CN107876098B - Catalyst for synthesizing polyether amine and preparation method and application thereof - Google Patents
Catalyst for synthesizing polyether amine and preparation method and application thereof Download PDFInfo
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- CN107876098B CN107876098B CN201711167232.6A CN201711167232A CN107876098B CN 107876098 B CN107876098 B CN 107876098B CN 201711167232 A CN201711167232 A CN 201711167232A CN 107876098 B CN107876098 B CN 107876098B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Abstract
The invention relates to a catalyst for synthesizing polyether amine and a preparation method and application thereof. The invention discloses a supported catalyst, which comprises an activated carbon carrier and a metal oxide loaded on the carrier, wherein: the activated carbon carrier loaded with the metal oxide also contains an amide nitrogen group for carrying out surface modification on the activated carbon carrier. The invention also discloses a preparation method of the catalyst and application of the catalyst in synthesizing polyether amine. The catalyst of the invention can show high activity, high selectivity, high stability, excellent hydration resistance and metal loss resistance in application.
Description
Technical Field
The invention relates to the field of polyether amine preparation, and particularly relates to a catalyst for synthesizing polyether amine, a preparation method of the catalyst, and application of the catalyst in preparation of polyether amine.
Background
The Polyether amine is also called Amino-Terminated Polyether (ATPE for short) which is a polyoxyalkylene compound with a Polyether backbone and Amino-Terminated end. These amine-terminated polyethers mostly use polyethers (polyethylene glycol, polyoxypropylene ether, etc.) as reaction raw materials, and convert the terminal hydroxyl groups of polyether polyols into corresponding amine groups or amino groups (the terminal groups are usually primary, secondary or polyamine groups containing active hydrogen) by different chemical treatment methods. At present, only two companies, Huntsman and BASF, can industrialize the amino-terminated polyether amine internationally.
Due to the reactivity of the tail amino group or the amine group of the polyether framework, the polyether framework can react with various reactive groups, such as epoxy groups, isocyanate groups and the like; in addition, due to the existence of ether bonds in the polyether chain, the polyether amine is easy to dissolve in various organic matters, so that the application range of the polyether amine in the industrial field is greatly widened. Therefore, polyetheramines are widely used in the fields of epoxy resin curing agents, polyurethane (polyurea) industry, gasoline detergent dispersants, and the like, because of their excellent properties.
The synthesis method of the polyether amine mainly comprises a catalytic reductive amination method, a leaving group method and a cyanoalkylation method. At present, the industrial production mainly adopts a catalytic reduction amination method, namely, the polyether glycol is directly reacted with hydrogen and liquid ammonia in one step in the presence of a hydroamination catalyst (such as a Ni/Cu/Cr catalyst and a Raney Ni/Al catalyst). The key to the production process is the selection and preparation of the catalyst. Catalysts suitable for reductive amination contain metals such as Ni, Co and Cu as the active components, sometimes referred to as hydrogenation/dehydrogenation catalysts because they are active in both types of reactions. Other elements of the periodic table are also frequently introduced into the catalyst to provide the catalyst with optimal activity or selectivity.
US4766245 discloses a preparation method of a raney nickel/aluminium catalyst, in which the Ni content is 60-75%, the Al content is 25-40%.
CN102780571 discloses Al2O3A preparation method of a supported catalyst. Based on the total amount of the catalyst, the Ni content is 16-22%, the Co content is 17-21%, the Cu content is 9-11%, the Sn content is 0.5-2%, and the yttrium, lanthanum, cerium and/or hafnium content is 05-2% of Al2O3。
The above catalysts have a problem of deactivation. According to the reaction mechanism, the preparation of polyether amine by hydroamination of polyether polyol generally comprises the steps of dehydrogenation, ammonia addition, dehydration, hydrogenation and the like, and water generated in the reaction process is a main factor causing catalyst deactivation. Patent US4766245 states that the rate of deactivation of raney nickel/aluminum catalysts is proportional to the amount of water produced in the reaction, and that lower molecular weight polyethers produce more water during the reaction and deactivate the catalyst more rapidly than higher molecular weight polyethers. CN1165712 indicates that the deactivation of amination catalysts is due to the support Al2O3Partial or complete phase transition, i.e., rehydration, easily occurs during amination, resulting in a decrease or deactivation of catalyst activity.
In order to solve the problem of catalyst deactivation, researchers at home and abroad carry out modification research on the catalyst.
US5352835 discloses a process for preparing mechanically stable phase alumina supported catalyst comprising, based on the total catalyst, Ni 15-30%, Cu 3-20%, Mo 0.5-1%, and theta-Al as carrier2O3. The carrier is composed of gamma-Al2O3Is obtained by high-temperature roasting, and has better stability. However, the catalyst preparation process has the following problems: (1) the pore size distribution of the carrier is strict, and the difficulty in preparing the carrier meeting the requirements is high. (2) The preparation is carried out by a molten salt method, and the problem of carrier pore channel blockage caused by salting out exists in the dipping process. (3) The metal loading is high, the metal is dispersed unevenly, and the problems of difficult preparation and metal loss exist.
US20140179952 discloses CoO-Y2O3The catalyst has CoO content of 57-90 wt% and Y content2O3The content of (A) is 9-17%, and the content of PdO is 0.9-25.7%. The patent states that cobalt and yttrium in the catalyst have a higher affinity for amine compounds and hydrogen than for water, and therefore the catalyst has better stability. However, the catalyst has the following problems: (1) the coprecipitation method adopted for preparation process has the disadvantages of complex process and poor reproducibilityAnd (5) problems are solved. (2) The catalyst contains high content of cobalt, rare metal yttrium and noble metal palladium, and the content of active components in the supported catalyst is up to 50 percent (by weight), so the problem of high catalyst cost exists. (3) The catalyst is only used in batch process, and does not relate to application examples of continuous process.
The above prior art catalysts need further improvement in one or more of the aspects of preparation process, metal loading, catalyst stability, resistance to hydration, and resistance to metal loss.
Disclosure of Invention
The invention aims to provide a supported catalyst for synthesizing polyether amine, which overcomes the defect of poor hydration resistance of the existing hydroamination catalyst by modifying an active carbon carrier and has high activity and good selectivity.
It is another object of the present invention to provide a process for preparing the above supported catalyst.
It is a further object of the present invention to provide the use of the above-described catalysts for the synthesis of polyetheramines.
In order to achieve one aspect of the above object, the invention adopts the following technical scheme:
a supported catalyst comprising an activated carbon support, and a metal oxide supported on the support, wherein: the activated carbon support loaded with the metal oxide also contains amide nitrogen groups (i.e., nitrogen-containing amide groups or functional groups) for surface modification of the activated carbon support.
In the present invention, the activated carbon support may be an activated carbon support commonly used in the art, preferably, the activated carbon support is selected from one or more of wood charcoal, coconut charcoal, peach shell charcoal, apricot shell charcoal, and coal charcoal, and further preferably coconut shell charcoal and/or coal charcoal.
Preferably, the specific surface area of the activated carbon carrier is 200-600 m2G, e.g. 300m2/g、400m2G or 500m2The average pore diameter is 50-300 nm, such as 100, 150, 200 or 250nm, which is beneficial to further improving the catalytic activity.
According to the catalyst of the present invention, preferably, the amide nitrogen group is introduced into the catalyst by: and uniformly mixing the activated carbon carrier loaded with the metal oxide with organic amine, and roasting in an inert atmosphere to modify the surface of the activated carbon carrier to obtain the activated carbon supported catalyst containing the amide nitrogen group. For example, the organic amine is directly mixed with the activated carbon carrier in a liquid form to be uniform or is introduced into the activated carbon carrier in a gaseous form, and the activated carbon carrier is roasted to carry out surface modification on the activated carbon carrier. Of course, it is understood in the art that the amide nitrogen group may also be introduced by other means, such as dipping the activated carbon support into an organic amine solution, drying, and then modifying by calcination. The inert atmosphere is well known in the art, such as an argon atmosphere.
According to the catalyst of the present invention, those skilled in the art understand that, in the surface modification, an excessively low calcination temperature is difficult to initiate an effective reaction, and an excessively high reaction temperature is easy to cause excessive decomposition of reactants, preferably, the calcination temperature is 300 to 1000 ℃, preferably 400 to 800 ℃, such as 500, 600 or 700 ℃; the roasting time is 1-12 h, preferably 4-8h, such as 5, 6 or 7h, so as to facilitate the reaction of organic amine on the activated carbon. Preferably, the organic amine is selected from one or more of melamine, ethylenediamine or diethylenetriamine.
According to the catalyst of the invention, the mass content of the amide nitrogen group in the catalyst is preferably 0.01-5%, preferably 0.5-3%.
It is understood by those skilled in the art that the metal oxide supported on the activated carbon support typically includes the catalytically desirable active components and optional adjuvants, where "optional" means that it may or may not be present. For the catalyst of the present invention, the active component is nickel oxide, preferably in an amount of 1-20 wt%, preferably 5-15 wt%, such as 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt% or 12 wt% of the catalyst; the auxiliary agent is an oxide of one or more of Cu, Cr, Mo, Zr and Fe, and the content is preferably 0.1-10 wt%, preferably 0.5-5 wt%, such as 0.2 wt%, 0.4 wt%, 0.8 wt%, 1 wt%, 2 wt% or 4 wt% of the catalyst.
In order to achieve another aspect of the above object, the present invention provides a method for preparing the above catalyst, comprising:
(1) performing acid leaching treatment on the activated carbon by using a 10-30% dilute nitric acid solution, filtering, washing, drying, roasting in an inert atmosphere, and cooling to obtain acid-treated activated carbon; calcination is a common processing step in catalyst preparation in the field, and is well known in the art, and in the present invention, the calcination temperature is preferably 300 to 500 ℃, for example, the calcination time at 400 ℃ is 2 to 4 hours;
(2) according to the content composition of the catalyst, immersing the acid-treated activated carbon obtained in the step (1) into a soluble metal salt solution corresponding to the metal oxide, and drying and roasting after adsorption to obtain an activated carbon carrier loaded with the metal oxide; preferably, the roasting temperature is 200-600 ℃, such as 300, 400 or 500 ℃, and the roasting time is 1-8 hours, such as 3, 4, 5 or 6 hours, so as to facilitate the decomposition load of the metal salt;
(3) uniformly mixing the activated carbon carrier loaded with the metal oxide obtained in the step (2) with organic amine, and roasting in an inert atmosphere to modify the surface of the activated carbon carrier to obtain an activated carbon supported catalyst with amide nitrogen groups; for the modification, it is to be noted that although a small amount of organic amine can also achieve a certain modification effect on the activated carbon, the optimal modification effect is difficult to achieve, and certainly, an excessive amount of organic amine is not necessary, and preferably, the molar ratio of the activated carbon to the organic amine is 1: 1-1: 10; more preferably 1:2 to 1:5, such as 1: 3. 1:4 or 1: 8.
in the present invention, the soluble metal salt includes, but is not limited to, one or more of halide, nitrate, organic acid salt, etc. of the metal, which are well known in the art and will not be described herein.
Among the above methods, methods for adsorbing the metal salt solution by using the carrier are well known in the art, and those skilled in the art understand that the adsorption amount of the metal salt in the carrier can be adjusted by adjusting the solution concentration, the impregnation time, and the like, thereby controlling the content of the active component or the auxiliary agent in the catalyst, and the adsorption process can also be performed once or repeatedly for a plurality of times. In one embodiment, the volume ratio of the metal salt solution to the carrier may be controlled within a suitable range so that the metal salt solution can be substantially completely absorbed by the carrier or the resulting solid-liquid mixture of the carrier and the solution is subjected to evaporation drying to remove the excess solvent; preferably, the impregnation is completed by adopting an equal-volume impregnation method at one time, and the preparation process is simple.
In order to achieve a further aspect of the above objects, the present invention also provides the use of the above catalyst for the synthesis of polyetheramines, the catalyst of the present invention being particularly suitable for the reductive amination of polyols having a polyether as backbone unit, said polyether polyol preferably having an Ethylene Oxide (EO) and/or Propylene Oxide (PO) backbone and an average molecular weight of 100-.
Of course, those skilled in the art understand that before the catalytic synthesis of the polyether amine, the catalyst needs to be subjected to reduction activation treatment, for example, reduction activation is performed at about 220 ℃ under pure hydrogen-containing atmosphere, for example, reduction is performed for 2-24 h, preferably 8-16 h at 150-500 ℃, preferably 200-400 ℃ under hydrogen atmosphere.
According to the application of the invention, preferably, polyether glycol is used for hydro-ammoniation reaction to synthesize polyether amine under the action of a catalyst; in a preferred embodiment, a continuous fixed bed process is adopted, ammonia with the molar weight 5-30 times that of polyether polyol and hydrogen with the molar weight 0.1-10 times that of polyether polyol are introduced, and the hydroamination reaction is carried out at the reaction temperature of 180-240 ℃ and the reaction pressure of 10.0-18.0 MPa.
According to the use of the present invention, preferably, the molecular structural formula of the starting polyether polyol is selected from the group consisting of formulae (a) and (b):
wherein R in the formula (a)1Is C1～C4Hydroxyalkyl radical, R2And R3Are each independently selected from linear or branched aliphatic C2～C4A group; m: 0 to 115, such as 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100; n: 0 to 115, such as 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100; m + n: 1 to 115, such as 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100;
wherein R is hydrogen or methyl; r4、R5And R6Are each independently selected from linear or branched aliphatic C2～C4A group; x: 0 to 40, such as 2, 5, 10, 20 or 30; y: 0 to 40, such as 2, 5, 10, 20 or 30; z: 0 to 40 parts by weight; x + y + z: 1 to 115, such as 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100.
In the above numerical selection, those skilled in the art understand that when 0, it means not included.
Compared with the prior art, the invention has the following advantages:
(1) the invention takes the activated carbon as a carrier, adopts organic amine for surface modification, generates amide nitrogen groups, enhances the non-polarity of the surface of the carrier, is beneficial to leading water generated by reaction to be separated from the surface of the catalyst quickly, and avoids Al2O3The rehydration phenomenon of the support during amination leads to the problem of catalyst deactivation;
(2) research shows that the catalyst of the invention is applied to the reaction of preparing polyether amine by hydroamination of polyether polyol, especially for preparing polyether amine with low molecular weight (molecular weight less than 500) (such as D230, D400, T403 and the like), and has excellent activity, selectivity, stability and metal loss resistance;
(3) compared with the existing catalyst, the catalyst can be impregnated at one time by adopting an isometric impregnation method, the preparation process is simple, the metal loading is low, and the activity and the selectivity of the catalyst are kept better.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples listed, and it should also include equivalent modifications and variations to the technical solutions defined in the claims appended to the present application.
Determination of amide nitrogen groups: the content of the nitrogen-containing amide functional group is characterized by X-ray photoelectron spectroscopy (XPS) (see Carbon,1995, Vol.33:1021-1027 for a specific characterization method);
the reactor in the examples is a fixed bed reactor.
Coconut shell activated carbon with specific surface area of 400m2(ii)/g, average pore diameter 200 nm;
peach shell activated carbon with specific surface area of 500m2(ii)/g, average pore diameter is 100 nm;
coal-based activated carbon with specific surface area of 300m2In g, the mean pore diameter is 150 nm.
Unless otherwise specified, the chemicals used are analytically pure and the contents referred to in the present invention are all mass contents.
The first embodiment is as follows: preparation and application of 10% NiO-4% CuO/AC-1 catalyst
Preparing a catalyst: weighing 50g of coconut shell activated carbon (4-8 meshes), treating with 30% dilute nitric acid solution at 80 ℃ for 4h, filtering and washing to neutrality, drying, standing at 300 ℃ in Ar atmosphere for 2h, and naturally cooling. According to the content composition of the catalyst, the activated carbon is immersed into an aqueous solution containing 22.6g of nickel nitrate and 7.1g of copper nitrate by an isometric immersion method, is dried after adsorption balance, and is roasted for 4 hours at 400 ℃ to obtain the activated carbon loaded with metal oxides. Uniformly mixing the activated carbon and the ethylenediamine according to the molar ratio of 1:2.5, heating to 500 ℃ at the temperature rising rate of 2 ℃ in the Ar atmosphere, keeping for 8 hours, and cooling to obtain the amide nitrogen functional group-containing supported catalyst 10% NiO-4% CuO/AC-1; the amide nitrogen group content of the catalyst was determined to be 0.5%.
Evaluation of catalyst: the polyether amine is prepared by hydroamination of polyether polyol D-2000 (with a bifunctional degree and a molecular weight of 2000) and evaluated by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 12 hours at 300 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is naturally reduced to 200 DEG CIncreasing the pressure to 15.0MPa, stabilizing the system, and then adding NH in a molar ratio3Pumping the liquid flow with the/D-2000-20 ratio into a reactor by a pump, introducing hydrogen with the molar weight 5 times that of the D-2000, reacting for a period of time, filtering, vacuumizing and distilling to obtain the polyether amine product. By chemical analysis, the reaction conversion rate is 98.7%, and the primary amine selectivity is 98.8%.
Example two: 8% NiO-2% CuO-2% Fe2O3Preparation and application of/AC-2 catalyst
Weighing 50g of peach shell activated carbon (4-8 meshes), treating with 30% dilute nitric acid solution at 60 ℃ for 8h, filtering and washing to neutrality, drying, standing at 400 ℃ in Ar atmosphere for 2h, and naturally cooling. According to the content composition of the catalyst, the activated carbon is immersed into an aqueous solution containing 17.7g of nickel nitrate, 3.5g of copper nitrate and 5.7g of ferric nitrate by an isometric immersion method, is dried after adsorption equilibrium is achieved, and is roasted for 3 hours at 500 ℃ to obtain the activated carbon loaded with the metal oxide. Uniformly mixing the activated carbon and the melamine according to the molar ratio of 1:3, heating to 450 ℃ at the temperature rise rate of 2 ℃ in the Ar atmosphere, keeping for 6h, and cooling to obtain the supported catalyst containing the amide nitrogen functional group, namely 8% NiO-2% CuO-2% Fe2O3(ii) AC-2; the amide nitrogen group content of the catalyst was determined to be 2%.
Evaluation of catalyst: taking polyether polyol T-3000 (with three functionality degrees and a molecular weight of 3000) to prepare polyether amine by hydroamination as an example, a continuous method fixed bed process is adopted for evaluation. Before the catalyst is used, the catalyst is reduced for 24 hours at 200 ℃ in a hydrogen gas flow (under normal pressure). The temperature in the reactor is naturally cooled to 210 ℃, the pressure is increased to 18.0MPa, and the molar ratio NH is adjusted after the system is stable3Pumping the liquid with the molar weight of 30/T-3000 into a reactor, introducing hydrogen with the molar weight of 3 times of that of the T-3000, reacting for a period of time, filtering, and vacuum distilling to obtain the polyether amine product. By chemical analysis, the reaction conversion rate is 96.5%, and the primary amine selectivity is 99.0%.
Example three: 6% NiO-4% Fe2O3-1％MoO3Preparation and application of/AC-3 catalyst
Weighing 50g of coal-based activated carbon (4-8 meshes), treating with 30% dilute nitric acid solution at 100 deg.C for 6h, filtering and washingWashing to neutrality, drying, heating at 400 deg.C in Ar atmosphere for 2h, and naturally cooling. According to the content composition of the catalyst, the activated carbon is immersed into an aqueous solution containing 13.1g of nickel nitrate, 11.4g of ferric nitrate and 4.8g of ammonium molybdate by an isometric immersion method, is dried after adsorption equilibrium is achieved, and is roasted for 4 hours at 550 ℃ to obtain the activated carbon loaded with metal oxides. Uniformly mixing the activated carbon and the diethylenetriamine according to the molar ratio of 1:2, heating to 500 ℃ at the temperature rise rate of 2 ℃ in the Ar atmosphere, keeping for 6h, cooling and cooling to obtain the supported catalyst containing the amide nitrogen functional group, namely 6% NiO-4% Fe2O3-1％MoO3(ii) AC-3; the amide nitrogen group content of the catalyst was determined to be 1.5%.
Evaluation of catalyst: taking polyether polyol D-5000 (with bifunctional degree and molecular weight of 5000) to prepare polyether amine by hydroamination as an example, a continuous method fixed bed process is adopted for evaluation. Before the catalyst is used, the catalyst is reduced for 16h at 350 ℃ in a hydrogen stream (under normal pressure). Naturally cooling the temperature in the reactor to 180 ℃, increasing the pressure to 13.0MPa, stabilizing the system, and then adding NH with a molar ratio3Pumping the liquid with the molar weight of D-5000-15 into a reactor by a pump, introducing hydrogen with the molar weight of D-5000 being 6 times, reacting for a period of time, filtering, vacuumizing and distilling to obtain the polyether amine product. By chemical analysis, the reaction conversion rate is 97.0%, and the primary amine selectivity is 98.5%.
Example four: 12% NiO-1% Fe2O3-0.8％ZrO2Preparation and application of/AC-4 catalyst
Weighing 50g of coconut shell activated carbon (4-8 meshes), treating with 30% dilute nitric acid solution at 80 ℃ for 4h, filtering and washing to neutrality, drying, standing at 300 ℃ in Ar atmosphere for 3h, and naturally cooling. According to the content composition of the catalyst, the activated carbon is immersed into an aqueous solution containing 26.9g of nickel nitrate, 2.9g of ferric nitrate and 0.6g of zirconium acetate by an isometric immersion method, is dried after adsorption equilibrium, and is roasted for 4 hours at 550 ℃ to obtain the activated carbon loaded with the metal oxide. Uniformly mixing the activated carbon and the diethylenetriamine according to the molar ratio of 1:4, heating to 600 ℃ at the temperature rise rate of 2 ℃ in the Ar atmosphere, keeping for 4h, cooling and cooling to obtain the amide nitrogen functional group-containing supported catalyst 12% NiO-1% Fe2O3-0.8％ZrO2(ii) AC-4/AC-4; the amide nitrogen group content of the catalyst was determined to be 3%.
Evaluation of catalyst: the polyether amine is prepared by hydroamination of polyether polyol D-2000 (with a bifunctional degree and a molecular weight of 2000) and evaluated by a continuous fixed bed process. Before the catalyst is used, the catalyst is reduced for 8 hours at 400 ℃ in a hydrogen gas flow (under normal pressure). Naturally cooling the temperature in the reactor to 215 ℃, boosting the temperature to 14.0MPa, stabilizing the system, and then adding NH with a molar ratio3Pumping the liquid flow of which the/D-2000 is 18 into a reactor by a pump, introducing hydrogen with the molar weight 2 times that of the D-2000, reacting for a period of time, filtering, vacuumizing and distilling to obtain the polyether amine product. By chemical analysis, the reaction conversion rate is 96.8%, and the primary amine selectivity is 99.5%.
Example five: 2% NiO-5% CuO-4% MoO3Preparation and application of/AC-5 catalyst
Weighing 50g of coal-based activated carbon (4-8 meshes), treating with 30% dilute nitric acid solution at 100 ℃ for 6h, filtering and washing to neutrality, drying, standing at 400 ℃ in Ar atmosphere for 2h, and naturally cooling. According to the content composition of the catalyst, the activated carbon is immersed into an aqueous solution containing 4.4g of nickel nitrate, 8.5g of copper nitrate and 19.3g of ammonium molybdate by an isometric immersion method, is dried after adsorption equilibrium is achieved, and is roasted for 4 hours at 550 ℃ to obtain the activated carbon loaded with metal oxides. Uniformly mixing the activated carbon and the ethylenediamine according to the molar ratio of 1:2, heating to 600 ℃ at the temperature rise rate of 2 ℃ in the Ar atmosphere, keeping for 6 hours, cooling and cooling to obtain the supported catalyst containing the amide nitrogen functional groups, wherein the supported catalyst contains 2% of NiO, 5% of CuO and 4% of MoO3(ii) AC-5; the amide nitrogen group content of the catalyst was determined to be 1%.
Evaluation of catalyst: taking polyether polyol T-403 (with three functionality degrees and molecular weight of 440) to prepare polyether amine by hydroamination as an example, a continuous method fixed bed process is adopted for evaluation. Before the catalyst is used, the catalyst is reduced for 16h at 350 ℃ in a hydrogen stream (under normal pressure). The temperature in the reactor is naturally cooled to 225 ℃, the pressure is increased to 10.0MPa, and the molar ratio NH is adjusted after the system is stable3Pumping the liquid with the molar weight of 25/T-403 into a reactor, introducing hydrogen with the molar weight of 8 times of that of the T-403, reacting for a period of time, filtering, and vacuum distilling to obtain the productPolyetheramine products. By chemical analysis, the reaction conversion rate is 99.5%, and the primary amine selectivity is 99.8%.
Example six: 4% NiO-0.8% CuO-4% Cr2O3Preparation and application of/AC-6 catalyst
Weighing 50g of coconut shell activated carbon (4-8 meshes), treating with 30% dilute nitric acid solution at 80 ℃ for 8h, filtering and washing to neutrality, drying, standing at 400 ℃ in Ar atmosphere for 5h, and naturally cooling. According to the content composition of the catalyst, the activated carbon is immersed into an aqueous solution containing 8.5g of nickel nitrate, 1.3g of copper nitrate and 11.5g of chromium nitrate by an isometric immersion method, is dried after adsorption balance, and is roasted for 4 hours at 500 ℃ to obtain the activated carbon loaded with the metal oxide. Uniformly mixing the activated carbon and the ethylenediamine according to the molar ratio of 1:2.5, heating to 500 ℃ at the temperature rising rate of 2 ℃ in the Ar atmosphere, keeping for 6 hours, cooling and cooling to obtain the supported catalyst containing the amide nitrogen functional groups, wherein the supported catalyst contains 4% of NiO, 0.8% of CuO and 4% of Cr2O3(ii)/AC-6; the amide nitrogen group content of the catalyst was determined to be 2.5%.
Evaluation of catalyst: taking polyether polyol T-403 (with three functionality degrees and molecular weight of 440) to prepare polyether amine by hydroamination as an example, a continuous method fixed bed process is adopted for evaluation. Before the catalyst is used, the catalyst is reduced for 8 hours at 400 ℃ in a hydrogen gas flow (under normal pressure). Naturally cooling the temperature in the reactor to 240 ℃, increasing the pressure to 11.0MPa, stabilizing the system, and then adding NH with a molar ratio3Pumping the liquid with the molar weight of 10/T-403 into a reactor, introducing hydrogen with the molar weight of 3 times that of the T-403, reacting for a period of time, filtering, and vacuum distilling to obtain the polyether amine product. By chemical analysis, the reaction conversion rate is 98.5%, and the primary amine selectivity is 98.4%.
Example seven: 15% NiO-0.8% Fe2O3-0.5％Cr2O3Preparation and application of/AC-7 catalyst
Weighing 50g of coal-based activated carbon (4-8 meshes), treating with 30% dilute nitric acid solution at 100 ℃ for 6h, filtering and washing to neutrality, drying, standing at 400 ℃ in Ar atmosphere for 2h, and naturally cooling. According to the content composition of the catalyst, the activated carbon is immersed into a solution containing 34.9g of nickel nitrate, 2.4g of ferric nitrate and 1.6g of nitric acid by an isovolumetric immersion methodAnd (3) drying the chromium in the aqueous solution after the adsorption balance, and roasting the chromium at 550 ℃ for 4 hours to obtain the metal oxide loaded active carbon. Uniformly mixing the activated carbon and the melamine according to the molar ratio of 1:3, heating to 600 ℃ at the temperature rise rate of 2 ℃ in the Ar atmosphere, keeping for 6h, and cooling to obtain the amide nitrogen functional group-containing supported catalyst 15% NiO-0.8% Fe2O3-0.5％Cr2O3(ii) AC-7; the amide nitrogen group content of the catalyst was determined to be 1%.
Evaluation of catalyst: taking polyether polyol D-400 (with a bifunctional degree and a molecular weight of 430) to prepare polyether amine by hydroamination as an example, the evaluation is carried out by adopting a continuous method fixed bed process. Before the catalyst is used, the catalyst is reduced for 15h at 200 ℃ in a hydrogen gas flow (under normal pressure). Naturally cooling the temperature in the reactor to 220 ℃, increasing the pressure to 17.0MPa, stabilizing the system, and then adding NH with a molar ratio3Pumping the liquid with the molar weight of D-400 being 15 into a reactor through a pump, introducing hydrogen with the molar weight being 1 time of that of D-400, reacting for a period of time, filtering, vacuumizing and distilling to obtain the polyether amine product. By chemical analysis, the reaction conversion rate is 96.0%, and the primary amine selectivity is 98.0%.
Example eight:
taking the polyether polyol PPG-230 (with the bifunctional degree and the molecular weight of 230) to prepare the polyether amine D230 by hydroamination as an example, the catalyst of the invention is evaluated by a continuous method fixed bed process.
Fixed bed process conditions of the continuous method: before the catalyst is used, the catalyst is reduced for 18h at 300 ℃ in a hydrogen gas flow (under normal pressure). Naturally cooling the temperature in the reactor to 210 ℃, increasing the pressure to 14.0MPa, stabilizing the system, and then adding NH with a molar ratio3Pumping the liquid flow of/PPG-230 ═ 5 into a reactor through a pump, introducing hydrogen with the molar weight of 1.5 times that of PPG-2000, sampling every 4h, filtering and vacuumizing the sample to obtain a polyether amine product, and obtaining the reaction conversion rate and the primary amine selectivity through chemical analysis.
After the catalyst of 10% NiO-4% CuO/AC-1 in example 1 is continuously operated for 500h, the activity and the selectivity of the catalyst are kept unchanged, the reaction conversion rate is 98.6%, and the primary amine selectivity is 99.2%. Without the catalyst having rehydration problems.
Comparative example 1
The difference from example eight is that the catalyst is 19.9% Ni-7.6% Cu/theta-Al prepared according to the method for preparing the catalyst in example XIX of patent US5352835A2O3A catalyst. After the catalyst is continuously operated for 200 hours, the activity is obviously reduced, the reaction conversion rate is 90.5 percent, and the primary amine selectivity is 98.0 percent. The extent of rehydration of the alumina component was estimated to be 25% by X-ray derivative spectroscopy using the integrated intensity of the boehmite peak to the theta alumina peak.
From the above, the catalyst of the present invention has excellent hydration resistance, and the stability of the catalyst of the present invention is significantly superior to that of the prior art alumina-supported catalyst.
According to the continuous fixed bed evaluation process of the catalyst in example eight and comparative example one, samples were taken every 4 hours, and the metal content in each sample was subjected to the ICP test, and the results are shown in table 2.
TABLE 2 determination of Metal content in reaction solution
"-" indicates no metal was detected.
This example demonstrates that the catalyst of the present invention has superior resistance to metal loss compared to prior art alumina supported catalysts.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes or modifications of the technical solution of the present invention are within the spirit of the present invention.
Claims (17)
1. A supported catalyst comprising an activated carbon support, and a metal oxide supported on the support, characterized in that: the activated carbon carrier loaded with the metal oxide also contains an amide nitrogen group for carrying out surface modification on the activated carbon carrier; the amide nitrogen group is introduced into the catalyst by: uniformly mixing the activated carbon carrier loaded with the metal oxide with organic amine, and roasting the mixture in an inert atmosphere to modify the surface of the activated carbon carrier to obtain an activated carbon supported catalyst containing an amide nitrogen group; the mass content of the amide nitrogen group in the catalyst is 0.01-5%.
2. The catalyst according to claim 1, wherein the calcination temperature is 300 to 1000 ℃ during surface modification; the roasting time is 1-12 h.
3. The catalyst as claimed in claim 2, wherein the calcination temperature is 400-800 ℃ during the surface modification; the roasting time is 4-8 h; the organic amine is selected from one or more of melamine, ethylenediamine or diethylenetriamine.
4. The catalyst according to any one of claims 1 to 3, wherein the mass content of the amide nitrogen group in the catalyst is 0.5 to 3%.
5. The catalyst according to any one of claims 1 to 3, wherein the metal oxide comprises an active component and an optional auxiliary agent, wherein the active component is nickel oxide and is 1-20 wt% of the catalyst; the auxiliary agent is one or more oxides of Cu, Cr, Mo, Zr and Fe, and the content of the auxiliary agent is 0.1-10 wt% of the catalyst.
6. The catalyst of claim 5, wherein the active component is nickel oxide in an amount of 5 to 15 wt% of the catalyst; the auxiliary agent is one or more oxides of Cu, Cr, Mo, Zr and Fe, and the content of the auxiliary agent is 0.5-5 wt% of the catalyst.
7. According to claims 1-3The catalyst according to any one of the above items, wherein the activated carbon carrier has a specific surface area of 200 to 600m2(ii)/g, the average pore diameter is 50 to 300 nm.
8. The catalyst of any one of claims 1-3, wherein the activated carbon support is selected from one or more of wood charcoal, coconut charcoal, peach shell charcoal, apricot shell charcoal, and coal charcoal.
9. The catalyst according to claim 8, wherein the activated carbon support is coconut shell carbon and/or coal carbon.
10. A method for preparing a catalyst according to any one of claims 1 to 9, characterized in that it comprises:
(1) performing acid leaching treatment on the activated carbon by using a 10-30% dilute nitric acid solution, filtering, washing, drying, roasting in an inert atmosphere, and cooling to obtain acid-treated activated carbon;
(2) according to the content composition of the catalyst, immersing the acid-treated activated carbon obtained in the step (1) into a soluble metal salt solution corresponding to the metal oxide, drying after adsorption balance, and roasting at 200-600 ℃ for 1-8 h to obtain an activated carbon carrier loaded with the metal oxide;
(3) and (3) uniformly mixing the activated carbon carrier loaded with the metal oxide obtained in the step (2) with organic amine, and roasting in an inert atmosphere to modify the surface of the activated carbon carrier, so as to obtain the activated carbon supported catalyst with amide nitrogen groups.
11. The preparation method of the catalyst according to claim 10, wherein in the step (1), the roasting temperature is 300-500 ℃, and the roasting time is 2-4 h; in the step (3), the molar ratio of the activated carbon to the organic amine is 1: 1-1: 10.
12. The method for preparing the catalyst according to claim 11, wherein in the step (3), the molar ratio of the activated carbon to the organic amine is 1:2 to 1: 5.
13. Use of the catalyst according to any one of claims 1 to 9 or the catalyst prepared by the preparation process according to any one of claims 10 to 12 for the synthesis of polyetheramines; wherein, before the polyether amine is synthesized by catalysis, the catalyst is subjected to reduction activation treatment.
14. Use according to claim 13, characterized in that polyetheramines are synthesized by hydroamination of polyether polyols.
15. The application of the method as claimed in claim 14, wherein a continuous fixed bed process is adopted, ammonia with a molar weight 5-30 times that of polyether polyol and hydrogen with a molar weight 0.1-10 times that of polyether polyol are introduced, and the hydroamination reaction is carried out at a reaction temperature of 180-240 ℃ and a reaction pressure of 10.0-18.0 MPa.
16. The use as claimed in claim 14, wherein the polyether polyol has an EO and/or PO backbone and an average molecular weight of 100-.
17. The use as claimed in claim 16, wherein the polyether polyol has an average molecular weight of 200-600.
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