, and Cu and Zr replace Al in the molecular sieve framework in an atomic form to enter the molecular sieve framework, so that the bimetallic-framework high-silicon β molecular sieve catalyst is prepared, and the Cu/Zr bimetallic-framework high-silicon β molecular sieve catalyst is skillfully obtained while the loading and monatomic confinement of copper and zirconium metal atoms on the upper framework of the high-silicon β molecular sieve are realized.
Ethanol is subjected to ethanol dehydrogenation and ethanol acetaldehyde butadiene preparation relay catalytic reaction under the action of a Cu/Zr double-metal framework type high-silicon β molecular sieve catalyst, and butadiene preparation is realized by a one-step method.
A Cu/Zr bimetallic framework type high-silicon β 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 β 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 β molecular sieve by 100 parts by weight.
A preparation method of a Cu/Zr double-metal framework type high-silicon β molecular sieve catalyst comprises the following steps:
(1) grinding a high-silicon β 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 β 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 for 12-24h at room temperature, heating, purifying for 12-24h, filtering, washing for 3-5 times by using distilled water, and drying to obtain the Cu/Zr bimetallic framework type high-silicon β 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 temperature in the step (3) is 120-150 ℃ and the time is 4-8 h.
A method for directly preparing butadiene by catalyzing ethanol comprises the steps of filling a bed layer formed by a Cu/Zr double-metal framework type high-silicon β molecular sieve catalyst in a fixed bed reactor by taking ethanol as a raw material, and reacting at the temperature of 320-400 ℃, under the pressure of 0.5-1Mpa and at the weight space velocity of 1-3h-1Passing through the bed layer under the condition to obtain butadiene.
The invention has the advantages that:
1) the invention takes low-cost coal-based ethanol as raw material, adopts the gas phase high selectivity of a fixed bed reactor to realize the ethanol dehydrogenation and acetaldehyde ethanol relay catalytic reaction under the action of a bimetallic framework type high-silicon β molecular sieve catalyst, and realizes the preparation of high-selectivity butadiene in a high-silicon β catalyst pore channel;
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 β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide 5 parts, 8 parts of zirconium oxide, and the balance of a high-silicon β 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 β 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 β 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 for 24h at room temperature, heating at 90 ℃, purifying for 24h, filtering, washing for 3-5 times by using distilled water, and drying for 4h at 150 ℃ to obtain the Cu/Zr bimetallic framework type high-silicon β molecular sieve catalyst.
The catalyst was numbered YCSY-01.
Example 2
A Cu/Zr bimetallic framework type high-silicon β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide and 6 parts of zirconium oxide, and the balance of a high-silicon β 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 bimetallic framework type high-silicon β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide 5 parts, 2 parts of zirconium oxide, and the balance of a high-silicon β 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 β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 8 parts of zirconium oxide and the balance of a high-silicon β 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 β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 6 parts of zirconium oxide and the balance of a high-silicon β 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 β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 6 parts of zirconium oxide and the balance of a high-silicon β 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 β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 8 parts of zirconium oxide and the balance of a high-silicon β 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 β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide 5 parts, 2 parts of zirconium oxide, and the balance of a high-silicon β 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 β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 2 parts of zirconium oxide and the balance of a high-silicon β 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 bimetallic framework type high-silicon β molecular sieve catalyst comprises, by weight, 100 parts of cuprous oxide, 2 parts of zirconium oxide and the balance of a high-silicon β 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 butadiene from ethanol comprises filling a bed layer composed of Cu/Zr bimetallic framework type high-silicon β molecular sieve catalyst in a fixed bed reactor at a reaction temperature of 320-400 deg.C, a reaction pressure of 0.5-1Mpa, and a weight space velocity of 1-3h-1Passing 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 β molecular sieve catalyst, the selectivity of butadiene is greater than 95%, and the conversion rate of ethanol is greater than 90%.
Claims (7)
1. The Cu/Zr bimetallic framework type high-silicon β molecular sieve catalyst is characterized by comprising, by weight, 1-5 parts of cuprous oxide, 2-8 parts of zirconium oxide and the balance of a high-silicon β molecular sieve with the Si/Al ratio of 100, based on 100 parts of the catalyst.
2. The Cu/Zr double-metal-framework type high-silicon β molecular sieve catalyst of claim 1, wherein the catalyst comprises, by weight, 2 parts of cuprous oxide, 6 parts of zirconium oxide and the balance high-silicon β molecular sieve per 100 parts of the catalyst.
3. The preparation method of the Cu/Zr bimetallic framework type high-silicon β molecular sieve catalyst according to claim 1 or 2, characterized by comprising the following steps:
(1) grinding a high-silicon β 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 β 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 for 12-24h at room temperature, heating, purifying for 12-24h, filtering, washing for 3-5 times by using distilled water, and drying to obtain the Cu/Zr bimetallic framework type high-silicon β molecular sieve catalyst.
4. The method for preparing the Cu/Zr bimetallic framework type high-silicon β molecular sieve catalyst according to claim 3, wherein the mesh number of the grinding in the step (1) is 80-100 meshes.
5. The method for preparing Cu/Zr double-metal-framework type high-silicon β molecular sieve catalyst according to claim 3, wherein the heating temperature in step (3) is 70-90 ℃.
6. The method for preparing the Cu/Zr double-metal-framework type high-silicon β molecular sieve catalyst according to claim 3, wherein the drying temperature in step (3) is 120-150 ℃ and the drying time is 4-8 h.
7. A method for directly preparing butadiene by catalyzing ethanol is characterized in that ethanol is used as a raw material in a fixed bed reactor, a bed layer formed by the Cu/Zr double-metal framework type high-silicon β molecular sieve catalyst as claimed in claim 1 or 2 is filled, and the reaction temperature is 320-400 ℃, the reaction pressure is 0.5-1Mpa, and the weight space velocity is 1-3h-1Butadiene is obtained by passing through a Cu/Zr bimetallic framework type high-silicon β molecular sieve catalyst bed layer under the condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010320800.7A CN111437877B (en) | 2020-04-22 | 2020-04-22 | Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010320800.7A CN111437877B (en) | 2020-04-22 | 2020-04-22 | Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111437877A true CN111437877A (en) | 2020-07-24 |
| CN111437877B CN111437877B (en) | 2023-03-10 |
Family
ID=71656118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010320800.7A Active CN111437877B (en) | 2020-04-22 | 2020-04-22 | Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111437877B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112206776A (en) * | 2020-07-28 | 2021-01-12 | 陕西延长石油（集团）有限责任公司 | Composite metal oxide, raw material composition, preparation method and application thereof |
| CN113134387A (en) * | 2021-04-28 | 2021-07-20 | 陕西延长石油（集团）有限责任公司 | Inner framework metal high-silicon beta molecular sieve catalyst and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1910115A (en) * | 2004-01-07 | 2007-02-07 | 开洛莱特公司 | Chiral inorganic-organic composite porous material and method for preparing the same |
| CN101185902A (en) * | 2007-12-19 | 2008-05-28 | 天津大学 | Catalyst for carbonylsynthesizing diethyl carbonate byethanol gas-phase oxidation and preparation method thereof |
| CN103772494A (en) * | 2014-01-23 | 2014-05-07 | 浙江大学 | Antibacterial peptide secreted by clostridium butyricum as well as preparation method and application thereof |
| US20140294706A1 (en) * | 2011-10-24 | 2014-10-02 | Haldor Topsøe A/S | Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides |
| WO2014199348A2 (en) * | 2013-06-13 | 2014-12-18 | Basf Se | Metal doped silicate catalysts for the selective conversion of ethanol to butadiene |
| CN104707648A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院大连化学物理研究所 | Ionothermal post-synthesis for synthesis of functional heteroatomic molecular sieve |
| CN105777488A (en) * | 2016-03-29 | 2016-07-20 | 青岛科技大学 | Method for catalytically preparing fatty alcohol |
| CN106861752A (en) * | 2017-01-09 | 2017-06-20 | 北京化工大学 | Solid catalyst and its preparation and application for ethanol synthesis butadiene |
| CN109608420A (en) * | 2019-01-17 | 2019-04-12 | 中国科学院长春应用化学研究所 | A method of functionalization 1,3- butadiene is synthesized based on biomass chemicals |
| CN109894144A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of synthetic method of 1,3- butadiene and its preparation method of catalyst |
-
2020
- 2020-04-22 CN CN202010320800.7A patent/CN111437877B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1910115A (en) * | 2004-01-07 | 2007-02-07 | 开洛莱特公司 | Chiral inorganic-organic composite porous material and method for preparing the same |
| CN101185902A (en) * | 2007-12-19 | 2008-05-28 | 天津大学 | Catalyst for carbonylsynthesizing diethyl carbonate byethanol gas-phase oxidation and preparation method thereof |
| US20140294706A1 (en) * | 2011-10-24 | 2014-10-02 | Haldor Topsøe A/S | Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides |
| WO2014199348A2 (en) * | 2013-06-13 | 2014-12-18 | Basf Se | Metal doped silicate catalysts for the selective conversion of ethanol to butadiene |
| CN104707648A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院大连化学物理研究所 | Ionothermal post-synthesis for synthesis of functional heteroatomic molecular sieve |
| CN103772494A (en) * | 2014-01-23 | 2014-05-07 | 浙江大学 | Antibacterial peptide secreted by clostridium butyricum as well as preparation method and application thereof |
| CN105777488A (en) * | 2016-03-29 | 2016-07-20 | 青岛科技大学 | Method for catalytically preparing fatty alcohol |
| CN106861752A (en) * | 2017-01-09 | 2017-06-20 | 北京化工大学 | Solid catalyst and its preparation and application for ethanol synthesis butadiene |
| CN109894144A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of synthetic method of 1,3- butadiene and its preparation method of catalyst |
| CN109608420A (en) * | 2019-01-17 | 2019-04-12 | 中国科学院长春应用化学研究所 | A method of functionalization 1,3- butadiene is synthesized based on biomass chemicals |
Non-Patent Citations (1)
| Title |
|---|
| 黄锐著，: "稀土在高分子工业中的应用", 《稀土在高分子工业中的应用》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112206776A (en) * | 2020-07-28 | 2021-01-12 | 陕西延长石油（集团）有限责任公司 | Composite metal oxide, raw material composition, preparation method and application thereof |
| CN112206776B (en) * | 2020-07-28 | 2023-04-28 | 陕西延长石油（集团）有限责任公司 | Composite metal oxide, raw material composition, preparation method and application thereof |
| CN113134387A (en) * | 2021-04-28 | 2021-07-20 | 陕西延长石油（集团）有限责任公司 | Inner framework metal high-silicon beta molecular sieve catalyst and preparation method and application thereof |
| CN113134387B (en) * | 2021-04-28 | 2022-12-20 | 陕西延长石油（集团）有限责任公司 | Inner framework metal high-silicon beta molecular sieve catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111437877B (en) | 2023-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111437877B (en) | Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst and preparation method and application thereof | |
| TW201427933A (en) | Method and device for coproducing cyclohexanol and alkanol | |
| CN109529946A (en) | A kind of method that solid-carrying type Cu-Ni bimetallic catalyst and its catalysis furfural complete hydrogenation prepare tetrahydrofurfuryl alcohol | |
| CN109622050B (en) | Catalyst and method for preparing nerol and geraniol by using same | |
| CN112194577A (en) | Method for preparing cyclopentanone compounds from furfural and furfural derivatives through aqueous phase hydrogenation rearrangement | |
| CN109503388A (en) | The method of coproduction cyclohexylamine and dicyclohexyl amine and catalyst system for this method | |
| CN109796303B (en) | Preparation method of isoprene glycol | |
| CN105562046A (en) | Catalyst for condensing methanol and ethanol to prepare propyl alcohol and butanol and preparation method and application of catalyst | |
| CN101747152A (en) | Citral liquid-phase hydrogenation method for synthesizing unsaturated alcohols | |
| CN102451674B (en) | Catalyst for preparing isobutene by methyl tert-butyl ether cracking, preparation method, and application thereof | |
| CN109438153A (en) | A kind of method that citronellal selects decarbonylated reaction to prepare 2,6- dimethyl -2- heptene | |
| CN112387268B (en) | Solid base catalyst for preparing 3-hydroxybutyraldehyde and preparation method thereof | |
| CN105562018A (en) | Catalyst for preparing furfuryl alcohol through furfural gas-phase hydrogenation and preparing method | |
| CN114433152B (en) | Grading method of vanadium phosphorus oxide catalyst | |
| CN106890669A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN109369366A (en) | A kind of method that glycerine catalytic dehydrogenation prepares lactic acid | |
| CN105461526A (en) | Method for preparing cyclopentanone through dehydrogenation of cyclopentanol | |
| CN110694657B (en) | Simple high-carbon aldehyde synthesis catalyst | |
| CN101602006B (en) | Modified aluminum oxide catalyst for synthesizing dimethyl ether and preparation method thereof | |
| CN106890670A (en) | A kind of catalyst of Dimethyl ether carbonylation production methyl acetate and its application | |
| CN114685257B (en) | Method for synthesizing methyl isoamyl ketone | |
| CN104725187A (en) | Technology for directly preparing ethyl alcohol and co-generating methane from synthesis gas | |
| CN110963901A (en) | Preparation method of 3,3, 5-trimethylcyclohexanone | |
| CN102329222A (en) | Method for oxidizing cyclohexane to prepare hexane diacid through one-step method and catalyst used by same | |
| CN109647454A (en) | Aniline prepares the hydrogenation catalyst of cyclohexylamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |