CN108014821B - 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 PDF

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CN108014821B
CN108014821B CN201711251017.4A CN201711251017A CN108014821B CN 108014821 B CN108014821 B CN 108014821B CN 201711251017 A CN201711251017 A CN 201711251017A CN 108014821 B CN108014821 B CN 108014821B
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niobium
carrier
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CN108014821A (en
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任树杰
张聪颖
李鑫
刘振国
唐磊
刘志鹏
曹善健
黎源
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Wanhua Chemical Group Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen

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Abstract

The invention discloses a catalyst for synthesizing polyetheramine, which comprises NbAlO4Carrier and NiO and Au supported on the carrier2O3And SeO2Wherein the content of active component NiO in the catalyst is 1-15 wt%, and Au is calculated by the total weight of the catalyst2O3The content of (B) is 0.01-2 wt%, SeO2The content of (B) is 0.01-1 wt%, NbAlO4The support is prepared by a solid-state reaction between a niobium-containing compound and alumina. The invention also discloses a preparation method of the catalyst and application of the catalyst in synthesizing polyether amine, especially low molecular weight polyether amine. The catalyst of the invention can show high activity, high selectivity, high stability, excellent hydration resistance, carbon deposition resistance and sintering resistance in application.

Description

Catalyst for synthesizing polyether amine and preparation method and application thereof
Technical Field
The invention relates to the field of polyether amine preparation, and particularly relates to an improved catalyst for synthesizing polyether amine, a preparation method of the improved catalyst, and application of the improved catalyst in synthesizing polyether amine by carrying out hydroamination reaction on polyether polyol.
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. 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 reductive amination method, a leaving group method and a polyether nitrile reduction method. The reductive amination method is also called as hydroamination method, the process route is most advanced, and the produced product has the most stable quality and better meets the requirement of environmental protection, so the reductive amination method becomes the main industrial production method of the polyether amine at home and abroad.
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.
US4014933 discloses an alumina or silica supported Co-Ni-Cu catalyst and a process for the amination of polypropylene glycols. The catalyst comprises 10% of Co, 10% of Ni, 4% of Cu and 0.4% of phosphoric acid, and the balance of Al2O3. The catalyst is suitable for amination reaction of polyether polyol with molecular weight greater than 1400.
US4152353 and US4153581 disclose an alumina supported catalyst of Ni, Cu and one or two metals selected from Fe and Zn promoters comprising30% Ni (or 30% Co), 63% Cu, and 7% Fe and/or Zn, the balance being Al2O3. The catalyst has the problems of low activity and poor selectivity.
US4209424 discloses an alumina supported transition metal amination catalyst and its use in the amination of polyether polyols, the catalyst comprising at least one or two of Ni, Co and Cu, wherein the metal content is 30-70%, the remainder being Al2O3。
US4973761 discloses an alumina supported Ni, Co and Cu amination catalyst and its use for the amination of polytetrahydrofuran ether glycols. The catalyst is suitable for amination of polyether polyol with the molecular weight of 640-4000, and has the problems of low catalyst activity and poor product selectivity.
US5003107 discloses an alumina supported Ni, Cu, Cr, Mo amination catalyst and its use in the amination of polyoxytetramethylene glycol. The catalyst comprises 70-75% of Ni, 20-25% of Cu, 0.5-5% of Cr and 1-5% of Mo, and the balance of Al2O3. When a continuous tubular reactor is used, the raw material conversion rate reaches 91-96% and the product selectivity reaches 92-97% in the process of ammoniating polytetrahydrofuran polyether with the molecular weight of 1000 and 2000. The catalyst does not involve the amination of polyether polyols having a molecular weight of less than 500.
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%, the yttrium, lanthanum, cerium and/or hafnium content is 0.5-2%, and the rest is Al2O3。
CN106669731A discloses Al2O3A preparation method of a supported catalyst. Based on the total amount of the catalyst, the active component Ni content is 5-30 wt%, the Cu content is 5-25%, the Pd content is 0.3-2.0%, the auxiliary agents V, Cr, Mn, Fe, Co, Zn, Mo, W, Sn, Pb, Bi, La, Ce, Nd and/or Sm content is 0-5%, and the balance is Al2O3。
Problems common to the above supported catalysts: the activity of the catalyst decreases with the time of use during use, i.e. the catalyst deactivates. The factors causing the deactivation of the catalyst are many, and can be attributed to the influence of raw material impurities, the influence of reaction conditions and the deactivation caused by the change of catalyst components and structures in the reaction process, such as various factors of poisoning, carbon deposition, blockage, sintering, heat deactivation and the like. The reason for the deactivation of the synthesized polyether amine supported catalyst can be summarized as the following three aspects:
(1) according to the reaction mechanism, the synthesis of polyether amine generally comprises the steps of dehydrogenation, ammonia addition, dehydration, hydrogenation and the like, and a large amount of water is generated in the amination reaction process. 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. Under the reaction conditions of high temperature, high pressure and water, the reaction is carried out by using gamma-Al2O3The catalyst which is a carrier can generate a rehydration phenomenon, thereby causing the change of the microstructure of the catalyst, causing the reduction of the strength of the catalyst, even the collapse of a framework structure, the blockage of micropores, the reduction of pore volume and the great reduction of the specific surface area of the catalyst, and further leading the irreversible inactivation of the catalyst to be generated. Thus, gamma-Al2O3Is the first factor that leads to catalyst deactivation.
(2) According to the reaction mechanism, the amination reaction in the presence of a hydrogenation catalyst and hydrogen is a dehydrogenation/hydrogenation process, i.e. the alcohol is first dehydrogenated to form an aldehyde or ketone, which is then reacted with ammonia to form an imine, which is reduced to a primary amine under the action of the hydrogenation catalyst, and the primary amine and the carbonyl compound are reacted via a schiff base intermediate to form the corresponding secondary and tertiary amines. The second factor that leads to catalyst deactivation is that the imine formed is susceptible to oligomerization and polymerization with the hydrogenation catalyst to form carbon deposits.
(3) A third factor in catalyst deactivation is sintering. The active component copper is a low melting point metal, and when the temperature reaches 30% of the melting point of the active component copper, sintering easily occurs, so that the particle size is increased, the surface area is reduced, and the catalyst is deactivated.
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 is adopted for preparing the material, so that the problems of complex process and poor reproducibility exist. (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 hydration resistance, carbon deposition resistance, and sintering resistance, as well as in preparation processes, metal loading, catalyst cost, and the like. At the same time, the prior art catalysts show less than ideal catalyst stability for the amination of low molecular weight polyether polyols, especially polyether polyols having an average molecular weight of less than 500.
Disclosure of Invention
The invention aims to provide an improved catalyst for synthesizing polyether amine, which overcomes the defect of poor hydration resistance of the existing hydroamination catalyst by modifying active alumina, and has high activity and good selectivity.
The catalyst for synthesizing polyether amine comprises NbAlO4Carrier and NiO and Au supported on the carrier2O3And SeO2An active component.
Preferably, the content of the active component NiO in the catalyst is 1-15 wt%, and Au is calculated by the total weight of the catalyst2O3The content of (B) is 0.01-2 wt%, SeO2The content of (B) is 0.01-1 wt%.
More preferably, the content of the active component NiO is 5-10 wt% and the content of Au is 5-10 wt% of the total weight of the catalyst2O30.5-1.5 wt% of SeO2The content of (B) is 0.1-0.5 wt%.
Another aspect of the present invention provides a method for preparing the above catalyst, comprising the steps of:
(1) preparation of NbAlO4Carrier: the carrier is prepared by solid-state reaction between a niobium-containing compound and alumina, the niobium-containing compound and the alumina are uniformly mixed, dried, roasted and molded to obtain the carrier, and the carrier is optionally ground and sieved before drying;
(2) preparing a catalyst: according to the content composition of the catalyst, the carrier obtained in the step (1) is soaked in an aqueous solution containing soluble nickel salt, gold salt and selenium-containing compound, after adsorption equilibrium, the carrier is dried and roasted to obtain the catalyst, and the catalyst is preferably soaked in the same volume.
The niobium-containing compound in step (1) may be one or more selected from niobium nitrate, niobium sulfate, niobium hydroxide, niobium oxalate and niobium carbonate, and is preferably niobium hydroxide and/or niobium oxalate.
In the screening process in the step (1), the mesh number of the solid powder is preferably controlled within the range of 100-200 meshes.
The roasting temperature in the step (1) can be 700-1500 ℃, and is preferably 900-1100 ℃; the calcination time is 10-40h, preferably 20-30 h.
The nickel salt in the step (2) can be selected from one or more of sulfate, nitrate and organic acid salt, preferably nitrate; the gold salt may be selected from one or more of gold nitrate, gold chloride and chloroauric acid tetrahydrate, preferably gold nitrate; the selenium-containing compound can be one or more selected from selenious acid, sodium selenite, potassium selenite, and selenium oxychloride, preferably selenious acid.
The roasting temperature in the step (2) is 100-600 ℃, preferably 300-500 ℃, and the roasting time is 1-24h, preferably 8-16 h.
In a further aspect, the present invention provides the use of the above catalyst in the hydroamination of polyether polyols to produce polyether amines. The catalysts of the invention are particularly suitable for the reductive amination of polyols having polyether as backbone unit, preferably containing an Ethylene Oxide (EO) and/or Propylene Oxide (PO) backbone, and having an average molecular weight of 100-. The polyether polyol contains more than two hydroxyl groups.
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 8-16h at 150-500 ℃, preferably 200-400 ℃ under hydrogen atmosphere.
The invention also provides a method for synthesizing polyether amine, which comprises the step of synthesizing polyether amine by carrying out hydroamination reaction on polyether polyol under the action of the 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.
In this application, "optionally" means with or without subsequent operations.
The invention has the beneficial effects that: the catalyst of the invention is not only suitable for amination reaction of polyether polyol with large molecular weight, but also has extremely high activity, selectivity and stability for amination reaction of polyether polyol with low molecular weight (molecular weight is less than 500). The catalyst of the invention is used for catalyzing the amination reaction of polyether alcohol, in particular for catalyzing the amination of polyether polyol with the average molecular weight of less than 500, the yield of aminated products can reach more than 99.0 percent, and the conversion rate of raw materials can reach more than 99 percent.
In the present invention, it has surprisingly been found that Nb can be incorporated into activated alumina by solid phase reaction2O5The stability of alumina to rehydration is significantly improved. Generated NbAlO4Tends to attach to the majority of active sites on the alumina surface that are readily and rapidly rehydrated, leaving Al exposed on the support surface3+The number of (namely anion cavities) is reduced, and under the environment of high temperature, high pressure and water generation, water is adsorbed on the anion cavities on the surface of the alumina, so that the probability of the reaction of the alumina and the water is greatly reduced. Thus, Nb2O5The introduction of (2) can effectively inhibit the occurrence of alumina rehydration.
At the same time, SeO2The introduction of the catalyst increases the dispersion degree, the active surface area and the anti-sintering performance of Ni and Au in the catalyst, thereby improving the activity and the selectivity of the catalyst.
According to the amination mechanism, the dehydrogenation of alcohols produces reactive aldehydes, which form imines with amines, and the transfer of hydrogen from the alcohol to the imine forms the amine. The introduction of Au in the active component is beneficial to the transfer of hydrogen, inhibits the oligomerization and polymerization of imine and enhances the carbon deposition resistance of the catalyst.
The catalyst disclosed by the invention is low in metal loading capacity, good in hydration resistance, carbon deposition resistance and sintering resistance, simple in preparation process, good in economy and good in application prospect.
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.
Gas chromatograph: shimadzu GC-2014(FID) detector, SE-30 capillary column (phi 0.30mm x 30m), injection port 270 deg.C, detector 270 deg.C; temperature rising procedure: the temperature is kept constant at 70 ℃ for 1min, and then the temperature is increased to 240 ℃ at the speed of 40 ℃/min and kept for 5 min.
Hydroxyl value determination method: see GB/T12008.3-2009.
Method for determining total amine value: titrating the product by adopting 0.5mol/L hydrochloric acid solution, and calculating the total amine value of the product according to the mass of the consumed hydrochloric acid.
Conversion rate of raw material: the total amine value of the product/the total hydroxyl value of the raw material is multiplied by 100 percent.
The product yield is as follows: the mass of the polyetheramine product/the mass of the raw material polyether polyol is multiplied by 100%.
The reductive amination reactor in the examples is a fixed bed reactor.
Polyether polyol (PPG-230, D-400, D-2000, D-5000, T-403, T-2000): vanhua chemical group, Inc.
Example 1
(1) Preparation of carrier NbAlO from niobium hydroxide4
99.1g of niobium hydroxide and 28.5g of alumina are uniformly mixed in a mortar, ground and sieved to obtain a mixture of 100 meshes and 200 meshes, and then the mixture is transferred into a crucible, dried at 110 ℃ for 24h and then calcined in air at 1050 ℃ for 20h (the temperature rise rate: 3 ℃/min; the temperature rise rate means that the temperature is raised from room temperature to the final temperature at a certain rate per minute). Yield: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity higher than 98%4). Tabletting and forming to obtain 3X 3mm columnar carrier.
(2)7％NiO-1％Au2O3-0.2％SeO2/NbAlO4Preparation of the catalyst
According to the content composition of the catalyst, the carrier is immersed into an aqueous solution containing 29.7g of nickel nitrate, 1.68g of gold nitrate and 0.25g of selenious acid by an isometric immersion method, is dried after adsorption equilibrium is achieved, and is roasted for 11 hours in air at 450 ℃ to obtain a catalyst precursor of 7% NiO-1% Au2O3-0.2％SeO2/NbAlO4。
(3) Evaluation of catalyst
Taking the polyether polyol PPG-230 (with a bifunctional degree and a molecular weight of 230) to prepare the polyether amine by hydroamination as an example, the evaluation is carried out by adopting a continuous method fixed bed process. Before the catalyst is usedReducing for 10h at 280 ℃ in hydrogen flow (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-230-15 into a reactor by a pump, introducing hydrogen with 5 times of the molar weight of PPG-230, reacting for a period of time, filtering, and vacuum distilling to obtain the polyether amine product. By chemical analysis, the reaction conversion rate is 100.0%, and the primary amine selectivity is 99.5%. The catalyst is continuously operated for 1000h, sampled and analyzed, and the result is unchanged.
Example 2
(1) Preparation of carrier NbAlO from niobium carbonate4
136.0g of niobium carbonate and 28.5g of alumina were put into a mortar and mixed uniformly, and then the mixture was ground and sieved to obtain a mixture of 100 meshes and 200 meshes, and then the mixture was transferred into a crucible, dried at 120 ℃ for 24 hours, and then calcined at 900 ℃ in air for 24 hours (rate of temperature rise: 5 ℃/min. rate of temperature rise means that the temperature was raised from room temperature to the final temperature at a definite rate per minute). Yield: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity higher than 98%4). Tabletting and forming to obtain 3X 3mm columnar carrier.
(2)10％NiO-0.7％Au2O3-0.3％SeO2/NbAlO4Preparation of the catalyst
According to the content composition of the catalyst, the carrier is immersed into an aqueous solution containing 43.7g of nickel nitrate, 1.21g of gold nitrate and 0.39g of selenious acid by an isometric immersion method, is dried after adsorption equilibrium is achieved, and is roasted in the air at 300 ℃ for 14 hours to obtain a catalyst precursor of 10% NiO-0.7% Au2O3-0.3％SeO2/NbAlO4。
(3) 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 raising the temperature in the reactor to 220 ℃, raising the pressure to 17.0MPa, stabilizing the system, and then adding NH with a molar ratio3The liquid stream of 15/D-400 is pumped into the reactor and D-400 mol is introducedReacting with 1 time hydrogen for a period of time, filtering, vacuumizing and distilling to obtain the polyether amine product. By chemical analysis, the reaction conversion rate is 100.0%, and the primary amine selectivity is 98.0%. The catalyst is continuously operated for 800h for sampling analysis, and the result is unchanged.
Example 3
(1) Preparation of carrier NbAlO from niobium nitrate4
226.5g niobium nitrate and 28.5g alumina are added into a mortar and mixed uniformly, and are ground and sieved to obtain a mixture with 200 meshes of 100, then the mixture is transferred into a crucible, dried at 120 ℃ for 20h, and then roasted at 1100 ℃ in air for 22h (the heating rate is 4 ℃/min, the heating rate is that the temperature is raised from room temperature to the final temperature at a determined rate of every minute), and the yield is as follows: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity higher than 97%4). And extruding to obtain 3X 3mm strip-shaped carriers.
(2)5％NiO-0.8％Au2O3-0.5％SeO2/NbAlO4Preparation of the catalyst
According to the content composition of the catalyst, the carrier is immersed into an aqueous solution containing 20.8g of nickel nitrate, 1.32g of gold nitrate and 0.62g of selenious acid by an isometric immersion method, is dried after adsorption equilibrium is achieved, and is roasted in the air at 400 ℃ for 12 hours to obtain a catalyst precursor of 5% NiO-0.8% Au2O3-0.5％SeO2/NbAlO4。
(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 98.8%, and the primary amine selectivity is 99.5%. The catalyst is continuously operated for 900h for sampling analysis, and the result is unchanged。
Example 4
(1) Preparation of carrier NbAlO from niobium oxalate4
301.3g niobium oxalate and 28.5g alumina were added to a mortar and mixed uniformly, and ground and sieved to obtain a mixture of 100 meshes and 200 meshes, and then the mixture was transferred to a crucible, dried at 130 ℃ for 16 hours, and then calcined in air at 1050 ℃ for 28 hours (rate of temperature rise: 5 ℃/min. Yield: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity of more than 99%4). Tabletting and forming to obtain 3X 3mm columnar carrier.
(2)6％NiO-1.4％Au2O3-0.4％SeO2/NbAlO4Preparation of the catalyst
According to the content composition of the catalyst, the carrier is immersed into an aqueous solution containing 25.3g of nickel nitrate, 2.35g of gold nitrate and 0.50g of selenious acid by an isometric immersion method, is dried after adsorption equilibrium is achieved, and is roasted for 9 hours in the air at 500 ℃ to obtain a catalyst precursor of 6% NiO-1.4% Au2O3-0.4％SeO2/NbAlO4。
(3) 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 100.0%, and the primary amine selectivity is 99.8%. The catalyst is continuously operated for 1200h, sampled and analyzed, and the result is unchanged.
Example 5
(1) Preparation of Carrier NbAlO from niobium sulfate4
186.4g of niobium sulfate and 28.5g of alumina were added to a mortar and mixed uniformlyUniformly mixing, grinding, sieving to obtain a mixture of 100-200 meshes, transferring the mixture into a crucible, drying at 110 ℃ for 20h, and calcining in air at 950 ℃ for 30h (the heating rate: 3 ℃/min. Yield: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity higher than 97%4). Tabletting and forming to obtain 3X 3mm columnar carrier.
(2)9％NiO-0.6％Au2O3-0.1％SeO2/NbAlO4Preparation of the catalyst
According to the content composition of the catalyst, the carrier is immersed into an aqueous solution containing 38.8g of nickel nitrate, 1.03g of gold nitrate and 0.13g of selenious acid by an isometric immersion method, is dried after adsorption equilibrium is achieved, and is roasted in air at 550 ℃ for 8 hours to obtain a catalyst precursor of 9% NiO-0.6% Au2O3-0.1％SeO2/NbAlO4。
(3) 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%. The catalyst is continuously operated for 1050h, sampled and analyzed, and the result is unchanged.
Comparative example 1
The difference from example 1 is that the catalyst is 19.9% Ni-7.6% Cu/theta-Al prepared according to the method of preparation of the catalyst in example XIX of patent US5352835A2O3A catalyst. After the catalyst is continuously operated for 500 hours, the activity is obviously reduced, the reaction conversion rate is 82 percent, and the primary amine selectivity is 97.0 percent. By X-ray derivative spectroscopy using the product of boehmite peak to theta-alumina peakThe rehydration degree of the alumina component was 30% by intensity estimation. The X-ray diffraction analysis of the catalyst after 1000h of continuous operation in example 1 shows that the catalyst support is still NbAlO with a purity of more than 98%4。
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.
Comparative example 2
7% NiO-1% Au was prepared according to the method of example 12O3-0.2％ZrO2/NbAlO4The catalyst was evaluated under the same process conditions as in example 1, and it was found that the activity of the catalyst was significantly reduced after the catalyst was continuously operated for 300 hours, the reaction conversion was 75%, and the primary amine selectivity was 95.5%. The metal dispersion degree is measured by adopting a pulse chemical adsorption method, and the result shows that the dispersion degree of metal Ni and Au is greatly reduced. And the result of pulse chemical adsorption analysis of the catalyst after 1000h of continuous operation in example 1 shows that the dispersion degree of Ni and Au in the catalyst is basically consistent with that of the fresh catalyst.
From the above, the catalyst SeO of the present invention2The introduction of (2) and the combination of a specific carrier increase the dispersion degree, the active surface area and the anti-sintering performance of Ni and Au in the catalyst, thereby improving the activity and the selectivity of the catalyst.
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 (12)

1. A catalyst for synthesizing polyetheramine, which comprises NbAlO4Carrier and NiO and Au supported on the carrier2O3And SeO2An active ingredient;
wherein the content of active component NiO in the catalyst is 1-15 wt%, and Au is calculated by the total weight of the catalyst2O3The content of (B) is 0.01-2 wt%, SeO2The content of (B) is 0.01-1 wt%.
2. The catalyst according to claim 1, wherein the content of the active component NiO is 5-10 wt% and Au is calculated by the total weight of the catalyst2O30.5-1.5 wt% of SeO2The content of (B) is 0.1-0.5 wt%.
3. A process for preparing the catalyst of claim 1 or 2, comprising the steps of:
(1) preparation of NbAlO4Carrier: uniformly mixing a niobium-containing compound and alumina, drying, roasting, forming to obtain a carrier, and optionally grinding and screening before drying;
(2) preparing a catalyst: according to the content composition of the catalyst, the carrier obtained in the step (1) is soaked in an aqueous solution containing soluble nickel salt, gold salt and selenium-containing compound, and after adsorption equilibrium, the carrier is dried and roasted to obtain the catalyst.
4. The method of claim 3, wherein the impregnation is an equal volume impregnation.
5. The production method according to claim 3, wherein the niobium-containing compound in the step (1) is one or more selected from the group consisting of niobium nitrate, niobium sulfate, niobium hydroxide, niobium oxalate and niobium carbonate;
the nickel salt in the step (2) is selected from one or more of sulfate, nitrate and organic acid salt;
the gold salt is selected from one or more of gold nitrate, gold chloride and chloroauric acid tetrahydrate;
the selenium-containing compound is one or more selected from selenious acid, sodium selenite, potassium selenite, and selenium oxychloride.
6. The production method according to claim 3, wherein the niobium-containing compound in the step (1) is selected from niobium hydroxide and/or niobium oxalate;
the nickel salt in the step (2) is selected from nitrate;
the gold salt is selected from gold nitrate;
the selenium-containing compound is selected from selenious acid.
7. The preparation method according to any one of claims 3 to 6, wherein the mesh number of the solid powder during the sieving in the step (1) is controlled within the range of 100-200 mesh.
8. The preparation method according to any one of claims 3 to 6, wherein the roasting temperature in the step (1) is 700-1500 ℃; the roasting time is 10-40 h;
the roasting temperature in the step (2) is 100-600 ℃, and the roasting time is 1-24 h.
9. The preparation method according to any one of claims 3 to 6, wherein the roasting temperature in the step (1) is 900-1100 ℃; the roasting time is 20-30 h;
the roasting temperature in the step (2) is 300-500 ℃, and the roasting time is 8-16 h.
10. Use of the catalyst according to claim 1 or 2 for the hydroamination of polyether polyols to give polyetheramines, which polyether polyols have an Ethylene Oxide (EO) and/or Propylene Oxide (PO) skeleton and an average molecular weight of 100-.
11. A method of synthesizing a polyetheramine, the method comprising: the polyether amine is synthesized by hydroamination of polyether polyol in the presence of the catalyst as set forth in claim 1 or 2.
12. The method as claimed in claim 11, 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.
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