CN112691674A - Ester hydrogenation catalyst, preparation method and application thereof - Google Patents
Ester hydrogenation catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN112691674A CN112691674A CN201911004011.6A CN201911004011A CN112691674A CN 112691674 A CN112691674 A CN 112691674A CN 201911004011 A CN201911004011 A CN 201911004011A CN 112691674 A CN112691674 A CN 112691674A
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- parts
- gas
- salt
- 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
Images
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to an ester hydrogenation catalyst, a preparation method and application thereof. The catalyst comprises the following components in parts by weight: a) 20-50 parts of metal copper oxide; b) 0-55 parts of a zinc oxide; c) 0-20 parts of zirconium oxide; d)0 to 20 parts of a cerium oxide; e) 1-20 parts of a carrier; the component b) is not zero and the components c) and d) are not zero at the same time. What is needed isThe X-ray diffraction pattern of the catalyst after hydrogen reduction shows that Cu is presented at 2 theta (43.5 +/-0.1 degrees)0Characteristic diffraction peaks. The catalyst is prepared by a step coprecipitation method, is suitable for the reaction of preparing alcohol by ester hydrogenation, and has high raw material conversion rate, high selectivity of 1, 4-cyclohexanedimethanol, high trans-proportion of 1, 4-cyclohexanedimethanol and good catalyst activity when being used for the selective hydrogenation of 1, 4-cyclohexanedicarboxylate.
Description
Technical Field
The invention belongs to the field of catalytic chemistry, and particularly relates to an ester hydrogenation catalyst, a preparation method and application thereof in preparation of high trans-1, 4-cyclohexanedimethanol.
Background
1, 4-Cyclohexanedimethanol (CHDM) is an important monomer for the production of modified polyesters. Due to the symmetrical molecular structure, the polyester product has better thermal stability, transparency, impact resistance, wear resistance and corrosion resistance than PET and PBT. The industrial CHDM product is a mixture of cis-trans isomers, and the CHDM for polymerization contains higher trans proportion and is more powerful because the melting point range (315-320 ℃) of a high polymer of trans-CHDM and terephthalic acid is higher than the melting point range (260-267 ℃) of a high polymer of cis-isomer and terephthalic acid, and the forming processing of the polymer is more convenient. Currently, the trans ratio in industry standard CHDM products is 68%. The worldwide CHDM consumption in 2017 exceeded 20 ten thousand tons per year and increased at an annual rate of 10%. Major producers are companies such as Eastman, Mitsubishi, korea SK, etc., in the united states, and products are hardly sold to the outside. At present, CHDM in China has the demand of 5 million tons/year, only Kai Ling chemical production capacity of 2 million tons/year, Jiangsu Kangheng chemical production capacity of 0.2 million tons/year, actual yield of less than 1 million tons/year, and large gap. At present, the CHDM is industrially produced mainly by taking dimethyl terephthalate as a raw material and carrying out two steps of benzene ring hydrogenation and ester group hydrogenation. Aiming at the ester group hydrogenation of the second step of 1, 4-dimethyl cyclohexanedicarboxylate (DMCD), how to realize the preparation of CHDM with high activity and high selectivity and high trans ratio becomes a research hotspot.
CN105237341A discloses a preparation method for synthesizing 1, 4-cyclohexanedimethanol, which is divided into two-stage hydrogenation reaction. Firstly, carrying out first-stage hydrogenation on terephthalic acid in methanol under the atmosphere of a palladium-containing catalyst and hydrogen; secondly, under hydrogen atmosphere, carrying out two-stage hydrogenation in the presence of a copper-zinc catalyst in methanol, wherein the reaction is carried out in a tank reactor, and the trans-proportion of the product 1, 4-cyclohexanedimethanol is not mentioned.
CN104829431A discloses an application of improving the proportion of trans-1, 4-cyclohexanedimethanol, copper, zinc and aluminum are used as active components, magnesium, barium and manganese are used for modification, polyethylene glycol is added in the preparation process of the catalyst to generate organic matter-containing wastewater, and the obtained high trans-proportion CHDM is obtained at the same time; however, the process conditions required for the hydrogenation are not listed.
CN103687833A discloses a process for the preparation of 1, 4-cyclohexanedimethanol from terephthalic acid, wherein in a 2-step process, the ester hydrogenation catalyst comprises at least one group VIII metal, a copper-containing catalyst, or a combination thereof; terephthalic acid is esterified with (4-methylcyclohexyl) methanol in the presence of a catalyst and the terephthalate ester is hydrogenated to 1, 4-cyclohexanedimethanol. The trans proportion of 1, 4-cyclohexanedimethanol in the process is said to be 74.07%.
In conclusion, when the Cu catalyst is applied to the process of preparing 1, 4-cyclohexanedimethanol by hydrogenating dimethyl 1, 4-cyclohexanedicarboxylate, the Cu-zn-al catalyst has become the mainstream choice in the hydrogenation reaction, but still needs to be further improved in the aspects of product selectivity, trans ratio, catalyst stability, etc.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an ester hydrogenation catalyst, in particular to an ester hydrogenation catalyst for preparing high trans-1, 4-cyclohexanedimethanol and a preparation method thereof.
One of the objects of the present invention is to provide an ester hydrogenation catalyst.
The ester hydrogenation catalyst comprises the following components in parts by weight:
a) 20-50 parts of metal oxide;
b) 0-55 parts of a zinc oxide;
c) 0-20 parts of zirconium oxide;
d)0 to 20 parts of a cerium oxide;
e) 1-20 parts of a carrier;
wherein the carrier is selected from at least one of alumina, silica and molecular sieve;
the component b) is not zero and the components c) and d) are not zero at the same time.
In particular, the amount of the solvent to be used,
in the catalyst of the present invention, the amount of the metal copper oxide is 20 to 50 parts, preferably 25 to 45 parts, and more preferably 30 to 45 parts, by weight, specifically for example: 20. 25, 30, 35, 40, 45 and 50 parts of a stabilizer; the amount of the metal zinc oxide is 0-55 parts, preferably 5-55 parts, more preferably 20-50 parts, specifically for example: 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 and 55 parts; the amount of the metal zirconium oxide is 0-20 parts, preferably 1-15 parts, more preferably 2-12 parts, specifically for example: 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 parts; the amount of the metal cerium oxide is 0-20 parts, preferably 1-15 parts, more preferably 2-12 parts, specifically for example: 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 parts; the amount of the carrier is 1 to 20 parts, preferably 1 to 15 parts, more preferably 3 to 15 parts, specifically for example: 1. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 parts. The contents of the components are based on 100 parts by weight of the total weight of the components.
In the carrier of the catalyst, the molecular sieve can be selected from molecular sieves commonly used in the field, and the molecular sieve is preferably selected from at least one of SBA-15, MCM-41 and MCM-48.
In the catalyst of the present invention, the metal copper oxide, the metal zinc oxide, the metal zirconium oxide and the metal cerium oxide respectively exist in the form of copper oxide, zinc oxide, zirconium oxide and cerium oxide, and specifically can be copper oxide (CuO), zinc oxide (ZnO) and zirconium dioxide (ZrO)2) Cerium oxide (CeO)2) Exist in the form of (1).
When the catalyst is applied to reaction, hydrogen reduction treatment is needed, and after hydrogen reduction, the metal copper in the catalyst mainly exists in the form of zero-valent copper and a small amount of monovalent copper, so that the catalyst has catalytic activity.
In the catalyst, the metal copper oxide and the metal zinc oxide can be called as active components of the catalyst and are sources of catalytic activity; the metal zirconium oxide and/or the metal cerium oxide can be called as an auxiliary agent of the catalyst of the invention, and can play a role in modifying the carrier and helping active components to be better distributed on the carrier.
The catalyst of the invention preferably comprises metal zirconium oxide and metal cerium oxide at the same time; more preferably, the weight ratio of the metal zirconium oxide to the metal cerium oxide is (1-9) to 1, and preferably (1-5) to 1. Within the proportion range, the reduction temperature (namely copper reduction temperature) required by the catalyst is obviously reduced, and the catalyst is more excellent in the conversion rate of the dimethyl 1, 4-cyclohexanedicarboxylate and the trans-proportion of the product in the reaction of preparing the 1, 4-cyclohexanedimethanol by selective hydrogenation of the 1, 4-cyclohexanedicarboxylate.
According to the catalyst, in-situ reduction XRD analysis is adopted, the catalyst is preferably 150-170 ℃ at the reduction temperature of 150-200 ℃, more preferably 160-170 ℃, and the X-ray diffraction spectrum shows Cu at the 2 theta of 43.5 +/-0.1 DEG0Characteristic diffraction peaks.
Another object of the present invention is to provide a process for preparing the alcohol catalyst.
The preparation method of the catalyst comprises the steps of coprecipitating the components on the carrier and then roasting.
The co-precipitation may include a one-step precipitation method, i.e. the components are co-precipitated together on the support; fractional precipitation may also be used.
The preparation method of the catalyst provided by the invention is preferably carried out by adopting a step-by-step precipitation method, and specifically comprises the steps of modifying a carrier, compounding active components and roasting.
The carrier modification step comprises the step of coprecipitating an auxiliary agent salt solution and a precipitator solution in the carrier modification step to obtain a modified carrier; the co-precipitation is preferably co-current co-precipitation;
the step of compounding the active components comprises the steps of coprecipitating an active component salt solution and a precipitator solution on the modified carrier; the co-precipitation is preferably co-current co-precipitation;
the roasting step comprises roasting the modified carrier compounded with the active component under the normal condition to obtain the catalyst of the invention.
In particular, the amount of the solvent to be used,
the solvent of the solution of the assistant salt solution can be at least one of water and an organic solvent; preferably an aqueous solution of a cerium salt and/or a zirconium salt. Wherein the organic solvent can be an organic solvent commonly used in the field as long as the auxiliary salt can be fully dissolved and does not react with each raw material of the coprecipitation; wherein the water is preferably deionized water.
The concentration of the adjuvant salt solution is not limited as long as the adjuvant salt can be sufficiently dissolved. The concentration of the auxiliary salt solution, preferably the auxiliary salt water solution, can be generally 0.2-2.0 mol/L (M), preferably 0.2-1.0 mol/L.
The auxiliary salt is preferably a water-soluble salt, such as at least one of nitrate, hydrochloride, acetate, and the like, and specifically may be: zirconium nitrate, zirconium chloride, zirconium acetate, cerium nitrate, cerium chloride, cerium acetate, and the like.
The active ingredient salt solution described above, the solvent of the solution may be at least one of water and an organic solvent; preferably an aqueous solution of a copper salt and a zinc salt. Wherein the organic solvent can be an organic solvent commonly used in the field as long as the salt of the active component can be fully dissolved and does not react with each raw material of the coprecipitation; wherein the water is preferably deionized water.
The concentration of the active ingredient salt solution is not limited as long as the active ingredient salt can be sufficiently dissolved. The concentration of the active ingredient salt solution, preferably the active ingredient salt solution, can be generally 0.2-2.0 mol/L (M), preferably 0.2-1.0 mol/L.
The active ingredient salt is preferably a water-soluble salt, such as at least one of nitrate, hydrochloride, acetate and the like, and specifically can be: copper nitrate, copper chloride, copper acetate, zinc nitrate, zinc chloride, zinc acetate, and the like.
The precipitants of the coprecipitation in the carrier modification step and the active component compounding step can be the same or different; the precipitant and coprecipitation conditions for coprecipitation can be those commonly used in coprecipitation in the prior art, and are preferably independently selected from the following ranges: the reaction is carried out at 50-90 ℃, preferably 60-80 ℃, and the pH of the end point is controlled to be 6.0-8.0.
The solvent of the precipitant solution can be at least one of water and an organic solvent; preferably an aqueous solution of the precipitating agent. Wherein the organic solvent can be an organic solvent commonly used in the field as long as the auxiliary salt can be fully dissolved and does not react with each raw material of the coprecipitation; wherein the water is preferably deionized water.
The concentration of the precipitant solution is not limited as long as the precipitant can be sufficiently dissolved. The concentration of the precipitant solution, preferably the precipitant aqueous solution, may be generally 1 to 20mol/L (M), preferably 1 to 15 mol/L.
The precipitant may be one commonly used in the coprecipitation method in the prior art, such as at least one selected from sodium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and ammonia water. Wherein the ammonia water can be directly used as a precipitator solution, and can also be added with a solvent for dilution.
The amount of the precipitant is also the amount used in the common coprecipitation method, and the molar ratio of the precipitant to the total molar amount of the metal ions in the auxiliary salt or the active component salt is not less than 1:1, and usually a little excess of the precipitant is needed.
The calcination step described above may be carried out by a calcination method and conditions that are generally used in the art. The modified carrier compounded with the active component is preferably roasted in an air atmosphere, and the specific roasting condition is preferably 300-600 ℃, preferably 400-500 ℃; roasting for 1-8 hours, preferably 2-6 hours.
In the method for preparing the catalyst of the present invention, the catalyst can be molded by a usual method after calcination, and the preferable molding method is tablet molding.
In the preparation method of the catalyst, the carrier modification step and the active component compounding step can comprise conventional treatment steps of carrying out suction filtration, washing, drying and the like on the obtained product, and the adopted conditions and equipment are conventional suction filtration, washing and drying conditions and equipment.
The preparation method of the catalyst of the invention, a preferred embodiment, specifically comprises:
(a) preparing an auxiliary agent salt into a solution I, (b) preparing a precipitator into a solution II, (c) placing a carrier into a base solution, and performing parallel flow precipitation on the solution I and the solution II at the temperature of 50-90 ℃, preferably 60-80 ℃, wherein the pH value of a terminal point is controlled to be 6.0-8.0; stirring and aging for 3-6 hours; then, carrying out suction filtration and washing for common treatment; (d) preparing a copper salt and a zinc salt into a solution III, (e) preparing a precipitator into a solution IV, (f) placing a modified carrier into a base solution, and performing concurrent flow precipitation on the solution III and the solution IV at the temperature of 50-90 ℃, preferably 60-80 ℃, wherein the pH value of a terminal point is controlled to be 6.0-8.0; stirring and aging for 3-6 hours; then, the conventional treatments such as filtration, washing, drying and the like can be carried out; (g) and roasting the modified carrier compounded with the active component in an air atmosphere at 300-600 ℃ to obtain the catalyst finished product.
The base solution may be at least one of water and an organic solvent; preferably deionized water. The dosage of the carrier is only required to ensure that the carrier can be immersed, so that the components can be stirred and mixed conveniently; the amount of the base solution is usually 1 to 5 times, preferably 2 to 4 times, the weight of the catalyst.
The finished product of the catalyst can be used only by introducing hydrogen into a reactor for reduction. The reduction conditions thereof adopt the conditions which are common in the field of hydrogen reduction of catalysts, and particularly, the reduction conditions preferably comprise: reducing under hydrogen, wherein the preferable reduction temperature is 100-300 ℃; the reduction time is 1-10 hours.
Because the precipitation values of all components of the catalyst are different, the catalyst is prepared by adopting a step-by-step precipitation method, so that all the components are well dispersed. The catalyst prepared by the fractional precipitation method is adopted to obviously improve the conversion rate and the trans-form proportion of the 1, 4-cyclohexane dicarboxylic acid dimethyl ester in the reaction of preparing the 1, 4-cyclohexane dimethanol by selective hydrogenation of the 1, 4-cyclohexane dicarboxylic acid ester compared with the catalyst prepared by the one-step precipitation method.
According to the catalyst, an in-situ reduction XRD is adopted for analysis, an X-ray diffraction spectrum before hydrogen reduction shows a CuO characteristic diffraction peak at a 2 theta of 38.9 +/-0.1 degrees, and after hydrogen reduction at a reduction temperature of 150-200 ℃, preferably at a temperature of 150-170 ℃, more preferably at a temperature of 160-170 ℃, the obtained catalyst shows a Cu0 characteristic diffraction peak at a 2 theta of 43.5 +/-0.1 degrees.
The invention also aims to provide the application of the alcohol preparation catalyst in the preparation of alcohol by ester hydrogenation.
Specifically, the catalyst provided by the invention can be suitable for the reaction for preparing 1, 4-cyclohexanedimethanol by selective hydrogenation of 1, 4-cyclohexanedicarboxylate, and is more preferably suitable for the reaction for preparing 1, 4-cyclohexanedimethanol by hydrogenation of 1, 4-cyclohexanedicarboxylate.
The catalyst can also be suitable for the reaction of preparing ethylene glycol by hydrogenation of oxalate;
the catalyst of the invention can also be applied to the reaction of preparing ethanol by acetate hydrogenation.
It is a fourth object of the present invention to provide a process for the preparation of 1, 4-cyclohexanedimethanol.
The method for preparing the 1, 4-cyclohexanedimethanol comprises the step of taking 1, 4-cyclohexanedicarboxylate and hydrogen as raw materials, and carrying out contact reaction with the ester hydrogenation catalyst to ensure that the 1, 4-cyclohexanedicarboxylate in the raw materials is hydrogenated and converted into the 1, 4-cyclohexanedimethanol. The 1, 4-cyclohexanedicarboxylate ester may preferably be dimethyl 1, 4-cyclohexanedicarboxylate.
In the technical scheme, the reaction conditions are as follows: the hydrogen/ester molar ratio is (100-200): 1, the volume space velocity is 0.1-1.5 hours-1The reaction temperature is 150-250 ℃, and the reaction pressure is 1.0-10.0 MPa;
the reaction conditions are preferably: the hydrogen-ester molar ratio is preferably 100-150; the preferred volume space velocity is 0.1-0.6 h-1(ii) a The reaction temperature is preferably 200-250 ℃; the reaction pressure is preferably 4.0-6.0 MPa.
Aiming at the reaction of preparing 1, 4-cyclohexanedimethanol by hydrogenating dimethyl 1, 4-cyclohexanedicarboxylate, three side reactions mainly exist: (1) the 1, 4-cyclohexane dimethyl phthalate is subjected to diester-group mono-hydrogenation to generate 4-hydroxymethyl cyclohexane methyl formate; (2) the product 1, 4-cyclohexanedimethanol is subjected to over-hydrogenation to generate 4-methyl cyclohexane methanol; (3) the product 1, 4-cyclohexanedimethanol is etherified with methanol generated by the reaction to generate 1, 4-cyclohexanedimethanol monomethyl ether. Wherein (2) and (3) are caused by excessive acidity of the surface of the carrier. Meanwhile, cis-trans isomers exist in the 1, 4-cyclohexanedimethanol generated by hydrogenation, and the 1, 4-cyclohexanedimethanol with high trans-form proportion needs to be obtained by considering the subsequent application of the product. From the compound conformation analysis, the high-temperature high-pressure reaction is favorable for generating the trans-1, 4-cyclohexanedimethanol with stable conformation, but the side reaction ratio is increased. In order to solve the problem, the invention ensures high dispersion of the active components of the catalyst and good thermal stability of the prepared catalyst by introducing zirconium and cerium elements. The catalyst has high raw material conversion rate, high selectivity of 1, 4-cyclohexanedimethanol, high trans-proportion 1, 4-cyclohexanedimethanol and good catalyst activity maintenance when being used for selective hydrogenation of 1, 4-dimethyl cyclohexanedicarboxylate.
In the reaction for preparing 1, 4-cyclohexanedimethanol by selective hydrogenation of 1, 4-cyclohexanedicarboxylate by using the catalyst prepared by the invention, for example, dimethyl 1, 4-cyclohexanedicarboxylate and hydrogen are used as raw materials, the reaction temperature is 230 ℃, the reaction pressure is 5.0MPa, the hydrogen/ester molar ratio is 140:1, and the space velocity is 0.3 h-1Under the conditions, the conversion rate of the 1, 4-cyclohexane dimethyl dicarboxylate is more than 99 percent, the liquid phase selectivity of the 1, 4-cyclohexane dimethanol is more than 97.5 percent, and the proportion of the trans-1, 4-cyclohexane dimethanol is more than 76.5 percent; the catalyst can be run continuously for 1000 hours. For the liquid phase selectivity of 1, 4-cyclohexanedimethanol, creative labor is required for increasing every 0.1% on the basis of 97%, and at the same time, trans-formThe 1, 4-cyclohexanedimethanol is limited by thermodynamic equilibrium, and creative labor is required for increasing the proportion of the trans-1, 4-cyclohexanedimethanol by 0.1% on the basis of 74%, so that the technical scheme of the invention achieves better technical effect.
Drawings
FIG. 1 is a view showing CuO-ZnO/Al obtained in comparative example 12O3And (3) carrying out in-situ reduction on the catalyst by XRD (X-ray diffraction) spectrum.
FIG. 2 is a view showing CuO-ZnO-ZrO obtained in example 12/Al2O3And (3) carrying out in-situ reduction on the catalyst by XRD (X-ray diffraction) spectrum.
FIG. 3 shows the CuO-ZnO-CeO obtained in example 32/Al2O3And (3) carrying out in-situ reduction on the catalyst by XRD (X-ray diffraction) spectrum.
FIG. 4 is a view showing CuO-ZnO-ZrO obtained in example 42-CeO2/Al2O3And (3) carrying out in-situ reduction on the catalyst by XRD (X-ray diffraction) spectrum.
Fig. 1-4 show that the catalyst is analyzed by in-situ reduction XRD, wherein, as can be seen from the spectrogram, the CuO characteristic diffraction peak overlaps with the ZnO characteristic diffraction peak within the range of 30 ° to 35.6 ° and is difficult to distinguish; and 38.7 DEG and 38.9 DEG are relatively independent characteristic diffraction peaks of CuO, and are respectively assigned to a CuO (111) crystal plane and a CuO (200) crystal plane. At the reduction temperature of 150-200 ℃, the independent CuO characteristic diffraction peak gradually weakens to disappear along with the increase of the reaction temperature, and Cu appears when 2 theta is 43.5 +/-0.1 DEG0Characteristic diffraction peaks.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
Test methods and standards related to the detailed description of the invention section:
1. in the specific embodiment of the invention, the conversion rate and the molar selectivity of 1, 4-cyclohexanedimethanol prepared by hydrogenation of dimethyl 1, 4-cyclohexanedicarboxylate are calculated, the product is analyzed by gas chromatography, and the conversion rate of raw materials, the product selectivity and the trans-CHDM ratio are determined by an area normalization method.
2. In a specific embodiment of the present invention, the composition of the catalyst was analyzed by ICP (inductively coupled plasma) and XRF (X-ray fluorescence) methods. The composition ratio of the metal and its oxide is determined by XPS (X-ray photoelectron spectroscopy). The ICP test conditions were: the Varian 700-ES series XPS instrument. XRF test conditions were: rigaku ZSX 100e model XRF instrument. XPS test conditions: perkin Elmer PHI 5000C ESCA type X-ray photoelectron spectrometer with Mg K exciting light source, operation voltage l0kV, current 40mA, vacuum degree 4.0X 10-8Pa。
3. The catalyst precursor and the catalyst of the invention are subjected to in-situ reduction XRD (X-ray diffraction) and the diffraction patterns of the catalyst precursor and the catalyst are analyzed; XRD test conditions: the device comprises a BUKER D8 ADVANCE type X-ray powder diffractometer, Cu-K target radiation, 0.1509nm, tube pressure 40kV, current 100mA, temperature range 150-200 ℃, temperature rise rate 5 degrees per minute, scanning range 5-80 degrees per minute and scanning rate 6 degrees per minute.
The various starting materials referred to in the detailed description of the invention are commercially available. The water is deionized water.
[ COMPARATIVE EXAMPLE 1 ]
Weighing 105.7 g of copper nitrate trihydrate and 213.0 g of zinc nitrate hexahydrate, and preparing an aqueous solution with the concentration of 0.6M, namely solution I; 134.8 g of sodium carbonate is weighed and prepared into 1.0M aqueous solution, namely solution II. Placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 70 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the pH value of a final point to be about 7.0, aging the obtained slurry for 3 hours, filtering, washing, drying at 90 ℃, roasting at 500 ℃ for 4 hours, and tabletting to obtain the catalyst CD1, wherein the composition and the evaluation result of the catalyst CD1 are shown in Table 1.
[ example 1 ]
Weighing 27.9 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.6M, namely a solution I; 9.1g of ammonia water with the mass fraction of 25 percent is weighed to obtain solution II. And (2) placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 70 ℃, dropwise adding the solution I and the solution II in a parallel flow manner, uniformly stirring, controlling the pH value of a terminal point to be 8.0, preparing gel, aging for 4 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 105.7 g of copper nitrate trihydrate and 183.6 g of zinc nitrate hexahydrate, and preparing a solution with the concentration of 0.6M, namely a solution III; 123.3 g of sodium carbonate is weighed to prepare a solution with the concentration of 1.0M, namely a solution IV. Placing the prepared modified carrier in a base solution (300g of deionized water), heating to 70 ℃, dropwise adding the solution III and the solution IV in a concurrent flow manner, controlling the pH value of the end point to be about 7.0, aging the obtained slurry for 3 hours, filtering, washing, drying at 90 ℃, roasting at 500 ℃ for 4 hours, and tabletting to obtain a catalyst C1, wherein the composition and evaluation results of the catalyst C1 are shown in Table 1.
[ example 2 ]
Weighing 105.7 g of copper nitrate trihydrate, 183.6 g of zinc nitrate hexahydrate and 27.9 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.8M, wherein the solution is a solution I; 125.6 g of sodium carbonate is weighed to prepare a solution with the concentration of 1.0M, namely a solution II. Placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 70 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the end point pH value to be about 7.0, aging the obtained slurry for 3 hours, filtering, washing, drying at 90 ℃, roasting at 500 ℃ for 4 hours, and tabletting to obtain the catalyst C2, wherein the composition and the evaluation result of the catalyst C2 are shown in Table 1.
[ example 3 ]
Weighing 12.6 g of cerous nitrate hexahydrate to prepare a solution with the concentration of 0.8M, namely a solution I; and 4g of ammonia water with the mass fraction of 25% is weighed to obtain a solution II. Placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 60 ℃, dropwise adding the solution I and the solution II in a parallel flow manner, uniformly stirring, controlling the pH value of a terminal point to be 7.0, preparing gel, aging for 3 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 105.7 g of copper nitrate trihydrate and 194.6 g of zinc nitrate hexahydrate, and preparing a solution with the concentration of 0.4M, namely a solution III; 127.6 g of sodium carbonate is weighed to prepare a solution with the concentration of 1.0M, namely the solution IV. Placing the prepared modified carrier in a base solution (300g of deionized water), heating to 60 ℃ for 6, dropwise adding the solution III and the solution IV in a concurrent flow manner, controlling the pH value of the end point to be about 6.0, aging the obtained slurry for 4 hours, filtering, washing, drying at 90 ℃, roasting at 600 ℃ for 2 hours, and tabletting to obtain the catalyst C3, wherein the composition and the evaluation result of the catalyst C3 are shown in Table 1.
[ example 4 ]
Weighing 12.6 g of cerous nitrate hexahydrate and 27.9 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.6M, namely a solution I; and weighing 13.2g of ammonia water with the mass fraction of 25 percent to obtain solution II. And (2) placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 80 ℃, dropwise adding the solution I and the solution II in a parallel flow manner, uniformly stirring, controlling the pH value of a terminal point to be 6.0, preparing gel, aging for 5 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 105.7 g of copper nitrate trihydrate and 165.3 g of zinc nitrate hexahydrate to prepare a solution with the concentration of 0.4M, namely a solution III; weighing 116.1 g of sodium carbonate to prepare a solution with the concentration of 1.0M, namely a solution IV. Placing the prepared alumina precursor in a base solution (300g of deionized water), heating to 80 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the pH value of the end point to be about 8.0, aging the obtained slurry for 5 hours, filtering, washing, drying at 90 ℃, roasting at 400 ℃ for 5 hours, and tabletting to obtain a catalyst C4, wherein the composition and the evaluation result of the catalyst C4 are shown in Table 1.
[ example 5 ]
Weighing 16.4 g of cerous nitrate hexahydrate and 22.7 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.6M, namely a solution I; 12.7g of ammonia water with the mass fraction of 25 percent is weighed to obtain solution II. And (2) placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 80 ℃, dropwise adding the solution I and the solution II in a parallel flow manner, uniformly stirring, controlling the pH value of a terminal point to be 6.0, preparing gel, aging for 5 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 105.7 g of copper nitrate trihydrate and 165.3 g of zinc nitrate hexahydrate to prepare a solution with the concentration of 0.4M, namely a solution III; weighing 116.1 g of sodium carbonate to prepare a solution with the concentration of 1.0M, namely a solution IV. Placing the prepared modified carrier in a base solution (300g of deionized water), heating to 80 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the pH value of a final point to be about 8.0, aging the obtained slurry for 5 hours, filtering, washing, drying at 90 ℃, roasting at 400 ℃ for 5 hours, and tabletting to obtain a catalyst C5, wherein the composition and the evaluation result of the catalyst C5 are shown in Table 1.
[ example 6 ]
Weighing 3.3 g of cerous nitrate hexahydrate and 40.8 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.6M, namely a solution I; 14.4g of ammonia water with the mass fraction of 25 percent is weighed to obtain solution II. And (2) placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 80 ℃, dropwise adding the solution I and the solution II in a parallel flow manner, uniformly stirring, controlling the pH value of a terminal point to be 6.0, preparing gel, aging for 5 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 105.7 g of copper nitrate trihydrate and 165.3 g of zinc nitrate hexahydrate to prepare a solution with the concentration of 0.4M, namely a solution III; weighing 116.1 g of sodium carbonate to prepare a solution with the concentration of 1.0M, namely a solution IV. Placing the prepared modified carrier in a base solution (300g of deionized water), heating to 80 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the pH value of a final point to be about 8.0, aging the obtained slurry for 5 hours, filtering, washing, drying at 90 ℃, roasting at 400 ℃ for 5 hours, and tabletting to obtain a catalyst C6, wherein the composition and the evaluation result of the catalyst C6 are shown in Table 1.
[ example 7 ]
Weighing 25.2 g of cerous nitrate hexahydrate and 10.5 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.6M, namely a solution I; 11.5g of ammonia water with the mass fraction of 25 percent is weighed to obtain solution II. And (2) placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 70 ℃, dropwise adding the solution I and the solution II in a parallel flow manner, uniformly stirring, controlling the pH value of a terminal point to be 7.0, preparing gel, aging for 4 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 105.7 g of copper nitrate trihydrate and 165.3 g of zinc nitrate hexahydrate to prepare a solution with the concentration of 0.4M, namely a solution III; weighing 116.1 g of sodium carbonate to prepare a solution with the concentration of 1.0M, namely a solution IV. Placing the prepared modified carrier in a base solution (300g of deionized water), heating to 70 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the pH value of a final point to be about 8.0, aging the obtained slurry for 5 hours, filtering, washing, drying at 90 ℃, roasting at 450 ℃ for 5 hours, and tabletting to obtain a catalyst C7, wherein the composition and the evaluation result of the catalyst C7 are shown in Table 1.
[ example 8 ]
Weighing 2.5 g of cerous nitrate hexahydrate and 17.5 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.6M, namely a solution I; 6.5g of ammonia water with the mass fraction of 25 percent is weighed to obtain solution II. And (2) placing 7.0 g of alumina powder in a base solution (300g of deionized water), heating to 80 ℃, dropwise adding the solution I and the solution II in a parallel flow manner, uniformly stirring, controlling the pH value of a terminal point to be 6.0, preparing gel, aging for 5 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 135.9 g of copper nitrate trihydrate and 153.5 g of zinc nitrate hexahydrate, and preparing a solution with the concentration of 0.4M, namely a solution III; 117.2 g of sodium carbonate is weighed to prepare a solution with the concentration of 1.0M, namely a solution IV. Placing the prepared modified carrier in a base solution (300g of deionized water), heating to 80 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the pH value of a final point to be about 8.0, aging the obtained slurry for 5 hours, filtering, washing, drying at 90 ℃, roasting at 400 ℃ for 5 hours, and tabletting to obtain a precursor of the catalyst C8, wherein the composition and the evaluation result of the catalyst C8 are shown in Table 1.
[ example 9 ]
Weighing 18.9 g of cerous nitrate hexahydrate and 26.2 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.4M, namely a solution I; 14.7g of ammonia water with the mass fraction of 25 percent is weighed to obtain solution II. And (2) placing 15.0 g of SBA-15 powder into a base solution (300g of deionized water), heating to 65 ℃, dropwise adding the solution I and the solution II in a concurrent flow manner, uniformly stirring, controlling the pH value of a terminal point to be 6.0, preparing gel, aging for 3 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 75.5 g of copper nitrate trihydrate and 165.3 g of zinc nitrate hexahydrate, and preparing a solution with the concentration of 0.8M, namely a solution III; 92.0 g of sodium carbonate is weighed to prepare a solution with the concentration of 1.0M, namely a solution IV. Placing the prepared modified carrier in a base solution (300g of deionized water), heating to 65 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the pH value of a final point to be about 8.0, aging the obtained slurry for 4 hours, filtering, washing, drying at 90 ℃, roasting at 500 ℃ for 5 hours, and tabletting to obtain a catalyst C9, wherein the composition and the evaluation result of the catalyst C9 are shown in Table 1.
[ example 10 ]
Weighing 18.9 g of cerous nitrate hexahydrate and 26.2 g of zirconium nitrate pentahydrate to prepare a solution with the concentration of 0.6M, namely a solution I; 14.7g of ammonia water with the mass fraction of 25 percent is weighed to obtain solution II. And (2) putting 10.0 g of silicon oxide and 5.0 g of alumina powder into a base solution (300g of deionized water), heating to 75 ℃, dropwise adding the solution I and the solution II in a parallel flow manner, uniformly stirring, controlling the pH value of a terminal point to be 6.0, preparing gel, aging for 2 hours, carrying out suction filtration, and washing to obtain the modified carrier.
Weighing 75.5 g of copper nitrate trihydrate and 165.3 g of zinc nitrate hexahydrate to prepare a solution with the concentration of 0.4M, namely a solution III; 92.0 g of sodium carbonate is weighed to prepare a solution with the concentration of 1.0M, namely a solution IV. Placing the prepared modified carrier in a base solution (300g of deionized water), heating to 75 ℃, dropwise adding the solution I and the solution II in a cocurrent flow manner, controlling the pH value of the end point to be about 8.0, aging the obtained slurry for 2 hours, filtering, washing, drying at 90 ℃, roasting at 500 ℃ for 5 hours, and tabletting to obtain the catalyst C10, wherein the composition and the evaluation result of the catalyst C10 are shown in Table 1.
[ example 11 ]
Evaluation experiment of catalyst: the catalysts obtained in examples 1 to 10 and comparative example 1 were used in a selective hydrogenation reaction of dimethyl 1, 4-cyclohexanedicarboxylate and evaluated.
Taking 30mL of each catalyst precursor obtained in examples 1-10 or comparative example 1, and reducing the precursor for 10h at 300 ℃ by adopting pure hydrogen to obtain the catalyst; 1, 4-cyclohexane dimethyl phthalate and pure hydrogen are taken as raw materials, the reaction temperature is 230 ℃, the reaction pressure is 5.0MPa, the hydrogen/ester molar ratio is 140:1, and the volume space velocity is 0.3 hour-1The hydrogenation was carried out under the conditions of (1), and the results of the reaction at 100 hours and 1000 hours, as analyzed by on-line chromatography, are shown in Table 1.
TABLE 1
Claims (18)
1. An ester hydrogenation catalyst comprises the following components in parts by weight:
a) 20-50 parts of metal copper oxide;
b) 0-55 parts of a zinc oxide;
c) 0-20 parts of zirconium oxide;
d)0 to 20 parts of a cerium oxide;
e) 1-20 parts of a carrier;
wherein the carrier is selected from at least one of alumina, silica and molecular sieve;
wherein the component b) is not zero and the components c) and d) are not simultaneously zero.
2. The catalyst of claim 1, wherein the metal copper oxide is present in an amount of 25 to 45 parts, preferably 30 to 45 parts, by weight; 5-55 parts of metal zinc oxide, preferably 20-50 parts; 1-15 parts of metal zirconium oxide, preferably 2-12 parts; 1-15 parts of metal cerium oxide, preferably 1-12 parts; the using amount of the carrier is 1-15 parts, and preferably 1-10 parts.
3. The catalyst according to claim 1, wherein the weight ratio of the metal zirconium oxide to the metal cerium oxide is (1-9) to 1, preferably (1-5) to 1.
4. The catalyst of claim 1, wherein the molecular sieve is selected from at least one of SBA-15, MCM-41, MCM-48.
5. The catalyst of claim 1, wherein the metallic copper oxide is copper oxide, the metallic zinc oxide is zinc oxide, the metallic zirconium oxide is zirconium dioxide, and the metallic cerium oxide is cerium dioxide.
6. According to claims 1 to 5The catalyst is characterized in that the catalyst presents a Cu diffraction pattern at 2 theta of 43.5 +/-0.1 degrees when analyzed by in-situ reduction XRD (X-ray diffraction) at the reduction temperature of 150-200 ℃, preferably 150-170 DEG0Characteristic diffraction peaks.
7. A method of preparing an ester hydrogenation catalyst according to any of claims 1 to 6, comprising the step of co-precipitating the components on the support followed by calcination.
8. The method according to claim 7, characterized in that the coprecipitation is preferably carried out by fractional precipitation, which includes the steps of carrier modification, compounding the active components.
9. The method of claim 7, comprising the steps of:
a step of modifying the carrier: co-precipitating an assistant salt solution and a precipitator solution on the carrier to obtain a modified carrier; the assistant salt solution is cerium salt and/or zirconium salt solution;
compounding active components: co-precipitating an active component salt solution and a precipitator solution on the modified carrier; the active component salt solution is copper salt and zinc salt solution;
and (3) roasting: the method comprises the steps of roasting the modified carrier compounded with the active component in air atmosphere to obtain the catalyst;
the co-precipitation described above is preferably co-current co-precipitation.
10. The production method according to claim 9,
the assistant salt solution is cerium salt and/or zirconium salt water solution; and/or the presence of a gas in the gas,
the active component salt solution is an aqueous solution of copper salt and zinc salt; and/or the presence of a gas in the gas,
the precipitant solution is a precipitant aqueous solution.
11. The production method according to claim 10,
the auxiliary salt is water-soluble salt, preferably at least one of nitrate, hydrochloride and acetate; and/or the presence of a gas in the gas,
the concentration of the auxiliary agent salt water solution is 0.2-2.0 mol/L; and/or the presence of a gas in the gas,
the active component salt is water-soluble salt, preferably at least one of nitrate, hydrochloride and acetate; and/or the presence of a gas in the gas,
the concentration of the active component salt solution is 0.2-2.0 mol/L; and/or the presence of a gas in the gas,
the precipitant is selected from at least one of sodium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate and ammonia water; and/or the presence of a gas in the gas,
the concentration of the precipitant solution is 1-20 mol/L.
12. The method according to any one of claims 7 to 11,
the coprecipitation is carried out at 50-90 ℃, preferably 60-80 ℃, and the pH of a terminal point is controlled to be 6.0-8.0; and/or the presence of a gas in the gas,
the roasting temperature is 300-600 ℃, and preferably 400-500 ℃; and/or the presence of a gas in the gas,
the roasting time is 1-8 hours, preferably 2-6 hours.
13. An ester hydrogenation catalyst prepared by the method of any one of claims 7 to 12.
14. A process for the preparation of 1, 4-cyclohexanedimethanol comprising the step of contacting a 1, 4-cyclohexanedicarboxylate ester and hydrogen with an ester hydrogenation catalyst according to any one of claims 1 to 6 or 13.
15. The process of claim 14 for the preparation of 1, 4-cyclohexanedimethanol, wherein the reaction conditions are: the hydrogen/ester molar ratio is (100-200): 1, preferably 100-150; volume airspeed of 0.1 &1.5 hours-1Preferably 0.1 to 0.6 hours-1(ii) a The reaction temperature is 150-250 ℃, preferably 200-250 ℃, and the reaction pressure is 1.0-10.0 MPa, preferably 4.0-6.0 MPa.
16. Use of an ester hydrogenation catalyst as claimed in any one of claims 1 to 6 or claim 13 in an ester hydrogenation reaction.
17. The use according to claim 16, comprising the use of the ester hydrogenation catalyst in a reaction of hydrogenating oxalate to ethylene glycol.
18. The use according to claim 16, comprising the use of the ester hydrogenation catalyst in the reaction of hydrogenation of acetate to ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911004011.6A CN112691674B (en) | 2019-10-22 | 2019-10-22 | Ester hydrogenation catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911004011.6A CN112691674B (en) | 2019-10-22 | 2019-10-22 | Ester hydrogenation catalyst, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112691674A true CN112691674A (en) | 2021-04-23 |
| CN112691674B CN112691674B (en) | 2023-08-29 |
Family
ID=75505460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911004011.6A Active CN112691674B (en) | 2019-10-22 | 2019-10-22 | Ester hydrogenation catalyst, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112691674B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354798A (en) * | 2019-07-17 | 2019-10-22 | 中国人民大学 | A kind of cerium zirconium zinc metal composite adsorbent and the preparation method and application thereof |
| CN113332989A (en) * | 2021-05-28 | 2021-09-03 | 浙江工业大学 | Alumina supported copper-rare earth metal oxide catalyst and preparation method and application thereof |
| CN115301248A (en) * | 2021-05-08 | 2022-11-08 | 中国石油化工股份有限公司 | Catalyst for preparing 1,4-cyclohexanedimethanol and preparation method and application thereof |
| CN116273008A (en) * | 2023-03-28 | 2023-06-23 | 江苏金聚合金材料有限公司 | Preparation method and application of methyl glycolate catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607044A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst and method for preparing 1, 6-hexanediol by hydrogenation of dialkyl 1, 6-adipate |
| CN106748704A (en) * | 2016-11-14 | 2017-05-31 | 中海油天津化工研究设计院有限公司 | A kind of method of the cyclohexanedimethanol of coproduction 1,4 and the dicarbaldehyde of cyclohexyl 1,4 |
| CN107008332A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院大连化学物理研究所 | A kind of catalyst of synthesizing methanol by hydrogenating carbon dioxide and its preparation and application |
| CN108014801A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Produce the catalyst and method of alcohol |
| CN108014805A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Prepare the catalyst and its method of alcohol |
| CN108014802A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Prepare the catalyst and application method of alcohol |
| CN108014815A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Prepare the catalyst and method of alcohol |
-
2019
- 2019-10-22 CN CN201911004011.6A patent/CN112691674B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607044A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst and method for preparing 1, 6-hexanediol by hydrogenation of dialkyl 1, 6-adipate |
| CN107008332A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院大连化学物理研究所 | A kind of catalyst of synthesizing methanol by hydrogenating carbon dioxide and its preparation and application |
| CN108014801A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Produce the catalyst and method of alcohol |
| CN108014805A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Prepare the catalyst and its method of alcohol |
| CN108014802A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Prepare the catalyst and application method of alcohol |
| CN108014815A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Prepare the catalyst and method of alcohol |
| CN106748704A (en) * | 2016-11-14 | 2017-05-31 | 中海油天津化工研究设计院有限公司 | A kind of method of the cyclohexanedimethanol of coproduction 1,4 and the dicarbaldehyde of cyclohexyl 1,4 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354798A (en) * | 2019-07-17 | 2019-10-22 | 中国人民大学 | A kind of cerium zirconium zinc metal composite adsorbent and the preparation method and application thereof |
| CN115301248A (en) * | 2021-05-08 | 2022-11-08 | 中国石油化工股份有限公司 | Catalyst for preparing 1,4-cyclohexanedimethanol and preparation method and application thereof |
| CN113332989A (en) * | 2021-05-28 | 2021-09-03 | 浙江工业大学 | Alumina supported copper-rare earth metal oxide catalyst and preparation method and application thereof |
| CN116273008A (en) * | 2023-03-28 | 2023-06-23 | 江苏金聚合金材料有限公司 | Preparation method and application of methyl glycolate catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112691674B (en) | 2023-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112691674B (en) | Ester hydrogenation catalyst, and preparation method and application thereof | |
| KR100922998B1 (en) | Process for preparing monohydric alcohols from monocarboxylic acids or derivatives thereof | |
| EP2994229B1 (en) | Process for the production of 1,3-butadiene | |
| KR100296811B1 (en) | Hydrogenation of Carboxylic Acid Ester Using Catalyst Composition | |
| US20080207953A1 (en) | Catalyst and Method for Hyrogenating Carbonyl Compounds | |
| JP2020534359A (en) | Catalyst for oxidative esterification of aldehydes to carboxylic acid esters | |
| CN103664524B (en) | The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol | |
| WO2013073705A1 (en) | Method for producing high-purity 1,5-pentanediol | |
| US10005068B2 (en) | Catalyst and manufacturing method thereof | |
| JP2012144491A (en) | Method for producing glycol from multihydric alcohol | |
| WO2018146978A1 (en) | Catalyst for reduction reaction of 3,4-dihydroxytetrahydrofuran, and method for producing 3,4-dihydroxytetrahydrofuran reduced product | |
| CN113244928A (en) | Novel catalyst for preparing ethanol by methyl acetate hydrogenation and preparation method thereof | |
| CN105582927B (en) | 1,4 cyclohexanedimethanol catalyst and its preparation method | |
| CN106140199B (en) | Acid resistant form ester through hydrogenation catalyst and its preparation method and application and ester through hydrogenation method | |
| CN112717941B (en) | Ester hydrogenation catalyst and preparation method and application thereof | |
| CN107519882B (en) | Preparation method of cyclohexyl acetate hydrogenation catalyst, prepared hydrogenation catalyst and cyclohexyl acetate hydrogenation method | |
| CN114436770B (en) | Method for preparing cyclohexanedimethanol by hydrogenation of cyclohexanedicarboxylic acid dibasic ester | |
| JP3921877B2 (en) | Method for producing 1,4-cyclohexanedimethanol | |
| CN106140200B (en) | Acid resistant form ester through hydrogenation catalyst and its preparation method and application and ester through hydrogenation method | |
| JP4479537B2 (en) | Methods for preparing copper-containing hydrogenation catalysts and producing alcohols | |
| CN114433097A (en) | Copper-containing catalyst and preparation method and application thereof | |
| JPH09221437A (en) | Production of ethanol | |
| CN112569949A (en) | Cyclohexanedimethanol catalyst, preparation method and application thereof | |
| JP7188543B2 (en) | Method for isomerizing allyl compound | |
| JP6988642B2 (en) | Isomerization method of allyl compound |
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 |