CN112387288A - Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof - Google Patents

Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN112387288A
CN112387288A CN201910754760.4A CN201910754760A CN112387288A CN 112387288 A CN112387288 A CN 112387288A CN 201910754760 A CN201910754760 A CN 201910754760A CN 112387288 A CN112387288 A CN 112387288A
Authority
CN
China
Prior art keywords
catalyst
temperature
cyclohexanol
medium
dehydrogenation catalyst
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
Application number
CN201910754760.4A
Other languages
Chinese (zh)
Other versions
CN112387288B (en
Inventor
潘罗其
陈正朝
彭涛
周小文
彭志斌
刘洪武
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Baling Co
Original Assignee
China Petroleum and Chemical Corp
Sinopec Baling Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Baling Co filed Critical China Petroleum and Chemical Corp
Priority to CN201910754760.4A priority Critical patent/CN112387288B/en
Publication of CN112387288A publication Critical patent/CN112387288A/en
Application granted granted Critical
Publication of CN112387288B publication Critical patent/CN112387288B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic 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 provides a preparation method and application of a medium-temperature cyclohexanol dehydrogenation catalyst. The catalyst takes silicon dioxide as a carrier, and simultaneously loads a composite oxide of copper, zinc and calcium as an active component and an active auxiliary agent component; the preparation of the catalyst adopts a deposition precipitation method, and the catalyst is subjected to aging, filtering, washing, drying, roasting and finally tabletting and forming; the catalyst has high-temperature catalyst (such as ZnO/CaCO)3) High conversion rate, low temperature catalyst (such as CuO-ZnO, CuO-SiO)2) High selectivity and good stability, and the cyclohexene in the product is less than or equal to 0.01 percent and the phenol is less than or equal to 0.1 percent.

Description

Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a medium-temperature cyclohexanol dehydrogenation catalyst, a preparation method thereof and application thereof in a reaction for preparing cyclohexanone by cyclohexanol dehydrogenation.
Technical Field
Cyclohexanone is an important organic chemical raw material, and more than 40% of cyclohexanone is prepared by catalytic dehydrogenation of cyclohexanol. The catalyst used in the process is roughly divided into two stages, namely, a Zn-Ca system is adopted in the early stage, the using temperature is 360-430 ℃, the conversion rate is high, but the selectivity is about 96%, the generated byproducts are more, and the service life is shorter. Later, a low-temperature Cu-Mg or Cu-Zn series catalyst is adopted, the activity of the catalyst is reduced along with the temperature, the catalyst is generally used at the temperature of 220 ℃ and 250 ℃, although the conversion rate is lower, the selectivity is obviously improved and can reach more than 98 percent, the service life is longer, and at present, the Cu series catalyst is mostly adopted in domestic devices. However, when the Cu-based catalyst is used, the reaction temperature is increased to 250 ℃ or higher, which accelerates the sintering of copper, reduces the active surface, and changes the carrier structure, thereby reducing the activity of the catalyst and deteriorating the stability of the catalyst. In view of the specificity of dehydrogenation, researchers have made a great deal of technological innovation.
Patent CN109331826A describes a catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol and its preparation method and application, and uses ZnAl2O4As carrier, CuO and ZnO as active components, La2O3Is an assistant, wherein the mass content of CuO is 10-15%, the mass content of ZnO is 20-25%, and La is used as a carrier2O3The mass content of the catalyst is 2-5 percent, and the catalyst is obtained by adopting an impregnation method. Patent CN200810234492.5 describes a catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol, which mainly comprises copper oxide with a content molar ratio of 25% -75%, zinc oxide with a content molar ratio of 30% -65%, aluminum oxide with a content molar ratio of 1% -10%, and a structural auxiliary agent which is a dilute with a content molar ratio of 0.1% -5%The metal compound mixture comprises a metal compound, and the active assistant is an alkali metal compound with the content molar ratio of 0-1.0%. Patent CN200810234493.x describes a preparation method of a catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, which is characterized in that a coprecipitation method is used for preparation, a mixed solution of nitrates of copper, zinc and aluminum and a precipitator are subjected to precipitation reaction, the precipitator can be one of potassium carbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, potassium hydroxide, sodium hydroxide or ammonia water, the precipitation temperature is controlled to be 20-90 ℃, after precipitation is finished, the mixture is aged for 25-35 min, and an auxiliary agent is added for filtration, washing, drying, calcination and tabletting molding to obtain the catalyst. Patent CN97196061.5 describes a preparation method and application of a catalyst for preparing cyclohexanone by dehydrogenation of cyclohexanol, and relates to a catalyst containing alpha-alumina as a carrier material and copper as an active component. Patent CN00133278.3 describes a catalyst for preparing cyclohexanone by dehydrogenizing cyclohexanol and a preparation method thereof, which mainly comprises copper oxide with the content (m/m) of 20-70%, zinc oxide with the content of 28-70%, aluminum oxide with the content of 1-10%, a mixture of rare metal compounds with the content (m/m) of 0.1-5% and alkali metal compounds with the content of 0-1.0%, and is prepared by adopting a coprecipitation method.
Patent CN103285849B describes a dehydrogenation catalyst, its preparation method and application, and a method for preparing cyclohexanone from cyclohexanol, wherein soluble salt of dehydrogenation active components and precipitant capable of precipitating cations of the soluble salt are subjected to contact reaction in water under the condition of coprecipitation, and then are filtered, cleaned, dried and roasted, wherein the active components are zinc and calcium, and the selective components are one or more of copper, magnesium, barium, platinum and palladium, and are co-ground with graphite into a preparation. Patent CN90105453.4 discloses a multi-component cyclohexanol dehydrogenation catalyst, which comprises, by weight, 10% -50% of copper oxide, 10% -40% of zinc oxide, 6% -15% of magnesium oxide, 5 ppm-30 ppm of calcium oxide and 2% of graphite co-grinding agent.
Patent CN02807661.3 describes a catalyst based on copper oxide for the dehydrogenation of cyclohexanol, which is a catalyst based on copper oxide-zinc oxide or based on copper oxide-silicon oxide additionally containing small amounts of palladium and platinum or rutheniumThe catalysts can be used for the production of cyclohexanone at reduced reaction temperatures compared with conventional catalysts. Patent CN201110210438.9 describes a method for preparing a catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol, which takes copper oxide, zinc oxide, zirconium oxide and silicon oxide as main active components, takes M2O as a catalyst modifier and is Na2O、K2O、Li2O、Cs2And O or a mixture of more than one of O. Patent CN20111020414.3 describes a method for preparing a catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol, which uses copper oxide, zinc oxide, zirconium oxide and silicon oxide as main active components, and MO as a catalyst modifier. Patent CN10451127A describes a catalyst for preparing cyclohexanone by dehydrogenation of cyclohexanol and a preparation method thereof, wherein the active component of the catalyst is copper, the mass percent of the active component is 18-28%, the carrier is silicon dioxide, the mass percent of the carrier is 70-85%, and an alkali metal and alkaline earth metal active auxiliary agent with the mass percent of 0.5-5.0% is additionally added, the catalyst preparation adopts a step-by-step precipitation method, the prepared catalyst carrier has large surface area, the active substance is uniform on the surface of the carrier, has a proper pore structure, the catalyst activity is high, the conversion rate of cyclohexanol is more than or equal to 60%, the selectivity of cyclohexanone is more than or equal to 99%, the bulk density of the catalyst is low, and the cyclohexene content of a byproduct can reach 200-400 ppm.
Some of the existing Zn series catalysts and Cu series catalysts use alumina as a carrier, so that the catalysts have strong acidity and a plurality of byproducts of cyclohexene; some magnesium oxide or zirconium oxide is used as a carrier, so that the selectivity is high but the conversion rate is low; some silica with weak acidity is used as a carrier, the specific surface of the catalyst is the largest, and a byproduct, namely cyclohexene is less, but the stability of the catalyst at high temperature is poor. It is difficult to maintain good activity, selectivity and stability at higher temperatures. Therefore, from the practical industrial application, the development of the cyclohexanol dehydrogenation catalyst with good activity, selectivity and stability at medium temperature is beneficial to improving the yield of cyclohexanone and reducing the energy consumption and material consumption of cyclohexanone production.
Disclosure of Invention
In view of the technical defects, the invention aims to develop a catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol, which has good activity, selectivity and stability at medium temperature and has less product impurity; the preparation method has the advantages of simple preparation, cheap raw materials and the like, and can be used for industrial production of cyclohexanone by dehydrogenation of cyclohexanol.
The second purpose of the invention is to provide a preparation method of the catalyst.
The third purpose of the method is to provide an application method of the catalyst in preparing cyclohexanone by catalyzing cyclohexanol dehydrogenation.
The prior cyclohexanol dehydrogenation catalyst can not have both the selectivity of a low-temperature catalyst and the conversion rate of a high-temperature catalyst, and has the problems of unsatisfactory long-term stability and the like. Therefore, the invention provides a heterogeneous catalyst with a completely new combination form, which comprises the following specific components in percentage by weight:
a moderate-temperature cyclohexanol dehydrogenation catalyst deposits active components and active auxiliary agents on a silicon dioxide carrier (namely, the catalyst comprises the silicon dioxide carrier and the active components and the active auxiliary agents loaded in situ,
the active components comprise oxides of copper, zinc and calcium;
the active auxiliary agent is manganese and/or lanthanum oxide.
The invention innovatively discovers that by taking silicon dioxide as a carrier, ternary oxides containing copper, zinc and calcium are deposited and precipitated on the surface of the carrier, and the ternary oxides are matched with the manganese and lanthanum, so that a synergistic effect can be generated, the catalyst can have excellent conversion rate and selectivity under a medium-temperature condition (230-280 ℃, preferably 260-270 ℃), the impurity content is reduced, and the long-term stability can be remarkably improved.
The key point of the catalyst is that the active component and the auxiliary agent are deposited and precipitated on the surface of the silicon dioxide, so that the carrier, the active component and the active auxiliary agent have excellent synergistic effect. The coordination of the ternary oxides of copper, zinc and calcium and the synergistic coordination of the ternary active component and the auxiliary agent are the keys for realizing the excellent catalytic performance of the catalyst and the long-acting stability at higher reaction temperature.
Preferably, the copper oxide is CuO; the oxide of zinc is ZnO, and the oxide of calcium is CaO.
It has also been found that further control of the ratio of the active ingredients and the ingredients and ratios of the adjuvants helps to further enhance the synergy between the active ingredients, adjuvants and carrier.
Preferably, in the active component, the mass ratio of the copper oxide to the zinc oxide to the calcium oxide is 20-50: 5-30: 1 to 10. Researches find that the synergistic effect of the active component, the auxiliary agent and the carrier in the optimal proportion is better, and the catalytic performance and the long-acting stability of the catalyst are further improved.
Preferably, the coagent is an oxide of manganese and lanthanum.
Researches show that the synergistic effect of the binary compound active auxiliary agent and the ternary active component is better.
Preferably, in the active assistant, the mass ratio of the manganese oxide to the lanthanum oxide is 0.05-1: 0.1 to 1; more preferably 0.05 to 0.8:0.1 to 0.9.
The research of the invention finds that the proportion among the carrier, the active ingredient and the active auxiliary agent is further controlled, which is beneficial to further improving the cooperativity among the ingredients and further synergistically improving the catalytic effect and the long-acting stability.
Preferably, the mass fraction of the silicon dioxide carrier is 40-85%, the mass fraction of the active component is 14-58%, and the mass fraction of the active additive is 1-2%.
The invention also provides a preparation method of the medium-temperature cyclohexanol dehydrogenation catalyst, which is characterized in that a precursor is prepared by adopting a deposition precipitation method (an in-situ loading deposition method), and then the precursor is obtained by roasting.
The present inventors have surprisingly found that it is possible to synthesize a completely new catalyst of the present invention with in situ deposited active components and co-agents on silica and that the catalyst may surprisingly have superior catalytic performance, e.g. superior catalytic selectivity and cycling stability.
Preferably, the preparation method comprises the following steps:
(1) preparing silicon dioxide carrier powder and water into suspension in a precipitation kettle;
(2) preparing a corresponding metal water-soluble salt A forming the active component and a corresponding metal water-soluble salt B forming the active auxiliary agent into a mixed salt solution; preparing alkaline precipitant into alkaline solution.
(3) Under the condition of stirring, simultaneously dripping the mixed salt solution and the alkali solution in the step (2) into the suspension of the precipitation kettle, carrying out a deposition precipitation reaction, and controlling the pH value of the solution at the reaction end point to be 7-8;
(4) aging the precipitate at 60-100 ℃; filtering the precipitate, washing and drying to obtain a precursor; and roasting the precursor at 400-600 ℃ to obtain the catalyst.
Preferably, the silica carrier powder is fumed silica or a crushed macroporous silica gel.
The solid content of the suspension is preferably 10-30%.
Preferably, the metal water-soluble salt A is a water-soluble salt of Cu, Zn and Ca; preferably at least one of nitrate, hydrochloride and acetate.
Preferably, the metal water-soluble salt B is a water-soluble salt of Mn and/or La; (ii) a Preferably at least one of nitrate, hydrochloride and acetate.
Preferably, the solute concentration in the mixed salt solution is 10-30%.
Preferably, the alkaline precipitator is at least one of sodium hydroxide and sodium carbonate; the mass concentration of the alkaline precipitant is 10-20%.
Adding the mixed salt solution and the alkali solution into the suspension, carrying out deposition and precipitation reaction, depositing the hydroxide of the corresponding metal on the silicon dioxide carrier in situ, controlling the pH value of the reaction end point, and then carrying out aging, solid-liquid separation and washing to obtain the precursor.
Preferably, the aging time is 2 to 10 hours.
Preferably, the roasting time is 10-20 h.
After sintering, the sintering material can be molded by the existing method.
The preferred preparation method of the invention comprises the following steps:
1. preparing silicon dioxide carrier powder (obtained by crushing fumed silica or macroporous silica gel) and water into a suspension in a precipitation kettle, wherein the solid content of the aqueous solution is 10-30%;
2. preparing soluble salts (nitrate, hydrochloride, acetate and the like) of copper, zinc, calcium, manganese and/or lanthanum into mixed salt solution with the concentration of 10-30% according to the required proportion; preparing an alkaline precipitator (sodium hydroxide, sodium carbonate and the like) into a 10-20% solution.
3. Under the conditions of room temperature to 80 ℃ and strong stirring, simultaneously dripping the salt solution and the alkali solution in the step (2) into a precipitation kettle, controlling the dripping speed of the salt solution and the alkali solution, and controlling the PH of the solution to be between 7 and 8 so as to simultaneously deposit the oxides of copper, zinc, calcium, manganese and/or lanthanum on a SiO carrier2A surface.
4. Aging the precipitate at 60-100 ℃ for 2-10 h; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 100-160 ℃; roasting for 10-20 h at 400-500 ℃; and (6) tabletting and forming.
The invention also provides application of the prepared medium-temperature cyclohexanol dehydrogenation catalyst to catalyzing cyclohexanol dehydrogenation to prepare cyclohexanone.
Preferably, the application of the method comprises the steps of firstly carrying out hydrogen reduction on a catalyst at the temperature of 120-260 ℃ by using a tubular reactor, and then contacting cyclohexanol with the catalyst to carry out dehydrogenation reaction, wherein the mass space velocity of cyclohexanol is 0.5-2 h-1The reaction temperature is 230-280 ℃, and the reaction pressure is normal pressure-0.1 MPa (G).
Preferably, the reaction temperature is 260 to 270 ℃. The novel catalyst has better conversion rate, selectivity and stability in the preferred medium-temperature zone.
Advantageous effects
The invention simultaneously and uniformly deposits the oxides of copper, zinc, manganese and/or lanthanum on the SiO carrier of the carrier by controlling the appropriate concentration, temperature, stirring intensity, PH of the solution and the dropping rate of the solution and the alkali solution of the soluble salts of the active components of copper, zinc and calcium and the active additives of manganese and/or lanthanum2The obtained catalyst has large specific surface area and high temperature (such as ZnO/CaCO)3) High conversion rate, low temperature catalyst (such as CuO-ZnO, CuO-SiO)2) The selectivity is high, and simultaneously, because of the co-introduction of the manganese and/or lanthanum auxiliary agent, the dispersity of copper is improved, the sintering and aggregation of the copper in the operation process are slowed down, and the change process of the stability is slower. Detecting impurities in the product, wherein the generated main impurity is phenol, but the content of the phenol is less than or equal to 0.1 percent, which indicates that the catalyst has good and stable low-temperature activity; the cyclohexene content is less than or equal to 0.01 percent, which indicates that the manufacturing process of the catalyst and the components of the catalyst are reasonable. The catalyst of the invention is particularly suitable for replacing ZnO/CaCO3The catalyst can greatly reduce the reaction temperature, improve the selectivity and replace CuO-ZnO or CuO-SiO2) So as to improve the conversion rate of the reaction and maintain good stability.
Researches show that the catalyst can obtain the conversion rate of more than 70% under the condition of medium temperature, the selectivity can be more than 99.5%, the reduction rate of the conversion rate can be only 1.7%/1000 h, and the catalyst has no obvious fluctuation in activity and excellent stability.
Drawings
FIG. 1 shows the results of experimental evaluation of the long-term stability of the catalyst of example 7.
Detailed Description
The invention is further described with reference to the following figures and specific examples. The following description is merely exemplary in nature and is in no way intended to limit the scope of the invention or its application.
Example 1
1. The catalyst used in the present invention was prepared.
Adding 10g of silicon dioxide powder obtained by crushing macroporous silica gel into a precipitation kettle, and adding 50ml of deionized water to prepare suspension; adding 1.82g of copper nitrate trihydrate, 1.46g of zinc nitrate hexahydrate, 0.42g of calcium nitrate tetrahydrate and 0.3g of 50% manganese nitrate solution into 11g of deionized water to prepare a salt solution; 4.28g of sodium carbonate decahydrate was added to 11.5g of deionized water to prepare an alkali solution.
Simultaneously dripping the salt solution and the alkali solution into a precipitation kettle under the conditions of stirring at 72 +/-2 ℃ and 1000n/min, controlling the dripping speed of the salt solution and the alkali solution, controlling the pH at the precipitation end point to be 7.5, aging the precipitate at the temperature of 74 ℃ for 3 hours, and simultaneously depositing copper, zinc and calcium oxide on a carrier SiO2A surface; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 120 ℃; roasting for 10-20 h at 400-500 ℃; and tabletting to form the catalyst A.
2. Evaluation of catalyst Performance
10g of the catalyst A prepared above is used for preparing cyclohexanone by removing cyclohexanol, and the inner diameter of a reactor is 20 mm. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 2.5h-1And the reduction time is 150 hours. Then the cyclohexanol enters a reactor at the flow rate of 5g/h, and contacts with a catalyst to perform dehydrogenation reaction at the reaction temperature of 240 ℃ and the reaction pressure of 0.1MPa (G), wherein the conversion rate of the cyclohexanol is 55.2 percent, and the selectivity is 99.56 percent.
Example 2
1. The catalyst used in the present invention was prepared.
The catalyst preparation was the same as in example 1.
2. Evaluation of catalyst Performance
10g of the catalyst A prepared above is used for preparing cyclohexanone by removing cyclohexanol, and the inner diameter of a reactor is 20 mm. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 2.5h-1And the reduction time is 150 hours. Then the cyclohexanol enters a reactor at the flow rate of 8g/h, and contacts with a catalyst to perform dehydrogenation reaction at the reaction temperature of 245 ℃ and the reaction pressure of 0.1MPa (G), wherein the conversion rate of the cyclohexanol is 62.8 percent, and the selectivity is 99.53 percent.
Example 3
1. The catalyst used in the present invention was prepared.
Adding 9g of silicon dioxide powder obtained by crushing macroporous silica gel into a precipitation kettle, and adding 40ml of deionized water to prepare suspension; adding 0.91g of copper nitrate trihydrate, 0.28g of zinc nitrate hexahydrate, 0.07g of calcium nitrate tetrahydrate and 0.16g of lanthanum nitrate hexahydrate into 10g of deionized water to prepare a salt solution; 1.6g of sodium carbonate decahydrate is added into 10.5g of deionized water to prepare an alkali solution.
Simultaneously dripping the salt solution and the alkali solution into a precipitation kettle under the conditions of stirring at 75 +/-2 ℃ and 1000n/min, controlling the dripping speed of the salt solution and the alkali solution, controlling the pH at the precipitation end point to be 7.2, aging the precipitate at the temperature of 80 ℃ for 3 hours, and simultaneously depositing copper, zinc and calcium oxide on a SiO carrier2A surface; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 120 ℃; roasting for 10-20 h at 400-500 ℃; and tabletting to form the catalyst B.
2. Evaluation of catalyst Performance
10g of the catalyst B prepared above is used for preparing cyclohexanone by cyclohexanol removal, and the inner diameter of a reactor is 20 mm. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 2.5h-1And the reduction time is 150 hours. Then the cyclohexanol enters a reactor at the flow rate of 12g/h, and contacts with a catalyst to perform dehydrogenation reaction at the reaction temperature of 250 ℃ and the reaction pressure of 0.07MPa (G), wherein the conversion rate of the cyclohexanol is 66.8 percent, and the selectivity is 99.49 percent.
Example 4
1. The catalyst used in the present invention was prepared.
The catalyst was prepared as in example 3.
2. Evaluation of catalyst Performance
10g of the catalyst B prepared above is used for preparing cyclohexanone by cyclohexanol removal, and the inner diameter of a reactor is 20 mm. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 2.5h-1And the reduction time is 150 hours. Then the cyclohexanol enters a reactor at the flow rate of 15g/h, and contacts with a catalyst to perform dehydrogenation reaction at the reaction temperature of 255 ℃ and the reaction pressure of 0.07MPa (G), wherein the conversion rate of the cyclohexanol is68.5 percent and the selectivity is 99.45 percent.
Example 5
1. The catalyst used in the present invention was prepared.
Adding 16g of silicon dioxide powder obtained by crushing macroporous silica gel into a precipitation kettle, and adding 42ml of deionized water to prepare suspension; adding 4.35g of copper nitrate trihydrate, 3.42g of zinc nitrate hexahydrate, 1.18g of calcium tetranitrate, 0.22g of 50% manganese nitrate aqueous solution and 0.11g of lanthanum nitrate hexahydrate into 18g of deionized water to prepare a salt solution; 10.3g of sodium carbonate decahydrate is added to 18g of deionized water to prepare an alkali solution.
Simultaneously dripping the salt solution and the alkali solution into a precipitation kettle under the conditions of stirring at 78 +/-2 ℃ and 1000n/min, controlling the dripping speed of the salt solution and the alkali solution, controlling the pH at the precipitation end point to be 7.8, aging the precipitate at 78 ℃ for 3 hours, and simultaneously depositing copper, zinc and calcium oxide on a SiO carrier2A surface; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 120 ℃; roasting for 10-20 h at 400-500 ℃; and (3) tabletting to form the catalyst C.
2. Evaluation of catalyst Performance
The catalyst C10 g prepared above is used for preparing cyclohexanone by removing cyclohexanol, and the inner diameter of the reactor is 20 mm. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 2.5h-1And the reduction time is 150 hours. Then the cyclohexanol enters a reactor at the flow rate of 18g/h, and contacts with a catalyst to perform dehydrogenation reaction at the reaction temperature of 260 ℃ and the reaction pressure of 0.03MPa (G), wherein the conversion rate of the cyclohexanol is 70.5 percent, and the selectivity is 99.38 percent.
Example 6
1. The catalyst used in the present invention was prepared.
The catalyst was prepared as in example 5.
2. Evaluation of catalyst Performance
The catalyst C10 g prepared above is used for preparing cyclohexanone by removing cyclohexanol, and the inner diameter of the reactor is 20 mm. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 2.5h-1And the reduction time is 150 hours. Then cyclohexanol was fed at a rate of 20g/hPutting into a reactor, contacting cyclohexanol with a catalyst to perform dehydrogenation reaction at the reaction temperature of 265 ℃ and the reaction pressure of 0.03MPa (G), wherein the conversion rate of the cyclohexanol is 72.5 percent, and the selectivity is 99.25 percent.
Example 7
1. The catalyst used in the present invention was prepared.
Adding 80g of silicon dioxide powder obtained by crushing macroporous silica gel into a precipitation kettle, and adding 500ml of deionized water to prepare suspension; adding 31.44g of copper nitrate trihydrate, 27.41g of zinc nitrate hexahydrate, 6.33g of calcium nitrate tetrahydrate, 4.2g of 50% manganese nitrate solution and 1.6g of lanthanum nitrate hexahydrate into 150g of deionized water to prepare a salt solution; 75.85g of sodium carbonate decahydrate were added to 110.5g of deionized water to prepare an alkaline solution.
Simultaneously dripping the salt solution and the alkali solution into a precipitation kettle under the conditions of stirring at 80 ℃ and 1000n/min, controlling the dripping speed of the salt solution and the alkali solution, controlling the pH at the end point of precipitation to be 7.5, aging the precipitate at 80 ℃ for 3 hours to simultaneously deposit copper, zinc and calcium oxide on a carrier SiO2A surface; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 120 ℃; roasting for 10-20 h at 400-500 ℃; and (3) tabletting to form the catalyst D.
2. Evaluation of catalyst Performance
100g of the prepared catalyst D is used for preparing cyclohexanone by dehydrogenating cyclohexanol, the inner diameter of a reactor is 32mm, the length of the reactor is 1000mm, and heat required by the reaction is provided by an electric heating tile outside the reactor; phi 3mm temperature-drawing guide pipe is arranged in the reaction center, and the temperature of the center of the reaction bed layer is measured. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 1.5h-1And the reduction time is 253 hours. Then using cyclohexanol (in which the cyclohexanol content is 90%, cyclohexanone content is 3.5% and ether intermediate impurity content is 6.5%) on the industrial equipment to make it enter into reactor at the flow rate of 100g/h, under the condition of reaction temp. of 265 deg.C and reaction pressure of 0.05MPa (G), making long-time stability experiment of contact dehydrogenation reaction of cyclohexanol and catalyst, and according to the analysis data of feed and discharge composition of reactor calculating to obtain conversion rate of cyclohexanol and selectivity of cyclohexanone. The results are shown in FIG. 1, after 1650 hours of catalyst operationThe conversion rate is reduced from 72.5% to 70.7%, the selectivity is gradually increased from 99.1% to 99.5%, the catalyst activity reduction speed is slow, the conversion rate reduction speed is 1.7%/1000 h, and the catalyst activity has no obvious fluctuation, which indicates that the catalyst stability is good. Detecting impurities in the product, wherein the produced main impurity is phenol, but the content of the phenol is less than or equal to 0.1 percent, which shows that the catalyst has good and stable low-temperature activity, and reduces the amount of phenol generated by disproportionation of ketene generated by dehydrogenation of cyclohexanone at high temperature; the content of cyclohexene is less than or equal to 0.01 percent, and the amount of light components such as cyclohexane and benzene generated by further disproportionation of cyclohexene is small, which indicates that the preparation process of the catalyst and the components of the catalyst are reasonable.
Comparative example 1
1. Preparing the conventional Cu-Zn-Ca-Mn-La catalyst.
Adding 31.44g of copper nitrate trihydrate, 27.41g of zinc nitrate hexahydrate, 6.33g of calcium nitrate tetrahydrate, 4.2g of 50% manganese nitrate solution and 1.6g of lanthanum nitrate hexahydrate into 150g of deionized water to prepare a salt solution; 75.85g of sodium carbonate decahydrate were added to 110.5g of deionized water to prepare an alkaline solution.
Simultaneously dripping the salt solution and the alkali solution into a precipitation kettle under the conditions of stirring at 80 ℃ and 1000n/min, controlling the dripping speed of the salt solution and the alkali solution, controlling the PH at the end point of precipitation to be 7.5, and aging the precipitation for 3 hours at the temperature of 80 ℃; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 120 ℃; roasting for 10-20 h at 400-500 ℃; comparative catalyst E was tablet molded.
2. Evaluation of catalyst Performance
100g of the prepared comparative catalyst E is used for preparing cyclohexanone by dehydrogenating cyclohexanol, the inner diameter of a reactor is 32mm, the length of the reactor is 1000mm, and heat required by the reaction is provided by an electric heating tile outside the reactor; phi 3mm temperature-drawing guide pipe is arranged in the reaction center, and the temperature of the center of the reaction bed layer is measured. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 1.5h-1And the reduction time is 253 hours. Then using cyclohexanol (in which the cyclohexanol content is 90%, cyclohexanone content is 3.5% and ether intermediate impurity content is 6.5%) on industrial equipment to make it be fed into reactor at 100g/h flow rate, and making reaction at 265 deg.C and pressureThe stability experiment of the contact dehydrogenation reaction of cyclohexanol and catalyst is carried out for a long time under the condition of 0.05MPa (G), and the conversion rate of cyclohexanol and selectivity of cyclohexanone are calculated according to the analysis data of the composition of the feed and the discharge of the reactor. The result shows that the catalyst has 68% conversion rate and 97.5% selectivity in the initial operation period, and after 500h operation, the conversion rate is reduced to 55% and the selectivity is 98.0%, the cyclohexene content in the product reaches 0.3%, and the phenol content reaches 0.5%. It shows that the catalyst not only has low activity and poor selectivity, but also has unstable activity at higher stability.
Comparative example 2
1. The coprecipitation method is adopted to prepare the silicon dioxide loaded copper-zinc-calcium-manganese-lanthanum catalyst.
Adding 31.44g of copper nitrate trihydrate, 27.41g of zinc nitrate hexahydrate, 6.33g of calcium nitrate tetrahydrate, 4.2g of 50% manganese nitrate solution and 1.6g of lanthanum nitrate hexahydrate into 150g of deionized water to prepare a salt solution; 75.3g of sodium metasilicate nonahydrate was added to 110.5g of deionized water to prepare an alkali solution.
Simultaneously dripping the salt solution and the alkali solution into a precipitation kettle under the conditions of stirring at 80 ℃ and 1000n/min, controlling the dripping speed of the salt solution and the alkali solution, controlling the PH at the end point of precipitation to be 7.5, and aging the precipitation for 3 hours at the temperature of 80 ℃; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 120 ℃; roasting for 10-20 h at 400-500 ℃; comparative catalyst F was tablet molded.
2. Evaluation of catalyst Performance
100g of the prepared comparative catalyst F is used for preparing cyclohexanone by dehydrogenating cyclohexanol, the inner diameter of a reactor is 32mm, the length of the reactor is 1000mm, and heat required by the reaction is provided by an electric heating tile outside the reactor; phi 3mm temperature-drawing guide pipe is arranged in the reaction center, and the temperature of the center of the reaction bed layer is measured. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 1.5h-1And the reduction time is 253 hours. Then using cyclohexanol (in which the cyclohexanol content is 90%, cyclohexanone content is 3.5% and ether intermediate impurity content is 6.5%) on the industrial equipment to make it be fed into reactor at 100g/h flow rate, under the condition of reaction temp. of 265 deg.C and reaction pressure of 0.05MPa (G), making the cyclohexanol and catalyst implement reaction for a long timeAnd (3) in a stability experiment of the contact dehydrogenation reaction, calculating the conversion rate of cyclohexanol and selectivity of cyclohexanone according to analysis data of the feed and discharge composition of the reactor. The results show that the conversion rate is 70% and the selectivity is 98.0% in the initial operation period of the catalyst, and after the catalyst is operated for 1000h, the conversion rate is reduced to 65%, the selectivity is improved, but only 98.4%, the cyclohexene content in the product is 0.2%, and the phenol content is 0.3%. It is shown that the initial activity, selectivity and stability of the catalyst are inferior to those of the catalyst provided by the invention.
Comparative example 3
1. Preparing the conventional Cu-Zn-Al-Mn-La catalyst. (aluminum instead of calcium)
Adding 31.44g of copper nitrate trihydrate, 27.41g of zinc nitrate hexahydrate, 3.9g of aluminum nitrate nonahydrate, 4.2g of 50% manganese nitrate solution and 1.6g of lanthanum nitrate hexahydrate into 150g of deionized water to prepare a salt solution; 76.76g of sodium carbonate decahydrate was added to 110.5g of deionized water to prepare an alkali solution.
Simultaneously dripping the salt solution and the alkali solution into a precipitation kettle under the conditions of stirring at 80 ℃ and 1000n/min, controlling the dripping speed of the salt solution and the alkali solution, controlling the PH at the end point of precipitation to be 7.5, and aging the precipitation for 3 hours at the temperature of 80 ℃; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 120 ℃; roasting for 10-20 h at 400-500 ℃; comparative catalyst G was tablet molded.
2. Evaluation of catalyst Performance
100G of the prepared comparative catalyst G is used for preparing cyclohexanone by dehydrogenating cyclohexanol, the inner diameter of a reactor is 32mm, the length of the reactor is 1000mm, and heat required by the reaction is provided by an electric heating tile outside the reactor; phi 3mm temperature-drawing guide pipe is arranged in the reaction center, and the temperature of the center of the reaction bed layer is measured. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 1.5h-1And the reduction time is 253 hours. Then using cyclohexanol (in which the cyclohexanol content is 90%, cyclohexanone content is 3.5% and ether intermediate impurity content is 6.5%) on the industrial equipment to make it be fed into reactor at 100g/h flow rate, under the condition of reaction temp. of 265 deg.C and reaction pressure of 0.05MPa (G), making long-time stability experiment of contact dehydrogenation reaction of cyclohexanol and catalyst, according to the inlet and outlet of reactorThe conversion rate of cyclohexanol and selectivity of cyclohexanone are calculated from the analysis data of material composition. The result shows that the catalyst has 75% conversion rate and 97.0% selectivity in the initial operation period, and after 500h operation, the conversion rate is reduced to 52%, the selectivity is improved to 98.2%, the cyclohexene content in the product reaches 0.35%, and the phenol content reaches 0.4%. The catalyst has high initial activity, but poor selectivity and stability.
Comparative example 4
1. Preparing the silicon dioxide loaded copper-zinc-aluminum catalyst. (manganese-free lanthanum addition agent)
Adding 80g of silicon dioxide powder obtained by crushing macroporous silica gel into a precipitation kettle, and adding 500ml of deionized water to prepare suspension; adding 31.44g of copper nitrate trihydrate, 27.41g of zinc nitrate hexahydrate and 6.33g of calcium nitrate tetrahydrate into 150g of deionized water to prepare a salt solution; 71.22g of sodium carbonate decahydrate is added to 110.5g of deionized water to prepare an alkali solution.
Simultaneously dripping the salt solution and the alkali solution into a precipitation kettle under the conditions of stirring at 80 ℃ and 1000n/min, controlling the dripping speed of the salt solution and the alkali solution, controlling the PH at the end point of precipitation to be 7.5, and aging the precipitation for 3 hours at the temperature of 80 ℃; filtering the precipitate, and washing the precipitate for 3-5 times by using desalted water until the sodium content is lower than 0.1%; drying for 6-10 h at 120 ℃; roasting for 10-20 h at 400-500 ℃; comparative catalyst H was tablet molded.
2. Evaluation of catalyst Performance
100g of the prepared comparative catalyst H is used for preparing cyclohexanone by dehydrogenating cyclohexanol, the inner diameter of a reactor is 32mm, the length of the reactor is 1000mm, and heat required by the reaction is provided by an electric heating tile outside the reactor; phi 3mm temperature-drawing guide pipe is arranged in the reaction center, and the temperature of the center of the reaction bed layer is measured. Firstly, carrying out hydrogen reduction on the catalyst at the temperature of 120-260 ℃, wherein the reduction space velocity is 1.5h-1And the reduction time is 253 hours. Then using cyclohexanol (in which the cyclohexanol content is 90%, cyclohexanone content is 3.5% and ether intermediate impurity content is 6.5%) on the industrial equipment to make it be fed into reactor at 100g/h flow rate, under the condition of reaction temp. of 265 deg.C and reaction pressure of 0.05MPa (G), making long-time stability experiment of contact dehydrogenation reaction of cyclohexanol and catalyst, according to the analysis of feed and discharge composition of reactorThe data are calculated to obtain the conversion rate of cyclohexanol and selectivity of cyclohexanone. The results show that the catalyst has 73.5% of conversion rate and 98.5% of selectivity in the initial operation period, and after 500 hours of operation, the conversion rate is reduced to 56%, the selectivity is 98.9%, the cyclohexene content in the product reaches 0.1%, and the phenol content reaches 0.15%. The catalyst has high initial activity, good selectivity and poor stability.
As can be seen from examples 1-7 and comparative examples, the selectivity and conversion of the catalyst provided by the present invention are higher than those of the copper-based and zinc-based catalysts used in the conventional industrial production of cyclohexanone by dehydrogenation of cyclohexanol. Example 7 also examined the long-term stability experiment of the catalyst, proved that the catalyst stability and selectivity are good, can satisfy the industrial production requirements.

Claims (13)

1. A medium-temperature cyclohexanol dehydrogenation catalyst is characterized in that active components and active auxiliary agents are deposited and precipitated on a silicon dioxide carrier,
the active components comprise oxides of copper, zinc and calcium;
the active auxiliary agent is manganese and/or lanthanum oxide.
2. An intermediate-temperature cyclohexanol dehydrogenation catalyst according to claim 1, wherein in the active component, the mass ratio of copper oxide, zinc oxide and calcium oxide is 20-50: 5-30: 1 to 10.
3. An intermediate-temperature cyclohexanol dehydrogenation catalyst as claimed in claim 1, wherein the co-agent is oxides of manganese and lanthanum.
4. An intermediate-temperature cyclohexanol dehydrogenation catalyst according to claim 3, wherein in the active assistant, the mass ratio of manganese oxide to lanthanum oxide is 0.05-1: 0.1 to 1.
5. A medium-temperature cyclohexanol dehydrogenation catalyst as claimed in any one of claims 1 to 4, wherein the mass fraction of the silica carrier is 40-85%, the mass fraction of the active ingredient is 14-58%, and the mass fraction of the active ingredient is 1-2%.
6. A preparation method of the medium-temperature cyclohexanol dehydrogenation catalyst according to any one of claims 1 to 5, characterized in that a precursor is prepared by a deposition precipitation method and then is obtained by roasting.
7. A process for the preparation of a medium-temperature cyclohexanol dehydrogenation catalyst according to claim 6, comprising the steps of:
(1) preparing silicon dioxide carrier powder and water into suspension in a precipitation kettle;
(2) preparing a corresponding metal water-soluble salt A forming the active component and a corresponding metal water-soluble salt B forming the active auxiliary agent into a mixed salt solution; preparing an alkaline precipitator into an alkaline solution;
(3) under the condition of stirring, simultaneously dripping the mixed salt solution and the alkali solution in the step (2) into the suspension of the precipitation kettle, carrying out a deposition precipitation reaction, and controlling the pH value of the solution at the reaction end point to be 7-8;
(4) aging the precipitate at 60-100 ℃; filtering the precipitate, washing and drying to obtain a precursor; and roasting the precursor at 400-600 ℃ to obtain the catalyst.
8. A process for preparing a medium-temperature cyclohexanol dehydrogenation catalyst according to claim 7,
the silicon dioxide carrier powder is fumed silica or a macroporous silica gel crushed material;
the solid content of the suspension is 10-30%.
9. A process for preparing a medium-temperature cyclohexanol dehydrogenation catalyst according to claim 7,
the metal water-soluble salt A is water-soluble salt of Cu, Zn and Ca;
the metal water-soluble salt B is a water-soluble salt of Mn and/or La;
the water-soluble salt is at least one of nitrate, hydrochloride and acetate of corresponding metals.
10. A process for preparing a medium-temperature cyclohexanol dehydrogenation catalyst according to claim 7,
the alkaline precipitator is at least one of sodium hydroxide and sodium carbonate.
11. A preparation method of a medium-temperature cyclohexanol dehydrogenation catalyst according to claim 6, wherein the aging time is 2-10 h;
the roasting time is 10-20 h.
12. An application of the medium-temperature cyclohexanol dehydrogenation catalyst of any one of claims 1 to 5 or the medium-temperature cyclohexanol dehydrogenation catalyst prepared by the preparation method of any one of claims 6 to 11, which is used for catalyzing cyclohexanol dehydrogenation to prepare cyclohexanone.
13. The use of a medium temperature cyclohexanol dehydrogenation catalyst according to claim 12, wherein the catalyst is subjected to hydrogen reduction at 120-260 ℃ by using a tubular reactor, and then cyclohexanol is contacted with the catalyst to perform dehydrogenation reaction, wherein the mass space velocity of cyclohexanol is 0.5-2 h-1The reaction temperature is 230-270 ℃, and the reaction pressure is normal pressure-0.1 MPa (G).
CN201910754760.4A 2019-08-15 2019-08-15 Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof Active CN112387288B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910754760.4A CN112387288B (en) 2019-08-15 2019-08-15 Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910754760.4A CN112387288B (en) 2019-08-15 2019-08-15 Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112387288A true CN112387288A (en) 2021-02-23
CN112387288B CN112387288B (en) 2024-01-30

Family

ID=74601660

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910754760.4A Active CN112387288B (en) 2019-08-15 2019-08-15 Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112387288B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116332722A (en) * 2021-12-23 2023-06-27 沈阳化工研究院有限公司 Auxiliary agent for preparing cyclohexanol by cyclohexene hydration and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877381A (en) * 1995-06-30 1999-03-02 Nitto Kagaku Kogyo Kabushiki Kaisha Particulate catalyst for use in a fluidized bed
KR100864313B1 (en) * 2007-05-21 2008-10-20 한국화학연구원 Preparation of surface functionalized porous organic-inorganic hybrid materials or mesoporous materials with coordinatively unsaturated metal sites and its catalytic applications
CN102247866A (en) * 2011-07-26 2011-11-23 烟台大学 Catalyst used for preparation of cyclohexanone by dehydrogenation of cyclohexanol and preparation method thereof
CN105148913A (en) * 2015-10-08 2015-12-16 宁波海越新材料有限公司 Catalyst for preparation of methyl ethyl ketone from sec-butyl alcohol, and preparation method for catalyst
CN106890641A (en) * 2015-12-18 2017-06-27 中国石油化工股份有限公司 A kind of preparing cyclohexanone by cyclohexanol dehydrogenation high-selectivity catalyst and preparation method
CN108855119A (en) * 2017-05-11 2018-11-23 中国石油化工股份有限公司 A kind of production gamma-butyrolacton catalyst and preparation method
CN109331826A (en) * 2018-09-13 2019-02-15 北京华和拓科技开发有限责任公司 A kind of cyclohexanone catalyst by cyclohexanol dehydrogenation, preparation method and application
KR20190063551A (en) * 2017-11-30 2019-06-10 주식회사 엘지화학 Catalyst system for oxidative dehydrogenation reaction, reactor for producing butadiene comprising the same system and method for preparing 1,3-butadiene

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877381A (en) * 1995-06-30 1999-03-02 Nitto Kagaku Kogyo Kabushiki Kaisha Particulate catalyst for use in a fluidized bed
KR100864313B1 (en) * 2007-05-21 2008-10-20 한국화학연구원 Preparation of surface functionalized porous organic-inorganic hybrid materials or mesoporous materials with coordinatively unsaturated metal sites and its catalytic applications
CN102247866A (en) * 2011-07-26 2011-11-23 烟台大学 Catalyst used for preparation of cyclohexanone by dehydrogenation of cyclohexanol and preparation method thereof
CN105148913A (en) * 2015-10-08 2015-12-16 宁波海越新材料有限公司 Catalyst for preparation of methyl ethyl ketone from sec-butyl alcohol, and preparation method for catalyst
CN106890641A (en) * 2015-12-18 2017-06-27 中国石油化工股份有限公司 A kind of preparing cyclohexanone by cyclohexanol dehydrogenation high-selectivity catalyst and preparation method
CN108855119A (en) * 2017-05-11 2018-11-23 中国石油化工股份有限公司 A kind of production gamma-butyrolacton catalyst and preparation method
KR20190063551A (en) * 2017-11-30 2019-06-10 주식회사 엘지화학 Catalyst system for oxidative dehydrogenation reaction, reactor for producing butadiene comprising the same system and method for preparing 1,3-butadiene
CN109331826A (en) * 2018-09-13 2019-02-15 北京华和拓科技开发有限责任公司 A kind of cyclohexanone catalyst by cyclohexanol dehydrogenation, preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JUNG, KD ET AL.: "Preparation of Cu/ZnO/M2O3 (M = Al, Cr) catalyst to stabilize Cu/ZnO catalyst in methanol dehydrogenation", 《CATALYSTS LETTERS》, vol. 84, no. 1, pages 21 - 25 *
耿彩军等: "助剂对甲醇乙醇合成异丁醛催化剂结构和催化性能的影响", 《天然气化工》, vol. 5, pages 5 - 7 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116332722A (en) * 2021-12-23 2023-06-27 沈阳化工研究院有限公司 Auxiliary agent for preparing cyclohexanol by cyclohexene hydration and application thereof

Also Published As

Publication number Publication date
CN112387288B (en) 2024-01-30

Similar Documents

Publication Publication Date Title
JP7019813B2 (en) Catalyst for producing α-phenylethanol by hydrogenation of acetophenone, its production method and application
CN114829004B (en) Method for preparing Ni-X-based oxide catalyst and application of Ni-X-based oxide catalyst in transfer hydrogenation
CN103028409A (en) Supported copper-based metal catalyst with high dispersion as well as preparation method and application thereof
EP1000658B1 (en) A copper-containing catalyst, a process for the preparation and use thereof
JP5716669B2 (en) Methanol synthesis catalyst
US20180273454A1 (en) Multicomponent heterogeneous catalysts for direct co2 hydrogenation to methanol
US3932514A (en) Catalyst for the preparation of cyclohexanone from phenol and process therefor
CN108126761B (en) Cobalt-based composite particle load, preparation and synthesis of carboxylic ester
CN112076762B (en) Catalyst for preparing neopentyl glycol
CN105363456A (en) Copper-based catalyst and preparation method and application thereof
CN106890641A (en) A kind of preparing cyclohexanone by cyclohexanol dehydrogenation high-selectivity catalyst and preparation method
CN104511277A (en) Catalyst for preparing cyclohexanone from cyclohexanol through gas-phase dehydrogenization and preparation method thereof
CN111672500A (en) Supported catalyst with specific composition and structure for preparing propylene by propane dehydrogenation and preparation method thereof
CN102463121A (en) High-stability Cu-based catalyst and preparation method thereof
CN1156425C (en) Process for preparing cyclohexanone by dehydrogenating cyclohexanol
CN112387288B (en) Medium-temperature cyclohexanol dehydrogenation catalyst and preparation method and application thereof
CN104437488B (en) A kind of preparation method of Hexalin gas-phase dehydrogenation preparing cyclohexanone catalyst
CN1164363C (en) Catalyst in oxychlorination reaction as well as its preparation method and application
CN113234012B (en) Preparation method of 3-methylaminopyridine and derivative or salt thereof
CN1150990C (en) Catalyst for liquid-phase dehydogenation of cyclohexanol
CN111992209A (en) Catalyst for synthesizing dimethyl oxalate and preparation method and application thereof
WO2018178805A1 (en) Aliovalent doped metal oxide fluorite catalysts for selective conversion of carbon dioxide and hydrogen to methanol
CN112517018B (en) Catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde and preparation method and application thereof
CN112823883B (en) Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof
CN111229201B (en) Mo-based catalyst taking scheelite oxide as precursor, and preparation method and application thereof

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