CN111790400A - Hydrogenation coupling catalyst, preparation method and application thereof - Google Patents

Hydrogenation coupling catalyst, preparation method and application thereof Download PDF

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Publication number
CN111790400A
CN111790400A CN202010468061.6A CN202010468061A CN111790400A CN 111790400 A CN111790400 A CN 111790400A CN 202010468061 A CN202010468061 A CN 202010468061A CN 111790400 A CN111790400 A CN 111790400A
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catalyst
hydrogenation
coupling
atmosphere
microwave
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CN111790400B (en
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余航
钟颖贤
侯丽琼
李义涛
张宏清
唐火强
石玲
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Dongguan HEC Tech R&D Co Ltd
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Dongguan HEC Tech R&D Co Ltd
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    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • 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
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/10—Heat treatment in the presence of water, e.g. steam
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
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    • 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
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a hydrogenation coupling catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) co-precipitating a solution containing coupling catalytic activity metal salt and alkaline earth metal salt, aging, performing microwave treatment, cooling, filtering, collecting precipitate, drying and roasting to obtain a catalyst precursor; (2) and (3) putting the catalyst precursor into an impregnation liquid containing a hydrogenation catalytic activity metal salt, and fully impregnating. The catalyst provided by the invention can be used for catalyzing hydrogenation coupling reaction. The catalyst should be activated before use to ensure high catalytic activity. When the catalyst is used for preparing 1,1,1,4,4, 4-hexafluoro-2-butene, the conversion rate of the catalyst on a substrate is high, and the catalytic selectivity on a target product is high.

Description

Hydrogenation coupling catalyst, preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, and particularly relates to a hydrogenation coupling catalyst, and a preparation method and application thereof.
Background
Chlorofluorocarbons (CFCs) are fluorocarbon derivatives of saturated hydrocarbons and have long been widely used as blowing agents, refrigerants, cleaning agents, and the like because of their chemical stability, non-toxicity, non-flammability, non-explosiveness, and low cost. A large number of experimental studies show that CFCs have high ODP (ozone depletion potential), can slowly destroy the atmospheric ozone layer, and threatens the global ecology; fluorinated Hydrocarbons (HFCs) have an Ozone Depletion Potential (ODP) of 0, but also have a very high GWP (global warming potential), have a strong greenhouse effect, and have an adverse effect on global climate.
1,1,1,4,4, 4-hexafluoro-2-butene (HFO-1336, R1336) is a class of Hydrofluoroolefin (HFO), has zero ozone layer depletion potential (ODP), very low greenhouse effect potential (GWP 9.7), has little influence on the environment, is considered to be a new generation of green environment-friendly foaming agent because the performance of the blowing agent is similar to that of CFC-11, HCFC-141b, HFC-245fa and the like, especially similar to HCFC-141b, and is a final green environment-friendly substitute for blowing agent products such as HCFC-141b and the like. At present, HFO-1336 is mainly applied to foaming agents, refrigerants, aerosols and the like for refrigerators, plate polyurethane heat-insulating materials, and the application field is continuously expanded with the continuous and deep research on the product application, and HFO-1336 can be expected to have wide market prospect.
With the wide application and increasing demand of HFO-1336, the synthetic method thereof has received wide attention from the fluorine chemical industry. At present, one of the main synthetic methods of HFO-1336 is to use Freon compounds CFC-113, HCFC-123, etc. as raw materials, and prepare them under the catalytic action of hydrogenation coupling catalyst. However, the hydrogenation coupling catalyst provided by the prior art has low conversion rate and coupling selectivity, many byproducts and high catalyst cost, and is not easy to realize continuous industrialization.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a hydrogenation coupling catalyst, and the catalyst prepared by the method has the advantages of large specific surface area, large pore diameter, uniform distribution of catalytic active ingredients and high catalytic efficiency of hydrogenation and coupling.
Specifically, the preparation method of the hydrogenation coupling catalyst comprises the following steps:
(1) co-precipitating a solution containing coupling catalytic activity metal salt and alkaline earth metal salt, aging, performing microwave treatment, cooling, filtering, collecting precipitate, drying and roasting to obtain a catalyst precursor;
(2) and (3) putting the catalyst precursor into an impregnation liquid containing a hydrogenation catalytic activity metal salt, and fully impregnating.
The catalyst is prepared by adopting a method of coprecipitation (namely step 1) and impregnation (namely step 2), so that coupling active metals can be uniformly dispersed inside and outside the carrier, and hydrogenation active metals are uniformly loaded in catalyst pore channels; the catalyst prepared by the method provided by the invention is used for catalytic reaction, so that the reactants can be ensured to contact with hydrogenation active metal in a pore channel first, and the aim of hydrogenation first and coupling later is fulfilled. If the catalyst is prepared by coprecipitation and then coprecipitation or impregnation, part of the channels in the catalyst may only contain coupling active metal, part of the channels may only contain hydrogenation active metal, or some of the coupling active metal is outside and the hydrogenation active metal is inside, so that the prepared catalyst cannot realize the effect of hydrogenation-followed-by-coupling, and more by-products of direct hydrogenation of R123, such as R133a (1,1, 1-trifluoro-2-chloroethane), R134a (1,1,1, 2-tetrafluoroethane), and the like, can be obtained.
In the invention, the coupling catalytic active metal in the step (1) is a main active component of coupling catalysis, alkaline earth metal is used as a carrier, and the coprecipitation of the metal can ensure that the coupling catalytic active metal is uniformly dispersed inside and outside the catalyst. Wherein the coupling catalytically active metal is preferably ruthenium (Ru). The alkaline earth metal is preferably calcium (Ca) or magnesium (Mg). The salts of the above metals are preferably inorganic salts, such as chloride salts.
As a preferred embodiment of the present invention, the mass ratio of the coupling catalytically active metal to the alkaline earth metal is 1: (25-35), for example: 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34, 1:35, etc.
In the present invention, the mass of the metal refers to the mass of the metal atom, for example: the mass of coupling-catalytically active metal is the mass of the metal atom in the coupling-catalytically active metal salt.
When the alkaline earth metal is two, the mass ratio refers to the mass ratio of the coupling catalytically active metal to each alkaline earth metal.
In a preferred embodiment of the present invention, the solution of the coprecipitation in step (1) further contains a ferric (Fe) salt. The iron salt is preferably an inorganic salt, such as a chloride salt. In the catalyst, ferric iron can be used as Lewis acid to adjust the surface acid sites of the catalyst, thereby improving the coupling catalytic activity. During preparation, the trivalent ferric salt is coprecipitated with the coupling catalytic active metal salt and the alkaline earth metal salt, so that the active metal components can be uniformly dispersed inside and outside the catalyst.
As a preferred embodiment of the present invention, the mass ratio of the coupling catalytically active metal to the ferric iron is 1: (5-10), for example: 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.
In a preferred embodiment of the present invention, the coprecipitation in step (1) is performed under alkaline conditions, preferably under conditions of pH 8 to 10. In one embodiment of the invention, ammonia (e.g., 25-30% by mass) may be added to the system, and the pH of the solution is adjusted to 8-10 to cause precipitation.
In the step (1) of the invention, after the coprecipitation is finished, the aging is needed. During the aging process, the precipitate is fully contacted with the mother liquor, and the structure of the precipitate is irreversibly changed along with time, such as crystal perfection and crystal transformation.
After aging, the step (1) of the invention introduces a microwave treatment process, aiming at intervening the crystallization process of precipitates, inhibiting the agglomeration of crystal grains and effectively adjusting the specific surface area and the pore size distribution of the catalyst. Under the microwave condition, the coprecipitated substance can be effectively dissolved and deposited, so that the coupling catalytic active metal is highly dispersed in the catalyst and can be fully utilized, the contact probability of the reaction substrate and the coupling catalytic active metal in the catalyst in the subsequent catalytic reaction is effectively improved, the catalytic efficiency is improved, and the cost is saved.
The power of the microwave treatment is preferably 250-400W. The microwave treatment time is preferably 2-5 h.
In a specific embodiment of the present invention, the power of the microwave treatment is: 250W, 300W, 350W, 400W, etc.; the microwave treatment time is as follows: 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc.
As a preferable scheme of the invention, the microwave treatment in the step (1) is carried out after aging is carried out for a certain period of time, and preferably, the microwave treatment is carried out after aging is carried out for 10-20 min. The microwave treatment is preferably carried out after the aging is carried out for 10-20 min, so that on one hand, the interference on the initial stage of crystal form transformation and perfection is avoided, the rapid forming of crystals is ensured, and on the other hand, the crystals can be dispersed to the greatest extent, and the agglomeration is prevented.
In a preferred embodiment of the present invention, in the step (1), the precipitate collected after filtration is repeatedly washed with water until the chloride ion content in the washed water is 400mg/L or less. The washing operation can avoid catalyst poisoning caused by a large amount of chloride ions, and ensure that the catalyst has good catalytic function and catalytic efficiency.
In a preferred embodiment of the present invention, the drying in step (1) is performed at 100 to 140 ℃. The drying time and the temperature are in a negative correlation relationship, and the drying time is further preferably 6-12 hours.
As a preferred embodiment of the present invention, the calcination in step (1) is carried out in N2The reaction is carried out in an atmosphere at 300-350 ℃. The roasting time and the temperature are in a negative correlation relationship, and the roasting time is further preferably 4-8 hours.
As a preferable embodiment of the present invention, the step (1) is to pulverize the product after the calcination. The crushing specifically comprises the following steps: pulverizing to obtain powder, adding pore-enlarging agent, and mixing by ball mill. The pore-expanding agent can be graphite. The addition mass of the pore-expanding agent is preferably 1-5% of the mass of the powder.
In a preferred embodiment of the present invention, step (1) is carried out by molding the product after pulverization. The forming means that: and (3) pressing and molding the crushed product. The shape of the product obtained by molding can be selected according to actual requirements, such as sheet, particle and the like.
In the step (2), the catalyst precursor is fully immersed in an immersion liquid containing hydrogenation catalytic activity metal salt, so that the hydrogenation catalytic activity component is attached to the pore channel of the catalyst. The hydrogenation catalytic active metal is preferably one or both of palladium (Pd) and nickel (Ni). The salts of the above metals are preferably inorganic salts, such as chloride salts.
In a preferred embodiment of the present invention, the impregnation solution in step (2) may further contain a metal auxiliary agent in addition to the hydrogenation catalyst active metal salt, for adjusting the dispersion degree of the active component (hydrogenation catalyst active metal) and suppressing the occurrence of side reactions. According to the invention, the metal auxiliary agent is preferably one, two or three of copper (Cu), zirconium (Zr) and cobalt (Co). In practice, the impregnation solution is charged with an inorganic salt of the above-mentioned metals, such as a chloride salt.
In a preferred embodiment of the present invention, in the impregnation, the hydrogenation catalyst active metal is palladium, and the metal promoter is copper, or cobalt and zirconium, or cobalt and copper. Or in the impregnation, the hydrogenation catalytic active metal is nickel, and the metal auxiliary agent is copper, or cobalt, or zirconium and copper, or cobalt and copper.
As a preferable embodiment of the present invention, in the step (2), the coupling catalytic activity and the hydrogenation catalytic activity of the catalyst can be adjusted by adjusting the relative amounts of the coupling catalytic active component and the hydrogenation catalytic active component in the catalyst, so as to achieve a balance between the coupling catalytic activity and the hydrogenation catalytic activity, and further achieve the catalytic effect of coupling after hydrogenation.
Specifically, the mass ratio of the catalyst precursor to the hydrogenation catalyst active metal is preferably 100: (1.5-3.5).
When the hydrogenation catalyst active metal is two or more, the mass ratio refers to the mass ratio of the catalyst precursor to each hydrogenation catalyst active metal.
In a specific embodiment of the present invention, the mass ratio of the catalyst precursor to the hydrogenation catalyst active metal is: 100:1.5, 100:2.0, 100:2.3, 100:2.5, 100:2.6, 100:2.7, 100:3.0, 100:3.5, etc.
When the dipping solution contains the metal auxiliary agent, the mass ratio of the catalyst precursor to the metal auxiliary agent is preferably 100: (1-4.5).
When the number of the metal assistants in the impregnation liquid is more than two, the mass ratio refers to the mass ratio of the catalyst precursor to each metal assistant.
In a specific embodiment of the present invention, the mass ratio of the catalyst precursor to each metal promoter is: 100:1.0, 100:1.5, 100:2.0, 100:2.5, 100:3.0, 100:3.5, 100:4.0, 100:4.5, and so forth.
When the dipping solution contains the metal auxiliary agent, the invention preferably has the mass ratio of the catalyst precursor, the hydrogenation catalytic active metal and the metal auxiliary agent of 100: (1.5-3.5): (1-4.5). In a preferred embodiment of the present invention, the catalyst precursor is modified by microwave impregnation using microwaves in the step (2), so that the particle size of the active metal on the surface of the catalyst precursor can be effectively reduced, and the dispersion degree of the active metal on the carrier can be improved.
The invention preferably adopts the microwave dipping in N2The microwave is carried out in the atmosphere, and the microwave power is 150-600W. The microwave dipping time and the power are in a negative correlation relationship, the higher the power is, the shorter the microwave dipping time is, and the microwave dipping time is further preferably 2-30 min. After the microwave impregnation is finished, N is2And cooling to room temperature in the atmosphere.
In order to further improve the impregnation effect and enable the hydrogenation catalytic active components to be more fully and uniformly attached to the surface and the pore channels of the catalyst, the catalyst precursor is preferably immersed in the impregnation solution overnight in the step (2), and then microwave impregnation is performed by adopting the method and the conditions.
As a specific embodiment of the present invention, the preparation method of the hydrogenation coupling catalyst comprises the following steps:
(1) weighing coupling catalytic activity metal salt, trivalent ferric salt and alkaline earth metal salt, dissolving in deionized water, fully stirring, adjusting the pH value to 8-10, carrying out precipitation reaction, and aging for 10-20 min after the reaction is finished; carrying out microwave hydrothermal treatment on the aged gel liquid for 2-5 h at 250-400W, fully reacting, cooling, filtering, collecting precipitate, washing with water until the content of chloride ions in water is less than or equal to 400mg/L, drying at 100-140 ℃ for 4-11 h, and then carrying out N2Roasting for 4-8 h at 300-350 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 1-5 wt% of a pore-expanding agent, grinding and mixing by using a ball mill, and performing compression molding to obtain a catalyst precursor;
(2) weighing a hydrogenation catalytic active metal salt and a metal auxiliary agent, and dissolving in deionized water to obtain an impregnation solution; placing the obtained catalyst precursor in a container, pouring the impregnation liquid, impregnating overnight, and then carrying out N2Microwave dipping is carried out for 3-30 min at 150-600W in the atmosphere, and N is added2And cooling to room temperature in the atmosphere to obtain the catalyst.
The invention uses a microwave coprecipitation method to prepare a catalyst precursor, introduces a microwave hydrothermal treatment catalyst gel system, inhibits the phenomenon of crystal grain agglomeration caused by temperature gradient in the precipitation method, effectively adjusts the specific surface area and the pore size distribution of the catalyst, increases the contact area with reactant molecules and enhances the catalytic activity. The invention further preferably uses a microwave dipping method to modify the catalyst precursor, can effectively reduce the granularity of the auxiliary metal on the surface of the catalyst precursor, improve the dispersion degree of the auxiliary metal on the carrier, enhance the catalytic activity and reduce the selectivity of byproducts. The invention further adjusts the combination of various additives of the catalyst in the process of designing the formula of the catalyst, thereby adjusting the coupling catalytic activity and the hydrogenation catalytic activity of the catalyst and effectively improving the activity of the catalyst and the yield of the coupling product.
The second purpose of the invention is to provide a hydrogenation coupling catalyst prepared by the method.
The catalyst prepared by the method has larger surface area and uniform pore size distribution, and the catalytic active ingredients are uniformly distributed in the catalyst and have high dispersity. The hydrogenation catalytic active component and the coupling catalytic active component have proper proportion and distribution, so that the coupling catalytic activity and the hydrogenation catalytic activity of the catalyst reach specific balance, and the hydrogenation reaction and the coupling reaction can be ensured to be carried out firstly during the catalytic reaction. When the catalyst is used for specific catalytic reaction, the substrate conversion rate is high, the coupling rate is high, the selectivity is strong, the yield of a target product is high, and the yield of a byproduct is low.
The third purpose of the invention is to provide the application of the catalyst in catalytic hydrogenation coupling reaction.
The hydrocoupling reaction is preferably: the reaction for preparing 1,1,1,4,4, 4-hexafluoro-2-butene (HFO-1336 or R1336) by using Freon compounds as raw materials. The 1,1,1,4,4, 4-hexafluoro-2-butene can be cis-form, trans-form or a mixture of cis-form and trans-form. The freon compound is preferably trifluorodichloroethane (freon 123, HCFC123 or R123).
In the actual reaction process, when the raw material passes through the catalyst, the raw material firstly contacts the surface of the catalyst (mainly hydrogenation catalytic activity), after dechlorination, the raw material contacts the main body of the catalyst (mainly coupling catalytic activity), and then the R1336 is synthesized by coupling.
In the raw material R123 (CF)3CHCl2) At the beginning of the reaction, the hydrogenation will remove the chlorine to form, for example, CF3Free radical of CH, then coupling of two free radicals to form CF3CH＝CHCF3(R1336). It is also possible to form e.g. CF first3Free radical of CHCl, then coupling of two free radicals to CF3CHCl-CHClCF3And then dechlorinated to R1336.
It is a fourth object of the present invention to provide a method for activating the catalyst. The catalyst provided by the invention is activated before being used for catalytic reaction so as to ensure that excellent catalytic effect can be realized.
As a preferred embodiment of the present invention, the method for activating the catalyst comprises: firstly, N is2Roasting in the atmosphere at 150-200 ℃, and then roasting in H2Activating under the conditions of atmosphere and 300-350 ℃. Wherein the roasting time is preferably 3-6 h. The activation time is preferably 3-5 h.
The activation can be carried out directly in the reactor of the catalytic reaction. After the activation is finished, the reaction conditions are adjusted, and the activated catalyst can be directly applied to catalytic reaction.
The fifth object of the present invention is to provide a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene using the hydrogenation coupling catalyst. The 1,1,1,4,4, 4-hexafluoro-2-butene can be cis-form, trans-form or a mixture of cis-form and trans-form.
As a preferred scheme of the invention, the method takes R123 and H2Is used as a reaction raw material. The method comprises the following steps: continuously feeding reaction raw materials R123 and H into a reactor filled with an activated hydrogenation coupling catalyst2. The reaction temperature in the reactor is preferably 200-350 ℃.
As a specific embodiment of the invention, 45-55 mL of the hydrogenation coupling catalyst is filled in a fixed bed reactor with the inner diameter of a reaction tube being 15-25 mm. After the catalyst is activated, the flow rate of R123 is 10-15 g/H, and H2The flow rate of the mixed raw material is 25-35 mL/min, and the mixed raw material is continuously introduced for reaction. The reaction product withdrawn from the reactor is,the impurities HCl and HF can be removed through water washing and alkali washing.
The product prepared by the method is analyzed by adopting gas chromatography, so that the conversion rate of the catalyst on a substrate R123 can reach more than 45%, and the catalytic selectivity on a target product can reach more than 25%.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
This example provides a hydrocoupling catalyst prepared by the following method:
(1) 605g of MgCl were weighed2·6H2O、90.34g FeCl3·6H2O and 6.04g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 10 for precipitation reaction, and aging for 15min after the reaction is finished; performing 300W microwave hydrothermal treatment on the aged gel liquid for 2h, fully reacting, cooling to room temperature, filtering, collecting precipitate, washing with water until the content of chloride ions in water is less than or equal to 400mg/L, drying at 120 deg.C for 8h, and performing N-ion exchange2Roasting for 8 hours at 310 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 6.86g CoCl was weighed2·6H2O、6.37g PdCl2And 19.59g ZrCl4Dissolving in 60 deg.C deionized water to obtain salt solution, weighing 170g of the obtained catalyst precursor, placing in a container, pouring the salt solution, soaking overnight, and then N2Microwave soaking at 300W for 22min in N2And cooling to room temperature in the atmosphere to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Roasting at 170 deg.C for 3 hr, and further roasting in H2Activating for 5h at 310 ℃ in atmosphere.
Example 2
This example provides a hydrocoupling catalyst prepared by the following method:
(1) 605g of MgCl were weighed2·6H2O、90.34g FeCl3·6H2O and 6.04g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 9 for precipitation reaction, and aging for 15min after the reaction is finished; subjecting the gel solution obtained after aging to 250W microwave hydrothermal treatment for 4h, fully reacting, cooling to room temperature, filtering, collecting precipitate, washing with water until the content of chloride ions in water is less than or equal to 400mg/L, drying at 120 deg.C for 9h, and performing N-ion exchange treatment2Roasting for 7h at 330 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 15.49g of NiCl were weighed2·6H2O and 16.19g CuCl2Dissolving in 60 deg.C deionized water to obtain salt solution, weighing 170g of the obtained catalyst precursor, placing in a container, pouring the salt solution, soaking overnight, and then N2Microwave soaking at 250W in N atmosphere for 28min2And cooling to room temperature in the atmosphere to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Roasting at 190 deg.C for 5H in an atmosphere of H2Activating for 4h at 300 ℃ in atmosphere.
Example 3
This example provides a hydrocoupling catalyst prepared by the following method:
(1) weighing 225g of CaCl2、101.47g FeCl3·6H2O and 6.78g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 8 for precipitation reaction, and aging for 15min after the reaction is finished; carrying out 300W microwave hydrothermal treatment on the aged gel liquid for 3 hours,cooling to room temperature after full reaction, filtering, collecting precipitate, washing with water until the content of chloride ion in water is less than or equal to 400mg/L, drying at 120 deg.C for 8h, and adding N2Roasting for 5h at 340 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 9.91g of PdCl are weighed out2、10.79g CuCl2Dissolving the salt in deionized water at 60 ℃ to obtain a salt solution, weighing 170g of the obtained catalyst precursor, placing the weighed catalyst precursor in a container, pouring the salt solution, soaking the catalyst precursor overnight, and then adding N2Microwave soaking at 150W in N atmosphere for 30min2And cooling to room temperature in the atmosphere to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Calcining at 150 deg.C for 4H in the atmosphere of H2Activating for 3h at 330 ℃ in atmosphere.
Example 4
This example provides a hydrocoupling catalyst prepared by the following method:
(1) weighing 225g of CaCl2、101.47g FeCl3·6H2O and 6.78g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 9 for precipitation reaction, and aging for 15min after the reaction is finished; subjecting the gel solution obtained after aging to 350W microwave hydrothermal treatment for 5h, fully reacting, cooling to room temperature, filtering, collecting precipitate, washing with water until the content of chloride ions in water is less than or equal to 400mg/L, drying at 120 deg.C for 6h, and performing N microwave hydrothermal treatment on the precipitate2Roasting for 8h at 300 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 20.59g CoCl was weighed2·6H2O、7.08g PdCl2And 13.06g ZrCl4Dissolving in 60 deg.C deionized water to obtain salt solution, weighing 170g of the obtained catalyst precursor, placing in a container, and pouring into the containerSoaking in the salt solution overnight, and then adding N2Microwave soaking at 400W in N atmosphere for 25min2And cooling to room temperature in the atmosphere to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Roasting at 200 deg.C for 6H in an atmosphere of H2Activating for 3h at 350 ℃ in atmosphere.
Example 5
This example provides a hydrocoupling catalyst prepared by the following method:
(1) 605g of MgCl were weighed2·6H2O、90.34g FeCl3·6H2O and 6.04g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 8 for precipitation reaction, and aging for 15min after the reaction is finished; subjecting the gel solution obtained after aging to 350W microwave hydrothermal treatment for 5h, fully reacting, cooling to room temperature, filtering, collecting precipitate, washing with water until the content of chloride ions in water is less than or equal to 400mg/L, drying at 120 deg.C for 7h, and performing N microwave hydrothermal treatment on the precipitate2Roasting for 5h at 350 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 10.30g CoCl was weighed2·6H2O、5.67g PdCl2、8.99g CuCl2Dissolving in 60 deg.C deionized water to obtain salt solution, weighing 170g of the obtained catalyst precursor, placing in a container, pouring the salt solution, soaking overnight, and then N2Soaking in 550W for 8min in N2And cooling to room temperature in the atmosphere to obtain the catalyst. The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Calcining at 160 deg.C for 3H in the atmosphere of H2Activating for 5h at 320 ℃ in atmosphere.
Example 6
This example provides a hydrocoupling catalyst prepared by the following method:
(1) 605g of MgCl were weighed2·6H2O、90.34g FeCl3·6H2O and 6.04g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 10 for precipitation reaction, and aging for 15min after the reaction is finished; subjecting the gel solution obtained after aging to 400W microwave hydrothermal treatment for 2h, fully reacting, cooling to room temperature, filtering, collecting precipitate, washing with water until the content of chloride ions in water is less than or equal to 400mg/L, drying at 120 deg.C for 4h, and further treating with N2Roasting for 7h at 300 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 13.73g CoCl was weighed2·6H2O and 24.10g NiCl2·6H2Dissolving O in deionized water at 60 ℃ to obtain a salt solution, weighing 170g of the obtained catalyst precursor, placing the weighed catalyst precursor in a container, pouring the salt solution, soaking overnight, and then adding N2Soaking in 350W microwave for 20min in N2And cooling to room temperature in the atmosphere to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Roasting at 180 deg.C for 4H in an atmosphere of H2Activating for 4h at 330 ℃ in atmosphere.
Example 7
This example provides a hydrocoupling catalyst prepared by the following method:
(1) weighing 225g of CaCl2、101.47g FeCl3·6H2O and 6.78g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 8 for precipitation reaction, and aging for 15min after the reaction is finished; subjecting the aged gel liquid to 400W microwave hydrothermal treatmentCooling to room temperature after reacting for 2h, filtering, collecting precipitate, washing with water until the content of chloride ion in water is less than or equal to 400mg/L, drying at 120 deg.C for 6h, and adding N2Roasting for 6h at 320 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) Weighing 18.93NiCl2·6H2O、12.59g CuCl2And 4.35g ZrCl4Dissolving in 60 deg.C deionized water to obtain salt solution, weighing 170g of the obtained catalyst precursor, placing in a container, pouring the salt solution, soaking overnight, and then N2Microwave soaking at 600W for 3min in N2And cooling to room temperature in the atmosphere to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Roasting at 160 deg.C for 3 hr, and then in H2Activating for 5h at 340 ℃ in atmosphere.
Example 8
This example provides a hydrocoupling catalyst prepared by the following method:
(1) weighing 225g of CaCl2、101.47g FeCl3·6H2O and 6.78g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 10 for precipitation reaction, and aging for 15min after the reaction is finished; subjecting the gel solution obtained after aging to 250W microwave hydrothermal treatment for 5h, fully reacting, cooling to room temperature, filtering, collecting precipitate, washing with water until the content of chloride ions in water is less than or equal to 400mg/L, drying at 120 deg.C for 11h, and performing N-ion exchange treatment2Roasting at 320 ℃ in the atmosphere for 5h, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 30.89g CoCl was weighed2·6H2O、10.33g NiCl2·6H2O and 3.60g CuCl2Dissolving in 60 deg.C deionized water to obtain salt solution, and mixing170g of the obtained catalyst precursor is weighed and placed in a container, the salt solution is poured in, the catalyst precursor is soaked overnight, and then N is added2Microwave soaking at 200W for 28min in N2And cooling to room temperature in the atmosphere to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Roasting at 190 deg.C for 5H in an atmosphere of H2Activating for 3h at 340 ℃ in atmosphere.
Example 9
This example provides a hydrocoupling catalyst prepared by the following method:
(1) 605g of MgCl were weighed2·6H2O、90.34g FeCl3·6H2O and 6.04g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 10 for precipitation reaction, and aging for 15min after the reaction is finished; performing 300W microwave hydrothermal treatment on the aged gel liquid for 2h, fully reacting, cooling to room temperature, filtering, collecting precipitate, washing with water until the content of chloride ions in water is less than or equal to 400mg/L, drying at 120 deg.C for 10h, and performing N-ion exchange2Roasting for 7h at 310 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) Weighing 4.25g of PdCl2And 15.49g of NiCl2·6H2Dissolving O in deionized water at 60 ℃ to obtain a salt solution, weighing 170g of the obtained catalyst precursor, placing the weighed catalyst precursor in a container, pouring the salt solution, soaking the catalyst precursor overnight in N2Microwave soaking at 450W in N atmosphere for 18min2And cooling to room temperature in the atmosphere to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Roasting for 5 hours at the temperature of 180 ℃ in the atmosphere,at H2Activating for 4h at 350 ℃ in atmosphere.
Example 10
This example provides a hydrocoupling catalyst prepared by the following method:
(1) weighing 225g of CaCl2、101.47g FeCl3·6H2O and 6.78 gCuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 9 for precipitation reaction, and aging for 15min after the reaction is finished; subjecting the aged gel liquid to 400W microwave hydrothermal treatment for 3h, reacting completely, cooling to room temperature, filtering, collecting precipitate, washing with water until the content of chloride ion in water is less than or equal to 400mg/L, drying at 120 deg.C for 9h, and performing N-ion exchange at N2Roasting for 4h at 340 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 20.66g of NiCl were weighed2·6H2And O, dissolving the precursor in deionized water at 60 ℃ to obtain a salt solution, weighing 170g of the obtained catalyst precursor, placing the weighed precursor in a container, pouring the salt solution, and soaking overnight to obtain the catalyst.
The embodiment further provides an activation method of the catalyst, which specifically comprises the following steps:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Calcining at 200 deg.C for 4H in the atmosphere of H2Activating for 3h at 300 ℃ in atmosphere.
Comparative example
This comparative example provides a hydrocoupling catalyst prepared by the following method:
(1) 605g of MgCl were weighed2·6H2O、90.34g FeCl3·6H2O and 6.04g RuCl3·3H2Dissolving O in deionized water, fully stirring, adding 28% ammonia water by mass, controlling the pH to 9 for precipitation reaction, and aging for 15min after the reaction is finished; filtering the aged gel solution, collecting precipitate, washing with water until the content of chloride ion in water is less than or equal to 400mg/L, drying at 120 deg.C for 8 hr, and adding N2Roasting for 6h at 330 ℃ in the atmosphere, crushing to obtain a powdery sample, adding 2 wt% of graphite, ball-milling and mixing by using a ball mill, and tabletting to obtain the catalyst precursor.
(2) 17.21g of NiCl was weighed2·6H2Dissolving O in deionized water at 60 ℃ to obtain a salt solution, weighing 170g of the obtained catalyst precursor, placing the weighed catalyst precursor in a container, pouring the salt solution, soaking the catalyst precursor overnight in N2Microwave soaking at 500W for 15min in N2And cooling to room temperature in the atmosphere to obtain the catalyst.
This comparative example further provides a method for activating the catalyst, specifically:
50mL of catalyst is filled in a fixed bed reactor, the material of a reaction tube is 316L, the inner diameter of the reaction tube is 20mm, and the catalyst is N2Roasting at 150 deg.C for 6 hr, and then in H2Activating for 4h at 310 ℃ in atmosphere.
Examples of the experiments
After activation according to the method provided in each of the examples and comparative examples, the reaction temperature was controlled to 260 ℃ and R123 was fed at a flow rate of 30g/H and H was fed at a flow rate of 55mL/min2Pressure of 0.2MPa, R123 and H2After mixing, the mixture enters a reactor for reaction. The product gas was analyzed by gas chromatography after washing with water and alkali to remove HCl and HF.
The target product R1336 of the experimental example is prepared by catalyzing two R123 molecules through catalyst coupling hydrogenation, and is easy to be over-hydrogenated to generate R336 due to the double bond. Since R336 can be obtained by a simple dehydrogenation reaction to R1336, the present invention, when evaluating the selectivity of the catalyst, sums the selectivity percentages of R1336 and R336 to give a coupling total. In the case of no significant difference in the total coupling, the higher the percent selectivity of the target product R1336 obtained by the catalysis of the catalyst is, and the lower the percent selectivity of the byproduct R336 is, indicating that the catalyst has more excellent selectivity.
The conversion of R123, selectivity to the target product R1336 (i.e., 1,1,1,4,4, 4-hexafluoro-2-butene), selectivity to the byproduct R336 (i.e., 1,1,1,4,4, 4-hexafluorobutane), and coupling are summarized in table 1.
TABLE 1 evaluation results of catalysts
Figure BDA0002513346300000161
Figure BDA0002513346300000171
As can be seen from the results in table 1, the comparative example, which was not subjected to microwave treatment in step (1), resulted in a lower substrate conversion and catalyst selectivity of the resulting catalyst. Compared with the comparative examples, the catalysts provided by the embodiments 1 to 10 of the invention have the advantages that the conversion rate of the substrate, the hydrogenation catalytic performance and the coupling catalytic performance of the catalyst are obviously improved.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (13)

1. A preparation method of a hydrogenation coupling catalyst is characterized by comprising the following steps:
(1) co-precipitating a solution containing coupling catalytic activity metal salt and alkaline earth metal salt, aging, performing microwave treatment, cooling, filtering, collecting precipitate, drying and roasting to obtain a catalyst precursor;
(2) and (3) putting the catalyst precursor into an impregnation liquid containing a hydrogenation catalytic activity metal salt, and fully impregnating.
2. The method of claim 1, wherein the coupling catalytically active metal is ruthenium; the alkaline earth metal is calcium or magnesium;
preferably, the mass ratio of the coupling catalytically active metal to the alkaline earth metal is 1: (25-35).
3. The method according to claim 1 or 2, wherein the coprecipitated solution further contains a trivalent iron salt;
preferably, the mass ratio of the coupling catalytically active metal to ferric iron is 1: (5-10).
4. The preparation method according to claim 1, wherein the coprecipitation is performed under alkaline conditions, preferably at a pH of 8 to 10.
5. The preparation method according to claim 1, wherein the microwave treatment power is 250 to 400W;
preferably, the microwave treatment is carried out for 2-5 hours after the aging is carried out for 10-20 min.
6. The method according to claim 1, wherein the precipitate collected after the filtration is repeatedly washed with water until the chloride ion content in the water is 400mg/L or less.
7. The production method according to any one of claims 1 to 6, wherein the hydrogenation catalyst active metal is one or both of palladium and nickel;
preferably, the mass ratio of the catalyst precursor to the hydrogenation catalyst active metal is 100: (1.5-3.5).
8. The method according to claim 1 or 7, wherein the impregnation liquid may further contain a metal auxiliary; the metal auxiliary agent is one, two or three of copper, zirconium and cobalt;
preferably, when the impregnation liquid contains a metal assistant, the mass ratio of the catalyst precursor to the metal assistant is 100: (1-4.5).
9. The method of claim 1, wherein the impregnating comprises microwave impregnating;
preferably, in N2Carrying out microwave impregnation in an atmosphere, wherein the microwave power is 150-600W;
more preferably, the impregnation is in particular: soaking overnight, then N2And carrying out microwave dipping for 3-30 min under the conditions of atmosphere and microwave power of 150-600W.
10. A hydrocoupling catalyst prepared by the process of any one of claims 1 to 9.
11. Use of a hydrocoupling catalyst according to claim 10 for catalysing hydrocoupling reactions;
preferably, the hydrocoupling reaction is: the reaction for preparing 1,1,1,4,4, 4-hexafluoro-2-butene by using Freon compounds as raw materials.
12. A method for activating the hydrogenation coupling catalyst according to claim 10;
preferably, the activation method comprises the steps of: firstly, N is2Roasting in the atmosphere at 150-200 ℃, and then roasting in H2Activating in the atmosphere at 300-350 ℃;
more preferably, the roasting time is 3-6 h, and the activation time is 3-5 h.
13. A process for preparing 1,1,1,4,4, 4-hexafluoro-2-butene using the hydrocoupling catalyst of claim 10;
preferably, the method comprises the steps of: continuously feeding reaction raw materials R123 and H into a reactor filled with an activated hydrogenation coupling catalyst2；
More preferably, the method comprises the steps of: filling 45-55 mL of the hydrogenation coupling catalyst into a fixed bed reactor with the inner diameter of a reaction tube being 15-25 mm; after the catalyst is activated, the flow rate of R123 is 10-15 g/H, and H2The flow rate of the mixed raw material is 25-35 mL/min, and the mixed raw material is continuously introduced to react at the temperature of 200-350 ℃.
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US5510545A (en) * 1992-05-26 1996-04-23 Hoechst Aktiengesellschaft Process for the preparation of hydrofluorocarbons
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CN109331864A (en) * 2018-10-26 2019-02-15 东莞东阳光科研发有限公司 A method of hydrogenation coupling catalyst and preparation method thereof and preparation 1,1,1,4,4,4- hexafluoro -2- butylene

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5510545A (en) * 1992-05-26 1996-04-23 Hoechst Aktiengesellschaft Process for the preparation of hydrofluorocarbons
CN106536462A (en) * 2014-02-07 2017-03-22 科慕埃弗西有限公司 Integrated process for the production of z-1,1,1,4,4,4-hexafluoro-2-butene
CN106008147A (en) * 2016-05-23 2016-10-12 北京宇极科技发展有限公司 Preparation method of Z-1,1,1,4,4,4-hexafluoro-2-butene
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