CN112121812B - Catalyst for preparing propane diamine, preparation method of catalyst and method for preparing propane diamine - Google Patents
Catalyst for preparing propane diamine, preparation method of catalyst and method for preparing propane diamine Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Abstract
The invention discloses a catalyst for preparing propane diamine, a preparation method thereof and a method for preparing propane diamine. The catalyst comprises a guanidine compound modified gamma-Al 2O3 carrier as a carrier, and NiO, CuO and WO as active components3、Sb2O3And an auxiliary agent ThO2. The guanidine compound is preferably tetramethylguanidine and/or aminoguanidine. Based on the weight of the gamma-Al 2O3 carrier, the NiO content is 1-20 percent, the CuO content is 1-10 percent, and the WO content is30.1-5% of Sb2O3The content of which is 0.05 to 1 percent and the auxiliary agent ThO2The content is 0.05-1%. The molar ratio of the guanidine compound to the gamma-Al 2O3 is 0.01-1: 1, preferably 0.1 to 0.5: 1. the catalyst of the invention is used for reductive amination of propylene glycol to prepare propane diamine, and the propane diamine has high activity, high selectivity and high stability.
Description
Technical Field
The invention relates to the field of organic synthesis and catalysts, in particular to a method for preparing propane diamine by reductive amination of propylene glycol.
Background
The propane diamine includes 1, 2-propane diamine and 1, 3-propane diamine. The 1, 2-propane diamine is an organic chemical intermediate and a raw material with wide application, has important application in the fields of medicines, pesticides, organic synthesis, lubricating oil antirust agents, epoxy resin curing accelerators, spandex, modified shellac coatings and the like, and can be used as rubber, coatings, raw materials, chelating agents, mineral dressing agents and the like, and can be used for producing 1, 2-propane diamine tetraacetic acid as an intermediate of anticancer medicine propane imine. The 1, 3-propane diamine is low-grade aliphatic diamine, has active chemical property, can be widely used in the industries of medicine, pesticide, dye, petrochemical industry, semiconductor manufacturing, polymer and the like, and is an important fine organic chemical intermediate. With the development of society and science and technology, the application range of 1, 2-propane diamine and 1, 3-propane diamine is continuously expanded, and the market demand is increased year by year. But at present, domestic manufacturers do not produce the products in a large scale, so that the domestic products are few, the market demands are met mainly by means of imports, and the price is high.
The preparation method of 1, 2-propane diamine can be divided into two methods according to different raw materials, and one method is a 1, 2-dichloropropane ammonolysis method. The production process is briefly described as follows: adding 1, 2-dichloropropane and liquid ammonia into an anticorrosive kettle-type reactor, cooling to control the reaction temperature to be about 160 ℃, after the reaction is finished, feeding the material into a neutralizer, and neutralizing hydrogen chloride in the material by using sodium hydroxide solution. Because the propane diamine is not azeotropic with water, more than 98 percent of propane diamine can be obtained by rectification separation. The method has low yield, and the organic chloride seriously pollutes the environment. The other method is to take propylene oxide, 1, 2-propylene glycol, isopropanolamine, 1, 3-propylene glycol, acrolein and acrylonitrile as raw materials to react with ammonia or react with ammonia firstly and then hydrogenate.
The preparation method of the 1, 3-propane diamine mainly comprises a halogenated hydrocarbon ammonolysis method, a propylene glycol ammonolysis method and an acrylonitrile ammonolysis reduction method. The halohydrocarbon ammonolysis method is a kettle type intermittent reaction, has serious corrosion to equipment, more three wastes, larger raw material consumption, more polyamine byproducts and selectivity of 1, 3-propane diamine not more than 30 percent, causes difficult product separation and is gradually eliminated. The reaction product obtained by the propylene glycol ammonolysis method is a mixture of primary, secondary and tertiary amines, and 1, 3-propane diamine can be used as a main product by adopting different reaction conditions and selecting a proper catalyst. Although the process flow of the method is simple, the disadvantages of expensive nickel and cobalt catalysts, more side reactions, difficult product separation and the like limit the industrial application of the method. The acrylonitrile ammonification reduction method is mainly characterized in that acrylonitrile is firstly reacted with ammonia to prepare 3-aminopropionitrile, and then the 1, 3-propane diamine is obtained through catalytic reduction, two steps of reaction are needed in the method, two sets of reactors are needed, and one-time investment and production cost of a production device are increased.
CN102718661A discloses a joint preparation method of 1, 2-propanediamine and dimethylpiperazine, ammonia and isopropanolamine are mixed, preheated and vaporized, the mixture is introduced into a fixed bed reactor, the reaction is carried out in the presence of a condensation amination catalyst under the conditions of pressure of 1.0-4.0 MPa, temperature of 300-350 ℃ and contact time of 1.0-3.0 seconds, the product stream is 1, 2-propanediamine, 2, 5-dimethylpiperazine, 2, 6-dimethylpiperazine and unreacted ammonia and isopropanolamine, and the product stream is distilled and separated to obtain 1, 2-propanediamine, 2, 5-dimethylpiperazine and 2, 6-dimethylpiperazine; wherein the weight ratio of ammonia to isopropanolamine is 10-16: 1, the condensation amination catalyst comprises the following components in percentage by weight: the method is mainly used for preparing 1, 2-propane diamine and dimethyl piperazine, wherein the HZSM-5 accounts for 97-99%, and the phosphorus accounts for 1-3%. However, in the method, the catalyst adopts a weakly acidic HZSM-5 molecular sieve and contains phosphorus, so that the stability of the catalyst needs to be further improved, and the problem of phosphorus loss exists, which can cause certain environmental pollution.
CN101891628B discloses a preparation method of 1, 2-propane diamine, which comprises the steps of adding isopropanolamine, water, ammonia, hydrogen and a catalyst into a high-pressure reaction kettle, stirring at a high speed, and carrying out catalytic and amination reaction at 100-250 ℃ and 5-15 MPa to obtain a mixture with 1, 2-propane diamine as a main component, wherein the product selectivity is more than 80%. The method adopts a kettle type reactor, water is required to be added as a solvent, so that intermittent operation is required, the separation of the catalyst and the product in the subsequent separation of the product is complex, a large amount of water is required to be separated, and the complexity and the cost of the operation are increased.
CN104693038B discloses a preparation method of 1, 2-propane diamine, and the invention relates to a method for preparing propane diamine by taking propylene glycol and ammonia as raw materials. Mixing propylene glycol and liquid ammonia according to a certain proportion, pumping into a reactor by a pump, and reacting in the presence of a catalyst and hydrogen. The production process has the problems of low conversion rate of propylene glycol raw materials (the highest conversion rate is 89.10%), poor selectivity of the propylene diamine (the highest selectivity is 89.14%) and the like, and a large amount of byproducts such as isopropanolamine, dimethylpiperazine and the like exist in the propylene diamine, so that the separation energy consumption is greatly increased. Also, the patent does not mention the problem of catalyst life.
US5247120A adopts a tubular reactor, takes a molecular sieve as a catalyst, and reacts at 90 ℃ and 18MPa pressure, the conversion rate of acrylonitrile is 100 percent, and the content of 3-aminopropionitrile in reaction liquid can reach 90.6 percent. EP0630886A also adopts a tubular reactor, takes acidic cation exchange resin (Amberlyst15) as a catalyst, and reacts at 50 ℃ and 15MPa pressure, the conversion rate of acrylonitrile is more than 99 percent, and the content of 3-aminopropionitrile in reaction liquid can reach 81 percent. The two methods are operated by adopting a fixed bed tubular reactor, the process flow is simple, the continuous production can be realized, the conversion rate and the selectivity are higher, the product is easy to refine, but the process adopts acrylonitrile as the raw material, the molar ratio of liquid ammonia to acrylonitrile is too high, the waste is caused, and simultaneously, acrylonitrile has serious harm to the environment, can cause pollution to water bodies, and limits the further application of the acrylonitrile.
From the existing literature and technology, the production technology of propane diamine mostly has the defects of poor selectivity, difficult product separation, harsh reaction conditions, low yield, high raw material toxicity and the like. Therefore, the research and optimization of the synthesis process of the propane diamine can fill the domestic blank, break through the foreign technical blockade and patent protection, and have important significance for the large-scale industrial production of the propane diamine and the derivatives thereof.
Because the propylene glycol has less harm to the environment and human bodies, the propylene glycol becomes a green chemical product which is greatly worried and encouraged to develop in developed countries, and therefore, the preparation of the propylene diamine by taking the propylene glycol as the raw material is a relatively green and environment-friendly path. However, the process has the main problems of harsh reaction conditions, low propylene glycol raw material conversion rate, poor selectivity of propylene diamine and difficult large-scale continuous industrial production. A new process for the preparation of propylene diamine is needed.
Disclosure of Invention
The invention relates to a catalyst for preparing propane diamine and a preparation method thereof, wherein the catalyst has high activity, high selectivity and high stability; the invention also relates to a method for preparing the propane diamine by the propylene glycol, which inhibits the generation of deamination side reaction in the reductive amination process, thereby greatly improving the selectivity and the yield of the propane diamine.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a catalyst for preparing propane diamine has guanidine compound modified gamma-Al 2O3 as carrier and NiO, CuO and WO as active components3、Sb2O3And an auxiliary agent ThO2。
In the catalyst, the contents of the active components are as follows: the NiO content is 1 to 20 percent, preferably 5 to 15 percent, based on the weight of the gamma-Al 2O3 carrier;
the CuO content is 1 to 10%, preferably 3 to 8%;
WO3the content is 0.1-5%, preferably 0.5-3%;
Sb2O3the content is 0.05-1%, preferably 0.1-0.5%.
In the catalyst of the invention, the auxiliary agent ThO2In an amount of 0.05 to 1%, preferably 0.1 to 0.5%, based on the weight of the γ -Al2O3 support.
A method of preparing the catalyst of the present invention comprises the steps of: according to the proportion,
(1) and (3) loading of an auxiliary agent: impregnating gamma-Al 2O3 carrier with soluble thorium salt solution, preferably impregnating in equal volume, drying at 100-150 deg.C for 4-6h after impregnating for 2-10h, and calcining at 300-500 deg.C for 3-8h to obtain ThO2/γ-Al2O3；
(2) Modification of the carrier: ThO obtained in the step (1)2The gamma-Al 2O3 and guanidine compounds are kept for 1 to 6 hours at the temperature of 100-300 ℃ in an oxygen-free atmosphere, then are roasted for 1 to 12 hours at the temperature of 400-600 ℃ and are cooled to obtain ThO2Modified gamma-Al 2O 3;
(3) loading of active components: impregnating step (2) with a soluble metal salt solution to obtain ThO2The/modified gamma-Al 2O3 is preferably impregnated in equal volume, and is dried at the temperature of 100-150 ℃ for 4-6h after being impregnated for 2-10h, and is calcined at the temperature of 300-500 ℃ for 1-8h to obtain the catalyst.
The specific surface area of the gamma-Al 2O3 in the step (1) of the invention is 100-400m2G, preferably 180-270m2(ii)/g; pore volume is 0.5-2.5ml/g, preferably 0.8-1.6 ml/g; the shape of the alumina is strip, cylinder, clover, seven-hole sphere, gear or plum blossom, preferably clover.
In the step (2) of the present invention, the guanidine compound is one or more of tetramethylguanidine, bicyclic guanidine, diphenylguanidine, dodecaguanidine acetate, aminoguanidine carbonate, 2-aminobenzimidazole, guanidine sulfamate, metformin, and aminoguanidine, preferably one or more of tetramethylguanidine, aminoguanidine carbonate, 2-aminobenzimidazole, and aminoguanidine, and more preferably tetramethylguanidine and/or aminoguanidine.
In the step (2), the molar ratio of the gamma-Al 2O3 to the guanidine compound is 1: 0.01-1, preferably 1: 0.1-0.5.
The active component is derived from salts of corresponding metals, wherein the nickel salt comprises one or more of nickel nitrate, nickel acetate and nickel sulfate, preferably nickel nitrate; copper salts include, but are not limited to, one or more of copper nitrate, copper sulfate, preferably copper nitrate; tungsten salts include, but are not limited to, tungsten nitrate and/or ammonium metatungstate, preferably ammonium metatungstate; antimony salts include, but are not limited to, antimony acetate and/or antimony nitrate, preferably antimony nitrate.
The thorium salts described in the present invention include, but are not limited to, thorium nitrate and/or thorium sulfate, preferably thorium nitrate.
The catalyst has catalytic activity after being activated. The method for activating the catalyst comprises the following steps: the absolute reaction pressure is 3.0-15.0MPa, preferably 6.0-10.0 MPa; the hydrogen flow rate is 1-10L/min/L cat, preferably 3-7L/min/L cat; the activation temperature is 200-500 ℃, preferably 300-400 ℃ for 2-12h, preferably 4-10 h.
A method for preparing propylene diamine from propylene glycol comprises the following steps: in the presence of hydrogen, liquid ammonia and the catalyst, propylene glycol is subjected to reductive amination reaction to prepare propylene diamine.
The method for preparing the propylene diamine by using the propylene glycol preferably adopts a continuous fixed bed process.
The absolute reaction pressure of the method for preparing the propane diamine by using the propylene glycol is 3.0-15.0MPa, and preferably 6.0-10.0 MPa.
The reaction temperature of the method for preparing the propylene diamine from the propylene glycol is 150-250 ℃, and preferably 180-230 ℃.
According to the method for preparing propylene diamine from propylene glycol, the molar ratio of liquid ammonia to propylene glycol is 1: 1-15: 1, preferably 4: 1-10: 1.
according to the method for preparing the propylene diamine by using the propylene glycol, the molar ratio of hydrogen to the propylene glycol is 1-10: 1, preferably 2 to 6: 1.
the method for preparing the propylene diamine by the propylene glycol has the liquid volume space velocity of the propylene glycol of 1-15h-1Preferably 5-10h-1。
The propylene glycol of the invention is 1, 2-propylene glycol or 1, 3-propylene glycol.
The propane diamine is 1, 2-propane diamine or 1, 3-propane diamine.
The reaction process is illustrated by taking 1, 2-propanediol reductive amination to synthesize 1, 2-propane diamine as an example:
according to the reaction mechanism, 1, 2-propanediol to prepare 1, 2-propanediamine undergoes dehydrogenation, imidization and hydrogenation. For the main reaction, 1, 2-propylene glycol is dehydrogenated to generate 2-hydroxypropionaldehyde and 1-hydroxyacetone, the 2-hydroxypropionaldehyde and the 1-hydroxyacetone are subjected to imidization and hydrogenation reaction to generate 2-amino-1-propanol and 1-amino-2-propanol, and the 2-amino-1-propanol and the 1-amino-2-propanol are continuously subjected to dehydrogenation, imidization and hydrogenation to generate the target product 1, 2-propylene diamine. As a side reaction, 1, 2-propanediamine is deaminated to form 2, 5-dimethylpiperazine and 2, 6-dimethylpiperazine.
The invention surprisingly discovers that the guanidine compound modified gamma-Al 2O3 carrier and the catalyst with special combination are adopted to control the reaction processes of propylene glycol dehydrogenation, imidization and hydrogenation, and the generation of deamination side reaction in the amination process is inhibited, so that the selectivity and the yield of the propane diamine are greatly improved, the conversion rate of raw materials reaches 100%, and the yield of the propane diamine is more than 99%.
In the invention, guanidine compounds are used for surface modification of the alumina carrier loaded with Th, molecules can preferentially occupy the surface adsorption sites of the alumina carrier containing Th, and active metals Ni, Cu, W and Sb can be directionally anchored to the naked Th surface, so that Ni-Cu-W-Sb-Th can be better matched, a synergistic effect is generated, and the activity and selectivity of the catalyst are improved.
Meanwhile, the guanidine compound modifies the surface of the alumina carrier, improves the surface property of the alumina carrier, reduces the surface acidity of the catalyst, can greatly inhibit 1, 2-propanediamine from undergoing deamination reaction to generate secondary amine 2, 5-dimethylpiperazine and 2, 6-dimethylpiperazine byproducts, and further improves the product selectivity.
In addition, the catalyst of the invention can obviously improve the anti-sintering performance of the catalyst by adding the auxiliary agent Th element, and further improve the stability of the catalyst.
The catalyst of the invention has simple preparation method and mature process technology, and is beneficial to the industrial production of the catalyst.
The invention adopts the propylene glycol which is a green chemical product as a raw material to prepare the propane diamine, and the method overcomes the problems of harsh reaction conditions, low raw material conversion rate, poor product selectivity and high separation energy consumption in the prior art.
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
The sample inlet is 280 ℃, and the detector is 300 ℃; temperature rising procedure: keeping the temperature at 80 deg.C for 5min, and raising the temperature to 280 deg.C at 30 deg.C/min for 10 min.
1, 2-propylene glycol: purchased from dow chemistry.
γ-Al2O3: purchased in a Zibo Ziziruifeng factory with the specific surface area of 240m2Per gram, pore volume 1.2ml/g, clover shape.
The method for measuring the metal content in the catalyst comprises the following steps: the metal content was determined using an inductively coupled plasma spectrometer (ICP-AEC) model Optima 7300DV from Perkinelmer.
Example 1
(1)0.1％ThO2Preparation of/gamma-Al 2O3
100g of gamma-Al is added by an isovolumetric immersion method2O3Adding a solution containing 0.2g of Th (NO)3)4·6H2Soaking in 100ml O water solution for 4 hr, drying at 120 deg.C for 5.5 hr, and calcining at 400 deg.C for 5 hr to obtain 0.1% ThO2/γ-Al2O3。
(2)0.1％ThO2Preparation of modified gamma-Al 2O3
Subjecting the 0.1% ThO obtained in step (1)2Uniformly mixing gamma-Al 2O3 and 22.6g of tetramethylguanidine, heating the mixed material to 120 ℃ under the protection of an oxygen-free atmosphere, and keeping for 3 hours; heating to 400 deg.C, calcining for 8 hr, cooling to obtain 0.1% ThO2Modified gamma-Al 2O 3.
(3)15％NiO-3％CuO-0.5％WO3-0.1％Sb2O3-0.1％ThO2Preparation of modified gamma-Al 2O3 catalyst
Adopting an equal volume impregnation method to impregnate the 0.1 percent ThO obtained in the step (2)2Modified gamma-Al 2O3 containing 58.4g of Ni (NO)3)2·6H2O、9.11g Cu(NO3)2·3H2O、0.53g(NH4)6H2W12O40And 0.21g Sb (NO)3)3Is dipped in 100ml of aqueous solution of (1), dried at 130 ℃ for 4h and roasted at 300 ℃ for 6h to obtain 15 percent NiO-3 percent CuO-0.5 percent WO3-0.1％Sb2O3-0.1％ThO2Modified gamma-Al 2O3 catalyst.
(4) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process, 100ml of catalyst being charged in a fixed bed reactor. Activating with hydrogen at 6MPa and 4L/min/L at 300 deg.C for 4 h.
Reducing the reaction temperature of the fixed bed reactor to 180 ℃, maintaining the reaction pressure at 6MPa, and after the system is stable, in the condition that the space velocity of 1, 2-propylene glycol is 5.0L/h/L Cat, the molar ratio of hydrogen to 1, 2-propylene glycol is 2: the molar ratio of 1, liquid ammonia and 1, 2-propylene glycol is 10: 1, reacting. The reaction conversion was 100.0%, the yield of 1, 2-propanediamine was 99.6%, the yield of 2, 5-dimethylpiperazine was 0.1% and the yield of 2, 6-dimethylpiperazine was 0.3% by gas chromatography analysis.
Comparative example 1
γ-Al2O3The support was not modified, and the rest of the conditions were the same as in example 1.
(1)0.1％ThO2Preparation of/gamma-Al 2O3
100g of gamma-Al is added by an isovolumetric immersion method2O3Adding a solution containing 0.2g of Th (NO)3)4·6H2Soaking in 100ml O water solution for 4 hr, drying at 120 deg.C for 5.5 hr, and calcining at 400 deg.C for 5 hr to obtain 0.1% ThO2/γ-Al2O3。
(2)15％NiO-3％CuO-0.5％WO3-0.1％Sb2O3-0.1％ThO2Preparation of/gamma-Al 2O3 catalyst
Adopting an equal volume impregnation method to impregnate the 0.1 percent ThO obtained in the step (1)2The/. gamma. -Al2O3 was charged with a solution containing 58.4g of Ni (NO)3)2·6H2O、9.11g Cu(NO3)2·3H2O、0.53g(NH4)6H2W12O40And 0.21g Sb (NO)3)3Is dipped in 100ml of aqueous solution of (1), dried at 130 ℃ for 4h and roasted at 300 ℃ for 6h to obtain 15 percent NiO-3 percent CuO-0.5 percent WO3-0.1％Sb2O3-0.1％ThO2The catalyst is/gamma-Al 2O 3.
(3) Evaluation of catalyst
The reaction conversion was 100.0%, the yield of 1, 2-propanediamine was 93.0%, the yield of 2, 5-dimethylpiperazine was 4.0% and the yield of 2, 6-dimethylpiperazine was 3.0% by gas chromatography analysis.
Comparative example 2
Unsupported adjuvant ThO2The other conditions were the same as in example 1.
(1) Modification of gamma-Al 2O3 support
Uniformly mixing 100g of gamma-Al 2O3 and 22.6g of tetramethylguanidine, heating the mixed material to 120 ℃ under the protection of an oxygen-free atmosphere, and keeping for 3 hours; heating to 400 ℃, roasting and activating for 8h, cooling and cooling to obtain the modified gamma-Al 2O3 carrier.
(2)15％NiO-3％CuO-0.5％WO3-0.1％Sb2O3Preparation of modified gamma-Al 2O3 catalyst
Adding the modified gamma-Al 2O3 obtained in the step (1) into a catalyst containing 58.4g of Ni (NO) by adopting an equal-volume impregnation method3)2·6H2O、9.11g Cu(NO3)2·3H2O、0.53g(NH4)6H2W12O40And 0.21g Sb (NO)3)3Is dipped in 100ml of aqueous solution of (1), dried at 130 ℃ for 4h and roasted at 300 ℃ for 6h to obtain 15 percent NiO-3 percent CuO-0.5 percent WO3-0.1％Sb2O3Modified gamma-Al 2O3 catalyst.
(3) Evaluation of catalyst
By gas chromatography analysis, the reaction conversion was 93.0%, the yield of 1, 2-propanediamine was 90.0%, the yield of 2, 5-dimethylpiperazine was 1.6%, and the yield of 2, 6-dimethylpiperazine was 1.4%. After 50 hours of operation, the reaction conversion was 60.0%, the yield of 1, 2-propanediamine was 51.2%, the yield of 2, 5-dimethylpiperazine was 5.6%, and the yield of 2, 6-dimethylpiperazine was 3.2%.
Comparative example 3
Firstly carrying out gamma-Al 2O3 carrier modification and then carrying out auxiliary agent ThO2The loading and other conditions were the same as in example 1.
(1) Modification of gamma-Al 2O3 support
Uniformly mixing 100g of gamma-Al 2O3 and 22.6g of tetramethylguanidine, heating the mixed material to 120 ℃ under the protection of an oxygen-free atmosphere, and keeping for 3 hours; heating to 400 ℃, roasting and activating for 8h, cooling and cooling to obtain the modified gamma-Al 2O3 carrier.
(2)0.1％ThO2Preparation of modified gamma-Al 2O3
Adopting an isometric immersion method to carry out the modification on the gamma-Al obtained in the step (1)2O3Adding a solution containing 0.2g of Th (NO)3)4·6H2Soaking in 100ml O water solution for 4 hr, drying at 120 deg.C for 5.5 hr, and calcining at 400 deg.C for 5 hr to obtain 0.1% ThO2Modified gamma-Al 2O 3.
(3) Evaluation of catalyst
By gas chromatography analysis, the reaction conversion was 95.0%, the yield of 1, 2-propanediamine was 94.0%, the yield of 2, 5-dimethylpiperazine was 0.5%, and the yield of 2, 6-dimethylpiperazine was 0.5%.
Comparative example 4
Unloaded WO3And Sb2O3The other conditions were the same as in example 1.
(1)15％NiO-3％CuO-0.1％ThO2Preparation of modified gamma-Al 2O3 catalyst
By the same volume immersion method, 0.1% ThO is added2Modified gamma-Al 2O3 containing 58.4g of Ni (NO)3)2·6H2O and 9.11g Cu (NO)3)2·3H2Soaking in 100ml O water solution for 4 hr, drying at 130 deg.C for 4 hr, and calcining at 300 deg.C for 6 hr to obtain 15% NiO-3% CuO-0.1% ThO2Modified gamma-Al 2O3 catalyst.
(2) Evaluation of catalyst
The reaction conversion was 89.6%, the yield of 1, 2-propanediamine was 80.0%, the yield of 2, 5-dimethylpiperazine was 5.4%, and the yield of 2, 6-dimethylpiperazine was 4.2% by gas chromatography analysis.
Comparative example 5
Unloaded Sb2O3The other conditions were the same as in example 1.
(1)15％NiO-3％CuO-0.5％WO3-0.1％ThO2Preparation of modified gamma-Al 2O3 catalyst
By the same volume immersion method, 0.1% ThO is added2Modified gamma-Al 2O3 containing 58.4g of Ni (NO)3)2·6H2O、9.11g Cu(NO3)2·3H2O and 0.53g (NH)4)6H2W12O40Is dipped in 100ml of aqueous solution of (1), dried at 130 ℃ for 4h and roasted at 300 ℃ for 6h to obtain 15 percent NiO-3 percent CuO-0.5 percent WO3-0.1％ThO2Modified gamma-Al 2O3 catalyst.
(2) Evaluation of catalyst
By gas chromatography analysis, the reaction conversion was 96.1%, the yield of 1, 2-propanediamine was 90.0%, the yield of 2, 5-dimethylpiperazine was 2.4%, and the yield of 2, 6-dimethylpiperazine was 3.7%.
Comparative example 6
Unloaded WO3The other conditions were the same as in example 1.
(1)15％NiO-3％CuO-0.1％Sb2O3-0.1％ThO2Preparation of modified gamma-Al 2O3 catalyst
By the same volume immersion method, 0.1% ThO is added2Modified gamma-Al 2O3 containing 58.4g of Ni (NO)3)2·6H2O、9.11g Cu(NO3)2·3H2O and 0.21g Sb (NO)3)3Is dipped in 100ml of aqueous solution of NiO for 4 hours, dried at 130 ℃ for 4 hours and roasted at 300 ℃ for 6 hours to obtain 15 percent of NiO-3 percent of CuO-0.1 percent of Sb2O3-0.1％ThO2Modified gamma-Al 2O3 catalyst.
(2) Evaluation of catalyst
Through gas chromatography analysis, the reaction conversion rate was 91.5%, the yield of 1, 2-propanediamine was 91.0%, the yield of 2, 5-dimethylpiperazine was 0.2%, and the yield of 2, 6-dimethylpiperazine was 0.3%.
Comparative example 7
The same procedure as in example 1 was repeated except that the support γ -Al2O3 was modified with ethylenediamine.
(1)0.1％ThO2Preparation of modified gamma-Al 2O3
0.1% ThO2Uniformly mixing gamma-Al 2O3 and 11.8g of ethylenediamine, heating the mixed material to 120 ℃ in an oxygen-free atmosphere, and keeping for 3 hours; heating to 400 deg.C, calcining for 8 hr, cooling to obtain 0.1% ThO2Modified gamma-Al 2O 3.
(2) Evaluation of catalyst
The reaction conversion was 100.0%, the yield of 1, 2-propanediamine was 90%, the yield of 2, 5-dimethylpiperazine was 4.1% and the yield of 2, 6-dimethylpiperazine was 5.9% by gas chromatography analysis.
Example 2
(1)0.2％ThO2Preparation of/gamma-Al 2O3
100g of gamma-Al is added by an isovolumetric immersion method2O3Adding a solution containing 0.4g of Th (NO)3)4·6H2Soaking in 100ml water solution of O for 2 hr, drying at 130 deg.C for 5 hr, and calcining at 300 deg.C for 6 hr to obtainTo 0.2% ThO2/γ-Al2O3。
(2)0.2％ThO2Preparation of modified gamma-Al 2O3
According to a molar ratio of 1: 0.5 ratio of 0.2% ThO obtained in step (1)2Uniformly mixing the/gamma-Al 2O3 and 36.3g of aminoguanidine, heating the mixed material to 150 ℃ under the protection of an oxygen-free atmosphere, and keeping for 4 hours; heating to 450 deg.C, calcining for 10 hr, cooling to obtain 0.2% ThO2Modified gamma-Al 2O 3.
(3)12％NiO-5％CuO-1.0％WO3-0.2％Sb2O3-0.2％ThO2Preparation of modified gamma-Al 2O3 catalyst
Adopting an equal volume impregnation method to impregnate the 0.2 percent ThO obtained in the step (2)2Modified gamma-Al 2O3 containing 46.7g of Ni (NO)3)2·6H2O、15.18g Cu(NO3)2·3H2O、1.06g(NH4)6H2W12O40And 0.42g Sb (NO)3)3Is immersed in 100ml of aqueous solution for 5 hours, dried at 120 ℃ for 5 hours, and calcined at 350 ℃ for 4 hours to obtain 12% NiO-5% CuO-1.0% WO3-0.2％Sb2O3-0.2％ThO2Modified gamma-Al 2O3 catalyst.
(4) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process, 100ml of catalyst being charged in a fixed bed reactor. Activating with hydrogen at 7MPa and 6L/min/L at 400 deg.C for 5 h.
Reducing the reaction temperature of the fixed bed reactor to 190 ℃, maintaining the reaction pressure at 7MPa, and after the system is stable, in the condition that the space velocity of 1, 2-propylene glycol is 6.0L/h/L Cat, the molar ratio of hydrogen to 1, 2-propylene glycol is 3: the molar ratio of 1, liquid ammonia and 1, 2-propylene glycol is 9: 1, reacting. Through gas chromatography analysis, the reaction conversion rate was 100.0%, the yield of 1, 2-propanediamine was 99.5%, the yield of 2, 5-dimethylpiperazine was 0.3%, and the yield of 2, 6-dimethylpiperazine was 0.2%.
Example 3
(1)0.3％ThO2Preparation of/gamma-Al 2O3
100g of gamma-Al is added by an isovolumetric immersion method2O3Adding a solution containing 0.61g of Th (NO)3)4·6H2Soaking in 100ml O water solution for 6 hr, drying at 140 deg.C for 4 hr, and calcining at 350 deg.C for 4 hr to obtain 0.3% ThO2/γ-Al2O3。
(2)0.3％ThO2Preparation of modified gamma-Al 2O3
Subjecting the 0.3% ThO obtained in step (1)2Uniformly mixing the/gamma-Al 2O3 and 13.3g of aminoguanidine carbonate, heating the mixed material to 300 ℃ under the protection of an oxygen-free atmosphere, and keeping the temperature for 1 hour; heating to 500 deg.C, calcining for 6 hr, cooling to obtain 0.3% ThO2Modified gamma-Al 2O 3.
(3)9％NiO-6％CuO-1.5％WO3-0.3％Sb2O3-0.3％ThO2Preparation of modified gamma-Al 2O3 catalyst
Adopting an equal volume impregnation method to impregnate the 0.3 percent ThO obtained in the step (2)2Modified gamma-Al 2O3 containing 35.0g of Ni (NO)3)2·6H2O、18.22g Cu(NO3)2·3H2O、1.59g(NH4)6H2W12O40And 0.63g Sb (NO)3)3Is immersed in 100ml of aqueous solution for 6 hours, dried at 110 ℃ for 6 hours, and calcined at 500 ℃ for 2 hours to obtain 9% NiO-6% CuO-1.5% WO3-0.3％Sb2O3-0.3％ThO2Modified gamma-Al 2O3 catalyst.
(4) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process, 100ml of catalyst being charged in a fixed bed reactor. Activating with hydrogen at activation pressure of 8MPa and hydrogen flow rate of 7L/min/L at 350 deg.C for 6 h.
Reducing the reaction temperature of the fixed bed reactor to 200 ℃, maintaining the reaction pressure at 8MPa, and after the system is stable, in the condition that the space velocity of 1, 2-propylene glycol is 7.0L/h/L Cat, the molar ratio of hydrogen to 1, 2-propylene glycol is 4: 1, the molar ratio of liquid ammonia to 1, 2-propanediol is 8: 1, reacting. The reaction conversion was 100.0%, the yield of 1, 2-propanediamine was 99.8%, the yield of 2, 5-dimethylpiperazine was 0.1% and the yield of 2, 6-dimethylpiperazine was 0.1% by gas chromatography analysis.
Example 4
(1)0.4％ThO2Preparation of/gamma-Al 2O3
100g of gamma-Al is added by an isovolumetric immersion method2O3Adding a solution containing 0.81g of Th (NO)3)4·6H2Soaking in 100ml O water solution for 8 hr, drying at 100 deg.C for 6 hr, and calcining at 500 deg.C for 8 hr to obtain 0.4% ThO2/γ-Al2O3。
(2)0.4％ThO2Preparation of modified gamma-Al 2O3
Subjecting the 0.4% ThO obtained in step (1)2Uniformly mixing the/gamma-Al 2O3 and 39.2g of 2-aminobenzimidazole, heating the mixed material to 250 ℃ under the protection of an oxygen-free atmosphere, and keeping for 2 hours; heating to 550 deg.C, calcining for 4 hr, cooling to obtain 0.4% ThO2Modified gamma-Al 2O 3.
(3)7％NiO-7％CuO-2％WO3-0.4％Sb2O3-0.4％ThO2Preparation of modified gamma-Al 2O3 catalyst
Adopting an equal volume impregnation method to impregnate the 0.4 percent ThO obtained in the step (2)2Modified gamma-Al 2O3 containing 27.3g of Ni (NO)3)2·6H2O、21.26g Cu(NO3)2·3H2O、2.13g(NH4)6H2W12O40And 0.84g Sb (NO)3)3Is dipped in 100ml of aqueous solution of (1), dried at 100 ℃ for 4.5h, and roasted at 450 ℃ for 8h to obtain 7% NiO-7% CuO-2% WO3-0.4％Sb2O3-0.4％ThO2Modified gamma-Al 2O3 catalyst.
(4) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process, 100ml of catalyst being charged in a fixed bed reactor. Activating with hydrogen at activation pressure of 9MPa and hydrogen flow rate of 5L/min/L at activation temperature of 450 deg.C for 8 h.
Reducing the reaction temperature of the fixed bed reactor to 210 ℃, maintaining the reaction pressure at 9MPa, and after the system is stable, at the space velocity of 1, 2-propylene glycol of 8.0L/h/L Cat, the molar ratio of hydrogen to 1, 2-propylene glycol is 5: 1, the molar ratio of liquid ammonia to 1, 2-propanediol is 7: 1, reacting. Through gas chromatography analysis, the reaction conversion rate was 100.0%, the yield of 1, 2-propanediamine was 99.6%, the yield of 2, 5-dimethylpiperazine was 0.2%, and the yield of 2, 6-dimethylpiperazine was 0.2%.
Example 5
(1)0.5％ThO2Preparation of/gamma-Al 2O3
100g of gamma-Al is added by an isovolumetric immersion method2O3Adding a solution containing 1.01g of Th (NO)3)4·6H2Soaking O in 100ml water solution for 10 hr, drying at 150 deg.C for 4 hr, and calcining at 450 deg.C for 7 hr to obtain 0.5% ThO2/γ-Al2O3。
(2)0.5％ThO2Preparation of modified gamma-Al 2O3
Subjecting the 0.5% ThO obtained in step (1)2Uniformly mixing gamma-Al 2O3 and 45.2g of tetramethylguanidine, heating the mixed material to 100 ℃ under the protection of an oxygen-free atmosphere, and keeping for 6 hours; heating to 600 deg.C, calcining for 2 hr, cooling to obtain 0.5% ThO2Modified gamma-Al 2O 3.
(3)5％NiO-8％CuO-2.5％WO3-0.5％Sb2O3-0.5％ThO2Preparation of modified gamma-Al 2O3 catalyst
Adopting an equal volume impregnation method to impregnate the 0.5 percent ThO obtained in the step (2)2Modified gamma-Al 2O3 containing 19.5g of Ni (NO)3)2·6H2O、24.29g Cu(NO3)2·3H2O、2.66g(NH4)6H2W12O40And 1.06g Sb (NO)3)3Is soaked in 100ml of aqueous solution for 10 hours, dried at 150 ℃ for 5.5 hours and roasted at 400 ℃ for 5 hours to obtain 5 percent NiO-8 percent CuO-2.5 percent WO3-0.5％Sb2O3-0.5％ThO2Modified gamma-Al 2O3 catalyst.
(4) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process, 100ml of catalyst being charged in a fixed bed reactor. Activating with hydrogen at 10MPa and 3L/min/L at 500 deg.C for 7 h.
Reducing the reaction temperature of the fixed bed reactor to 220 ℃, maintaining the reaction pressure at 10MPa, and after the system is stable, in the condition that the space velocity of 1, 2-propylene glycol is 9.0L/h/L Cat, the molar ratio of hydrogen to 1, 2-propylene glycol is 6: the molar ratio of 1, liquid ammonia and 1, 2-propylene glycol is 6: 1, reacting. By gas chromatography analysis, the reaction conversion was 100.0%, the yield of 1, 2-propanediamine was 99.7%, the yield of 2, 5-dimethylpiperazine was 0.2%, and the yield of 2, 6-dimethylpiperazine was 0.1%.
Example 6
(1)0.05％ThO2Preparation of/gamma-Al 2O3
100g of gamma-Al is added by an isovolumetric immersion method2O3Adding a solution containing 0.1g of Th (NO)3)4·6H2Soaking in 100ml O water solution for 5 hr, drying at 125 deg.C for 4.5 hr, and calcining at 400 deg.C for 3 hr to obtain 0.05% ThO2/γ-Al2O3。
(2)0.05％ThO2Preparation of modified gamma-Al 2O3
0.05 percent ThO obtained in the step (1)2Uniformly mixing the/gamma-Al 2O3 and 72.6g of aminoguanidine, heating the mixed material to 200 ℃ under the protection of an oxygen-free atmosphere, and keeping for 5 hours; heating to 400 deg.C, calcining for 4 hr, cooling to obtain 0.05% ThO2Modified gamma-Al 2O 3.
(3)20％NiO-1％CuO-3％WO3-1％Sb2O3-0.05％ThO2Preparation of modified gamma-Al 2O3 catalyst
Adopting an equal volume impregnation method to impregnate the 0.05 percent ThO obtained in the step (2)2Modified gamma-Al 2O3 containing 77.9g of Ni (NO)3)2·6H2O、3.04g Cu(NO3)2·3H2O、3.19g(NH4)6H2W12O40And 2.11g Sb (NO)3)3Is soaked in 100ml of aqueous solution for 2 hours, dried at 140 ℃ for 4 hours and roasted at 500 ℃ for 1 hour to obtain 20 percent NiO-1 percent CuO-3 percent WO3-1％Sb2O3-0.05％ThO2Modified gamma-Al 2O3 catalyst.
(4) Evaluation of catalyst
The catalyst evaluation was carried out by a continuous fixed bed process, 100ml of catalyst being charged in a fixed bed reactor. Activating with hydrogen at 12MPa and 8L/min/L at 400 deg.C for 10 h.
Reducing the reaction temperature of the fixed bed reactor to 230 ℃, maintaining the reaction pressure at 12MPa, and after the system is stable, at the space velocity of 1, 3-propylene glycol of 10.0L/h/L Cat, the molar ratio of hydrogen to 1, 3-propylene glycol is 8: 1, the molar ratio of liquid ammonia to 1, 3-propanediol is 4: 1, reacting. Through gas chromatographic analysis, the reaction conversion rate is 100.0 percent, the yield of the 1, 3-propane diamine is 99.5 percent, and N is1The yield of the (3-aminopropyl) propane-1, 3-propanediamine was 0.5%.
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. Catalyst for preparing propane diamine, carrier of which is gamma-Al modified by guanidine compound2O3Carrier, active components including NiO, CuO and WO3、Sb2O3And an auxiliary agent ThO2(ii) a The guanidine compound is one or more of tetramethylguanidine, bicyclic guanidine, diphenylguanidine, dodecaguanidine acetate, aminoguanidine carbonate, 2-aminobenzimidazole, guanidine sulfamate, metformin and aminoguanidine; the preparation method of the catalyst comprises the following steps: according to the proportion,
(1) and (3) loading of an auxiliary agent: impregnation of gamma-Al with soluble thorium salt solutions2O3Drying and roasting the carrier to obtain ThO2/γ-Al2O3；
(2) Modification of the carrier: ThO obtained in the step (1)2/γ-Al2O3Keeping with guanidine compounds for 1-6h at 100-300 ℃ in an oxygen-free atmosphere, and then roasting for 1-12h at 400-600 ℃ to obtain ThO2Modified gamma-Al2O3；
(3) Loading of active components: impregnating step (2) with a soluble metal salt solution to obtain ThO2Modified gamma-Al2O3Drying and roasting to obtain the catalyst.
2. The catalyst according to claim 1, wherein the impregnation in step (1) is an equal volume impregnation and the impregnation in step (3) is an equal volume impregnation.
3. The catalyst of claim 1, wherein the guanidine compound is reacted with γ -Al2O3In a molar ratio of 0.01 to 1: 1.
4. the catalyst of claim 1, wherein the guanidine compound is reacted with γ -Al2O3In a molar ratio of 0.1 to 0.5: 1.
5. the catalyst according to claim 1, characterized in that the active components are present in a content of: based on gamma-Al2O3The weight of the carrier is calculated,
the NiO content is 1-20%;
the CuO content is 1-10%;
WO3the content is 0.1-5%;
Sb2O3the content is 0.05-1%.
6. The catalyst according to claim 1, characterized in that the active components are present in a content of: based on gamma-Al2O3The weight of the carrier is calculated,
the NiO content is 5-15%;
the CuO content is 3-8%;
WO3the content is 0.5-3%;
Sb2O3the content is 0.1-0.5%.
7. Catalyst according to claim 1, characterized in that the promoter ThO2In an amount of 0.05-1% based on gamma-Al2O3Weight of carrier.
8. Catalyst according to claim 1, characterized in that the promoter ThO2In an amount of 0.1-0.5% based on gamma-Al2O3Weight of carrier.
9. The catalyst according to claim 1, wherein in the step (1), the impregnation time is 2-10h, the calcination temperature is 300-500 ℃, and the calcination time is 3-8 h; and/or, in the step (3), the dipping time is 2-10h, the roasting temperature is 300-500 ℃, and the roasting time is 1-8 h.
10. The catalyst of claim 1, wherein the guanidine compound is reacted with γ -Al2O3In a molar ratio of 0.01 to 1: 1.
11. the catalyst of claim 1, wherein the guanidine compound is reacted with γ -Al2O3In a molar ratio of 0.1 to 0.5: 1.
12. a method for preparing propylene diamine from propylene glycol comprises the following steps: preparing propylene diamine by reductive amination of propylene glycol in the presence of hydrogen, liquid ammonia and a catalyst according to any one of claims 1 to 11; the propylene glycol is 1, 2-propylene glycol and/or 1, 3-propylene glycol.
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