CN113332999A - Novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation - Google Patents
Novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation Download PDFInfo
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- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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Abstract
The invention relates to a novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation, which comprises a carrier and a metal component loaded on the carrier, wherein the metal component comprises a first active center component, a second active center component, a first auxiliary agent and a second auxiliary agent, the weight ratio of the first active center component is 0.05-1%, the weight ratio of the second active center component is 10-30%, the total weight ratio of the first auxiliary agent and the second auxiliary agent is 10-30%, and the balance is the carrier. The catalyst of the invention is applied to the reaction of preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation, the reaction conversion rate is up to 100%, the selectivity of the succinic anhydride is up to more than 99% when the reaction is carried out at low temperature and low pressure, the selectivity of the 1, 4-butanediol is up to more than 95% when the reaction is carried out at higher temperature and pressure, and different product compositions can be controlled by adjusting reaction conditions, thereby achieving the purpose of simultaneously preparing and producing two products, and reducing equipment cost and production cost.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation.
Background
Succinic anhydride and 1, 4-butanediol are important chemical raw materials, and the succinic anhydride and downstream products are widely applied to the fields of food, surfactants, coatings, medicines, agriculture, plastics and the like; 1,4 butanediol and downstream products are widely applied to the fields of organic solvents, plastics, pesticides, medicines, cosmetics and the like. Succinic anhydride is hydrolyzed by a simple process to obtain succinic acid, the succinic acid and 1, 4-butanediol are polymerized to synthesize degradable plastic PBS, and along with the push of plastic limiting orders, the market demand for degradable plastics is greatly increased, so that the demand for succinic anhydride and 1, 4-butanediol is increased.
Both succinic anhydride and 1, 4-butanediol can be prepared from maleic anhydride. Usually succinic anhydride is prepared by direct hydrogenation of maleic anhydride by using a noble metal Pd catalyst or a non-noble metal Ni catalyst, Chinese patent with publication number CN105833863A discloses a supported palladium catalyst for preparing succinic anhydride by low-temperature hydrogenation of maleic anhydride and a preparation method and application thereof, and Chinese patent with publication number CN101502802B discloses a Ni-based supported catalyst for continuously producing succinic anhydride by hydrogenation of maleic anhydride and a preparation method and application thereof. Usually, the 1, 4-butanediol is indirectly prepared by esterification and hydrogenation of maleic anhydride, reports on the preparation of the 1, 4-butanediol by direct hydrogenation of the maleic anhydride are few, and Chinese patent with the authorization number of CN1049207C discloses a method for preparing the 1, 4-butanediol by direct hydrogenation of the maleic anhydride and/or the succinic anhydride as raw materials under the action of a catalyst, the active components of the method are Cu, Zn, Cr and the like, and the results of 100 percent of maleic anhydride conversion rate, 66 percent of 1, 4-butanediol selectivity, 26 percent of gamma-butyrolactone selectivity and 4 percent of tetrahydrofuran selectivity are obtained under the conditions of 228 ℃ of reaction temperature, 7MPa of reaction pressure, 0.1h < -1 > of LHSV and 300 of hydrogen-anhydride ratio.
Maleic anhydride is firstly generated in the hydrogenation process of maleic anhydride, succinic anhydride is then hydrogenated and dehydrated to generate gamma-butyrolactone, the gamma-butyrolactone is hydrogenated to generate 1, 4-butanediol, meanwhile, the gamma-butyrolactone is hydrogenated and dehydrated to generate tetrahydrofuran, and the dehydration of the 1, 4-butanediol can also generate the tetrahydrofuran. Therefore, it is difficult to produce 1, 4-butanediol at high selectivity by the method of hydrogenating maleic anhydride, in the case where the selectivity of other by-products is low. It is more difficult to prepare succinic anhydride and 1, 4-butanediol simultaneously with high selectivity on the same catalyst.
Disclosure of Invention
The invention aims to solve the technical problems and the defects, and provides a novel catalyst for preparing succinic anhydride and 1, 4-butanediol by hydrogenating maleic anhydride, and a preparation method and application of the catalyst.
In order to solve the technical problems, the invention adopts the technical scheme that: a novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation comprises a carrier and a metal component loaded on the carrier, wherein the metal component comprises a first active center component, a second active center component, a first auxiliary agent and a second auxiliary agent, the first active center component is one or more of Pd, Ru, Pt or Au, the second active center component is one or more of Cu, Ni, Co and Cr, the first auxiliary agent is one or more of Zn, Mo, W and Fe, and the second auxiliary agent is one or more of La or Ce; in the catalyst composition, the weight ratio of the first active center component is 0.05-1%, the weight ratio of the second active center component is 10-30%, the total weight ratio of the first auxiliary agent and the second auxiliary agent is 10-30%, and the balance is a carrier.
As the further optimization of the novel catalyst for preparing the succinic anhydride and the 1, 4-butanediol by hydrogenating the maleic anhydride, the carrier is one or more of activated carbon, aluminum oxide, silicon dioxide, titanium dioxide or a silicon-aluminum molecular sieve.
A preparation method of a novel catalyst for preparing succinic anhydride and 1, 4-butanediol by hydrogenating maleic anhydride comprises the following steps:
1) dissolving one or more of metal salts of a second active center component Cu, Ni, Co and Cr in deionized water to obtain a second active solution, soaking the carrier in the second active solution in the atmosphere of nitrogen or other inert gases, heating in a rotating or oscillating state to remove moisture, and roasting in the atmosphere of nitrogen to obtain a supported catalyst precursor A for later use;
2) dissolving metal salts of first aids Zn, Mo, W and Fe in deionized water to obtain an aid solution, soaking the supported catalyst precursor A obtained in the step 1) in the aid solution in the atmosphere of nitrogen or other inert gases, heating to remove moisture in a rotating or oscillating state, and roasting in the atmosphere of nitrogen to obtain a supported catalyst precursor B for later use;
3) dissolving a nitrate of the second auxiliary agent La or Ce in deionized water to obtain a metal nitrate aqueous solution;
4) immersing the supported catalyst precursor B obtained in the step 2) into the metal nitrate aqueous solution in the step 3), heating and evaporating water under the state of rotation or oscillation to load the nitrate of La or Ce on the carrier; roasting in nitrogen atmosphere to obtain a supported catalyst precursor C for later use;
5) dissolving one or more of metal salts of Pd, Ru, Pt or Au as a first active center component in deionized water to obtain a first active solution, and mixing polyvinylpyrrolidone and absolute ethyl alcohol with the obtained first active solution; adding a reducing agent for reaction to obtain a mixed solution for later use;
6) mixing the supported catalyst precursor C obtained in the step 4) with the mixed solution obtained in the step 5), standing, filtering, washing, drying in a nitrogen atmosphere, and roasting in a nitrogen environment to obtain the catalyst.
As a further optimization of the preparation method of the novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation, the prepared catalyst comprises 0.05-1 wt% of a first active component, 10-30 wt% of a second active center component, 10-30 wt% of a first auxiliary agent and a second auxiliary agent, and the balance of a carrier.
As a further optimization of the preparation method of the novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation, the metal salt of Pd, Ru, Pt or Au is selected from palladium chloride, ruthenium chloride, chloroplatinic acid or chloroauric acid, the metal salt of Cu, Ni, Co or Cr is selected from metal sulfate, nitrate and chloride, the metal salt of auxiliary Zn, Mo, W or Fe is selected from metal sulfate, nitrate or chloride, and the nitrate of La and Ce is selected from lanthanum nitrate or cerium nitrate.
As a further optimization of the preparation method of the novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation, the reducing agent is one or more of hydrazine hydrate, sodium borohydride, potassium borohydride and formaldehyde.
The preparation method of the novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation is further optimized, the roasting temperature in the step 1) and the roasting temperature in the step 2) are 200-800 ℃, and the roasting time is 2-6 hours.
As a further optimization of the preparation method of the novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation, the roasting temperature in the step 4) is 300-600 ℃, and the roasting time is 2-6 h.
As a further optimization of the preparation method of the novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation, the roasting temperature in the step 6) is 100-500 ℃, and the roasting time is 2-6 h.
The application method of the catalyst in preparation of succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation comprises the steps of adopting a fixed bed for continuous reaction, placing the catalyst in a fixed bed reactor, controlling maleic anhydride solution and hydrogen to enter into the reaction through a feeding pump and a flow meter respectively under the reaction conditions of 60-200 ℃ and 0.5-4.0MPa, and obtaining succinic anhydride or 1, 4-butanediol or a mixture of the succinic anhydride and the 1, 4-butanediol as a product.
The invention has the following beneficial effects:
the novel catalyst has the characteristics of high conversion rate and high selectivity, and is applied to the reaction of preparing succinic anhydride and 1, 4-butanediol by hydrogenating maleic anhydride, the reaction conversion rate is up to 100%, the selectivity of the succinic anhydride is up to more than 99% when the reaction is carried out at low temperature and low pressure, and the selectivity of the 1, 4-butanediol is up to more than 95% when the reaction is carried out at higher temperature and pressure.
The catalyst of the invention can control different product compositions by adjusting reaction conditions, thereby achieving the purpose of preparing and producing two products at the same time by adopting the same catalyst with high selectivity, and greatly reducing equipment cost and production cost.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments.
Example 1
Dissolving 29.5g of copper nitrate in deionized water, adding 74.5g of alumina carrier into the solution, dipping for 1h under the protection of nitrogen, then rotating and heating, drying by distillation, and then roasting for 4h in a nitrogen atmosphere at 550 ℃ to obtain a supported catalyst precursor A for later use;
dissolving 29.0g of zinc nitrate in deionized water, adding a supported catalyst precursor A into a zinc nitrate solution, soaking for 1h under the protection of nitrogen, then carrying out rotary heating, evaporating to remove water, and then roasting for 4h in a nitrogen atmosphere at 550 ℃ to obtain a supported catalyst precursor B for later use;
dissolving 11.6g of cerium nitrate in deionized water, adding a supported catalyst precursor B into a cerium nitrate solution, soaking for 1h under the protection of nitrogen, then carrying out rotary heating, evaporating to remove water, and then roasting for 2h in a nitrogen atmosphere at 400 ℃ to obtain a supported catalyst precursor C for later use;
dissolving 0.83g of palladium chloride in deionized water to obtain a palladium chloride aqueous solution, adding 8g of polyvinylpyrrolidone, mixing 200ml of absolute ethyl alcohol and the palladium chloride aqueous solution for 20min, adding 200ml of reducing agent formaldehyde, and stirring and reacting for 2h at 80 ℃ to obtain a mixed solution for later use;
and adding the supported catalyst precursor C into the mixed solution, standing for 8h, filtering, washing, drying in a nitrogen atmosphere, and roasting in the nitrogen atmosphere at 300 ℃ for 2h to obtain the catalyst A.
Example 2
The procedure was followed in preparation of the catalyst in example 1 except that 0.83g of palladium chloride in example 1 was replaced with 1.33g of chloroplatinic acid to obtain catalyst B.
Example 3
The procedure was followed in example 1, except that 74.5g of the alumina carrier in example 1 was replaced with 74.5g of the silica carrier, to obtain catalyst C.
Example 4
Catalyst D was prepared in accordance with the procedure for the preparation of the catalyst of example 1, except that 29.5g of copper nitrate in example 1 was replaced with 44.3g of copper nitrate, 74.5g of the alumina carrier was replaced with 64.8g of the alumina carrier, 29.0g of zinc nitrate was replaced with 43.5g of zinc nitrate, and 0.83g of palladium chloride was replaced with 0.43g of palladium nitrate.
Example 5
The procedure was followed in example 1, except that in example 1, 29.5g of copper nitrate was replaced with 31.1g of nickel nitrate, 74.5g of the alumina carrier was replaced with 69.5g of the alumina carrier, 29.0g of zinc nitrate was replaced with 34.0g of ferrous chloride, 11.6g of cerium nitrate was replaced with 15.6g of lanthanum nitrate, and 0.83g of palladium chloride was replaced with 1.33g of chloroplatinic acid, to thereby obtain catalyst E.
Example 6
Catalyst F was prepared in accordance with the procedure for the preparation of the catalyst of example 1, except that 29.5g of copper nitrate in example 1 was replaced with a mixture of 23.6g of copper nitrate and 24.9g of nickel nitrate, 74.5g of alumina carrier was replaced with 68.5g of silica carrier, 29.0g of zinc nitrate was replaced with 20.4g of ammonium molybdate, 11.6g of cerium nitrate was replaced with 15.6g of lanthanum nitrate, and 0.83g of palladium chloride was replaced with 1.33g of chloroplatinic acid.
Example 7
Activating the catalyst A-F for 2h at 200 ℃ in a hydrogen atmosphere by adopting a fixed bed reactor, and then carrying out the reaction of maleic anhydride hydrogenation for preparing succinic anhydride and 1, 4-butanediol under different reaction conditions, wherein the space velocity of the maleic anhydride is 0.5h-1The results of the evaluation of the reaction of the catalysts A to F of examples 1 to 6 are shown in Table 1 below.
Table 1: evaluation results of catalysts A to F
In summary, the novel catalyst prepared in the invention is applied to the reaction of preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation, the reaction conversion rate is up to 100%, the selectivity of the succinic anhydride is up to more than 99% when the reaction is carried out at low temperature and low pressure, the selectivity of the 1, 4-butanediol can be up to more than 95% when the reaction is carried out at higher temperature and pressure, and different product compositions can be controlled by adjusting reaction conditions, so that the purpose of producing two products simultaneously is achieved, and the equipment cost and the production cost are greatly reduced.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A novel catalyst for preparing succinic anhydride and 1, 4-butanediol by hydrogenation of maleic anhydride is characterized in that: the catalyst comprises a carrier and a metal component loaded on the carrier, wherein the metal component comprises a first active center component, a second active center component, a first auxiliary agent and a second auxiliary agent, the first active center component is one or any more of Pd, Ru, Pt or Au, the second active center component is one or any more of Cu, Ni, Co and Cr, the first auxiliary agent is one or any more of Zn, Mo, W and Fe, and the second auxiliary agent is one or two of La or Ce; in the catalyst composition, the weight ratio of the first active center component is 0.05-1%, the weight ratio of the second active center component is 10-30%, the total weight ratio of the first auxiliary agent and the second auxiliary agent is 10-30%, and the balance is a carrier.
2. A novel catalyst for the hydrogenation of maleic anhydride to succinic anhydride and 1, 4-butanediol as claimed in claim 1, wherein: the carrier is one or more of active carbon, aluminum oxide, silicon dioxide, titanium dioxide or a silicon-aluminum molecular sieve.
3. A preparation method of a novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation is characterized by comprising the following steps: the method comprises the following steps:
1) dissolving one or more of metal salts of a second active center component Cu, Ni, Co and Cr in deionized water to obtain a second active solution, soaking the carrier in the second active solution in the atmosphere of nitrogen or other inert gases, heating in a rotating or oscillating state to remove moisture, and roasting in the atmosphere of nitrogen to obtain a supported catalyst precursor A for later use;
2) dissolving metal salts of first aids Zn, Mo, W and Fe in deionized water to obtain an aid solution, soaking the supported catalyst precursor A obtained in the step 1) in the aid solution in the atmosphere of nitrogen or other inert gases, heating to remove moisture in a rotating or oscillating state, and roasting in the atmosphere of nitrogen to obtain a supported catalyst precursor B for later use;
3) dissolving a nitrate of the second auxiliary agent La or Ce in deionized water to obtain a metal nitrate aqueous solution;
4) immersing the supported catalyst precursor B obtained in the step 2) into the metal nitrate aqueous solution in the step 3), heating and evaporating water under the state of rotation or oscillation to load the nitrate of La or Ce on the carrier; roasting in nitrogen atmosphere to obtain a supported catalyst precursor C for later use;
5) dissolving one or more of metal salts of Pd, Ru, Pt or Au as a first active center component in deionized water to obtain a first active solution, and mixing polyvinylpyrrolidone and absolute ethyl alcohol with the obtained first active solution; adding a reducing agent for reaction to obtain a mixed solution for later use;
6) mixing the supported catalyst precursor C obtained in the step 4) with the mixed solution obtained in the step 5), standing, filtering, washing, drying in a nitrogen atmosphere, and roasting in a nitrogen environment to obtain the catalyst.
4. A process for the preparation of a novel catalyst for the hydrogenation of maleic anhydride to succinic anhydride and 1, 4-butanediol as claimed in claim 3, wherein: the weight ratio of the first active component in the prepared catalyst is 0.05-1%, the weight ratio of the second active center component is 10-30%, the total weight ratio of the first auxiliary agent and the second auxiliary agent is 10-30%, and the balance is a carrier.
5. A process for the preparation of a novel catalyst for the hydrogenation of maleic anhydride to succinic anhydride and 1, 4-butanediol as claimed in claim 3, wherein: the metal salt of Pd, Ru, Pt or Au is selected from palladium chloride, ruthenium chloride, chloroplatinic acid or chloroauric acid, the metal salt of Cu, Ni, Co or Cr is selected from metal sulfate, nitrate and chloride, the metal salt of auxiliary Zn, Mo, W or Fe is selected from metal sulfate, nitrate or chloride, and the nitrate of La and Ce is selected from lanthanum nitrate or cerium nitrate.
6. A process for the preparation of a novel catalyst for the hydrogenation of maleic anhydride to succinic anhydride and 1, 4-butanediol as claimed in claim 3, wherein: the reducing agent is selected from one or more of hydrazine hydrate, sodium borohydride, potassium borohydride or formaldehyde.
7. A process for the preparation of a novel catalyst for the hydrogenation of maleic anhydride to succinic anhydride and 1, 4-butanediol as claimed in claim 3, wherein: the roasting temperature in the step 1) and the step 2) is 200-800 ℃, and the roasting time is 2-6 h.
8. A process for the preparation of a novel catalyst for the hydrogenation of maleic anhydride to succinic anhydride and 1, 4-butanediol as claimed in claim 3, wherein: the roasting temperature in the step 4) is 300-600 ℃, and the roasting time is 2-6 h.
9. A process for the preparation of a novel catalyst for the hydrogenation of maleic anhydride to succinic anhydride and 1, 4-butanediol as claimed in claim 3, wherein: the roasting temperature in the step 6) is 100-500 ℃, and the roasting time is 2-6 h.
10. Use of a catalyst according to claim 1 or 2 for the hydrogenation of maleic anhydride to succinic anhydride and 1, 4-butanediol, wherein: the application method comprises the steps of adopting a fixed bed to carry out continuous reaction, putting the catalyst in a fixed bed reactor, controlling the maleic anhydride solution and the hydrogen to enter the reaction through a feeding pump and a flow meter respectively under the reaction conditions of 60-200 ℃ and 0.5-4.0MPa, and obtaining succinic anhydride or 1, 4-butanediol or the mixture of the two from the product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113649049A (en) * | 2021-08-27 | 2021-11-16 | 中国石油化工股份有限公司 | Maleic anhydride selective hydrogenation catalyst, and preparation method and application method thereof |
| CN114181038A (en) * | 2021-12-24 | 2022-03-15 | 常州瑞华化工工程技术股份有限公司 | Method for producing 1, 4-butanediol and coproducing succinic anhydride by direct hydrogenation of maleic anhydride |
| CN114656331A (en) * | 2022-05-07 | 2022-06-24 | 抚顺石化东源化工助剂有限公司 | High yield 1, 4-butanediol production method |
| CN115739111A (en) * | 2022-11-17 | 2023-03-07 | 大连众智长兴精细化工有限公司 | Catalyst for preparing succinic anhydride by maleic anhydride hydrogenation and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058400A (en) * | 1991-08-28 | 1992-02-05 | 复旦大学 | Ordinary-pressure gas-phase hydrogenating synthesis of y-j lactone with cis-anhydride |
| JP2001046871A (en) * | 1999-08-03 | 2001-02-20 | Standard Oil Co | Improved catalyst for hydrogenating maleic acid to produce 1,4-butane diol |
| CN1890231A (en) * | 2003-12-09 | 2007-01-03 | 巴斯福股份公司 | Method for producing defined mixtures of THF BDO and GBL by gas phase hydrogenation |
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
-
2021
- 2021-06-03 CN CN202110616637.3A patent/CN113332999B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058400A (en) * | 1991-08-28 | 1992-02-05 | 复旦大学 | Ordinary-pressure gas-phase hydrogenating synthesis of y-j lactone with cis-anhydride |
| JP2001046871A (en) * | 1999-08-03 | 2001-02-20 | Standard Oil Co | Improved catalyst for hydrogenating maleic acid to produce 1,4-butane diol |
| CN1890231A (en) * | 2003-12-09 | 2007-01-03 | 巴斯福股份公司 | Method for producing defined mixtures of THF BDO and GBL by gas phase hydrogenation |
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 卢伟京等: ""Pd（Ni）对铜基催化剂的调变及对顺酐选择性加氢产物的调控"", 《催化学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113649049A (en) * | 2021-08-27 | 2021-11-16 | 中国石油化工股份有限公司 | Maleic anhydride selective hydrogenation catalyst, and preparation method and application method thereof |
| CN113649049B (en) * | 2021-08-27 | 2024-02-20 | 中国石油化工股份有限公司 | Maleic anhydride selective hydrogenation catalyst and preparation method and application method thereof |
| CN114181038A (en) * | 2021-12-24 | 2022-03-15 | 常州瑞华化工工程技术股份有限公司 | Method for producing 1, 4-butanediol and coproducing succinic anhydride by direct hydrogenation of maleic anhydride |
| CN114181038B (en) * | 2021-12-24 | 2022-10-11 | 常州瑞华化工工程技术股份有限公司 | Method for producing 1,4-butanediol and coproducing succinic anhydride by directly hydrogenating maleic anhydride |
| CN114656331A (en) * | 2022-05-07 | 2022-06-24 | 抚顺石化东源化工助剂有限公司 | High yield 1, 4-butanediol production method |
| CN115739111A (en) * | 2022-11-17 | 2023-03-07 | 大连众智长兴精细化工有限公司 | Catalyst for preparing succinic anhydride by maleic anhydride hydrogenation and preparation method |
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