CN111151256B - Catalyst for synthesizing hexamethylene diamine - Google Patents
Catalyst for synthesizing hexamethylene diamine Download PDFInfo
- Publication number
- CN111151256B CN111151256B CN202010064037.6A CN202010064037A CN111151256B CN 111151256 B CN111151256 B CN 111151256B CN 202010064037 A CN202010064037 A CN 202010064037A CN 111151256 B CN111151256 B CN 111151256B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hexamethylene diamine
- carrier
- hexanediol
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a catalyst for synthesizing hexamethylene diamine, and belongs to the field of chemical synthesis. The catalyst for synthesizing hexamethylene diamine consists of three parts, namely an active component, an auxiliary agent and a carrier; the active component is one or two of Ni or Co; the auxiliary agent is one or more of Pd, pt, re, ru, cr, B, cu and Na; the carrier is one or more of aluminum oxide, silicon oxide and silicon-aluminum oxide which are subjected to alkali treatment. On the basis of the prior art, the catalyst carrier is subjected to alkali treatment in advance, so that the catalytic effect of the catalyst is obviously enhanced. The catalyst is used for amination preparation of hexamethylene diamine under the condition of hexamethylene glycol hydrogenation, and obviously improves the conversion rate of hexamethylene diamine and the selectivity of hexamethylene diamine.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a catalyst for synthesizing hexamethylene diamine.
Background
The hexamethylene diamine is an important chemical raw material, can be used for producing nylon 66 salt through neutralization reaction with adipic acid, can be used for further producing nylon 66, can be used as an epoxy resin curing agent and a crosslinking agent, and is an unobtainable intermediate of synthetic materials. With the increase of the industrial level, the demand of engineering materials is continuously increased, and the demand of hexamethylene diamine materials is also increased worldwide.
Currently, the worldwide production capacity of hexanediamine is about 200 ten thousand tons/year, and the hexanediamine is mainly concentrated in western countries such as the United states, germany and the like. The domestic capacity is limited, and international oligopolistic production companies are often in short supply due to 'insufficiency' factors, which seriously influences the development of the synthetic fiber industry in China.
The prior methods for synthesizing hexamethylene diamine mainly comprise an adiponitrile catalytic hydrogenation method, a adipic acid method, a caprolactam method, a hexanediol method and the like. The adiponitrile catalytic hydrogenation method is the most important method for producing hexamethylene diamine internationally at present, and has two realization ways, namely a high-pressure method and a low-pressure method, wherein the high-pressure method mainly adopts an iron system and a cobalt-copper system, although the conversion rate can reach more than 95 percent, the pressure needs to be more than 30MPa or even 60MPa, the requirement on equipment is extremely high, and the method is adopted by DuPont company in the United states at present; the low pressure method uses Raney nickel as main catalyst, the preparation method of the catalyst is to use aluminum nickel to make alloy, then use alkali dissolving method to remove part of aluminum for activation, the method has the advantages of relatively mild conditions, the national Henan Shenma group and the Liaoning petrochemical company introduced the set of technology from abroad to carry out localization, but the method has some defects, such as the safety and stability problems of Raney nickel catalyst, the supply problem of adiponitrile raw material, etc. The adipic acid method is to produce adiponitrile by aminating adipic acid with ammonia and dehydrating, and to produce hexamethylenediamine by hydrogenating adiponitrile. The caprolactam method is to produce 6-aminocapronitrile by amination of caprolactam and ammonia under the condition of catalysis of phosphate, and 6-aminocapronitrile is hydrogenated again to generate hexamethylene diamine, the key step of the method is amination of caprolactam, small-scale application is obtained in some by-product caprolactam companies, and with surplus of domestic caprolactam capacity, the production cost of caprolactam is expected to be reduced, and the method is expected to be popularized again. The hexanediol method is a more ideal production technology of hexamethylenediamine, and takes hexanediol or amino hexanol as raw material to carry out amination reaction with ammonia under the action of a nickel-based catalyst to produce the hexamethylenediamine. However, the hexanediol method has a problem that it is difficult to obtain high-purity hexamethylenediamine with a large amount of by-products, and therefore, the development of a catalyst having high activity and high selectivity is a key problem of this technique.
CN106810454A discloses a method for preparing hexamethylene diamine from hexylene glycol or aminohexanol or a mixture of hexylene glycol and aminohexanol, wherein the catalyst uses one or two of Ni or Co as active component, and one or two additives are added and supported on a carrier composed of one or two of SiO2 or Al2O 3. The catalyst has a great improvement on the conversion rate of the hexanediol to synthesize the hexamethylenediamine, but the conversion rate of the hexanediol and the selectivity of the hexamethylenediamine still need to be further improved under the conditions of lower temperature (160 ℃) and lower pressure (8 MPa).
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a catalyst for synthesizing hexamethylene diamine.
The technical scheme of the invention is as follows:
a catalyst for synthesizing hexamethylene diamine comprises an active component, an auxiliary agent and a carrier; the active component is one or two of Ni or Co; the auxiliary agent is one or more of Pd, pt, re, ru, cr, B, cu and Na; the carrier is one or more of aluminum oxide, silicon oxide and silicon-aluminum oxide which are subjected to alkali treatment.
Compared with the Chinese patent with the application publication number of CN106810454A, the catalyst of the invention has the advantages that the carrier is treated by alkali in advance; in addition, a plurality of auxiliary agents are added; after the carrier is subjected to alkali treatment in advance, the conversion rate of the reaction and the selectivity of the hexamethylene diamine are both remarkably improved.
Preferably, the alkali is prepared into an aqueous solution with the mass percentage of 2-10%, the carrier is placed in an alkali liquor, the soaking treatment is carried out for 1-10 h at the temperature of 50-200 ℃, the washing is carried out until the eluate is neutral, and the baking is carried out for 2-10 h at the temperature of 300-800 ℃ after the drying. The treatment method is adopted to treat the carrier, so that the internal structure of the carrier is changed, and the catalytic effect is enhanced; after the carrier subjected to alkali treatment is loaded with effective components and the carrier, the conversion rate of hexanediol and the selectivity of hexamethylene diamine are effectively promoted.
The preparation process of the catalyst comprises the following steps: the carrier is subjected to alkali treatment in advance; the active component metal salt and the auxiliary component metal salt are prepared into aqueous solution with a certain concentration, the active component and the auxiliary are loaded on the carrier by an equal-volume impregnation method, and if the loading amount is larger, the active component and the auxiliary can be loaded by a plurality of times of impregnation methods.
Preferably, the alkali is one or more of sodium hydroxide, ethylenediamine and sodium bicarbonate.
As a preferred scheme, the active component accounts for 5-40% of the total mass of the catalyst.
As a preferred scheme, the auxiliary agent accounts for 1-10% of the total mass of the catalyst.
Preferably, the auxiliary agent is one or more of Pd, re, cr and B.
The catalyst is used for catalyzing the amination of hexanediol under the hydrogen condition to prepare the hexamethylene diamine: the activated catalyst is filled in a trickle bed or fixed bed reactor, and hexanediol and ammonia are used as reactants to prepare hexanediamine under the conditions of temperature of 100 to 200 ℃, pressure of 5 to 13MPa and hydrogen atmosphere; the ammonia-alcohol ratio is 2 to 20, and the hydrogen mole fraction is 1 to 30%. The modified catalyst of the invention catalyzes hexanediol to prepare hexamethylene diamine through amination under the hydrogen condition, and higher conversion rate and hexamethylene diamine yield can be obtained under the conditions of lower temperature and lower pressure. Excessive pressure is not needed, the requirement on equipment is reduced, and the equipment cost is reduced.
Preferably, the hexanediol and liquid ammonia are pumped into a trickle bed or fixed bed reactor using a high pressure pump.
Preferably, the activation temperature of the catalyst is 200 to 600 ℃, the pressure is 0.3 to 3MPa, and the space velocity is 100 to 2500h -1 。
The invention has the beneficial effects that:
on the basis of the prior art, the catalyst carrier is subjected to alkali treatment in advance, so that the catalytic effect of the catalyst is obviously enhanced. The catalyst is used for amination preparation of hexamethylene diamine under the condition of hexamethylene glycol hydrogenation, and obviously improves the conversion rate of hexamethylene diamine and the selectivity of hexamethylene diamine.
Detailed Description
The present invention will be described in detail with reference to specific examples.
1. The alkali treatment process of the carrier comprises the following steps:
100g of carrier and 1L 2-10 wt% of aqueous alkali are put into a reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is placed in a constant-temperature oven at 50-200 ℃ for standing treatment for 1-10h, the reaction kettle is washed by deionized water after being cooled until the eluate is neutral, the reaction kettle is dried in the constant-temperature oven at 120 ℃, and finally the reaction kettle is roasted for 6h at 500 ℃. The treatment result is marked as X-M-T-N (X represents the alkali source used, M represents the alkali solution concentration, T represents the standing treatment temperature, and N represents the treatment time), and NaOH-5-150-6 represents that sodium hydroxide with the alkali source accounting for 5 percent of the mass fraction is used for treatment at 150 ℃ for 6h.
2. Preparation of the catalyst
Example 1:
15%Ni-5%Co-3%Cu-2%B/Al 2 O 3 preparation of the catalyst
100g of the alumina support subjected to alkali treatment (NaOH-5 to 150-6) was dissolved in 300ml of water with 74.2g of nickel nitrate hexahydrate, 24.8g of cobalt nitrate hexahydrate, 11.3g of copper nitrate trihydrate and 11.4g of boric acid at 50 ℃ to prepare a solution. And uniformly adding half of the impregnation liquid into an alumina carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 2
15%Co-3%Re-3%Cu-1.5%B/Al 2 O 3 Preparation of the catalyst
100g of the alumina support after the alkali treatment (NaOH-3 to 120-8), 74.2g of cobalt nitrate hexahydrate, 4.4g of ammonium perrhenate, 11.3g of copper nitrate trihydrate, and 8.6g of boric acid were dissolved in 300ml of water, and the solution was dissolved at 50 ℃ to prepare an impregnation solution. And uniformly adding half of the impregnation liquid into an alumina carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 3
20%Ni-3.6%Re-2%B/SiO 2 Preparation of the catalyst
100g of base treatment (NaHCO) 3 -5 to 120 to 5), 99.0g of nickel nitrate hexahydrate, 5.2g of ammonium perrhenate and 11.4g of boric acid were dissolved in 300ml of water at 50 ℃ to prepare a dipping solution. And uniformly adding half of the impregnation liquid into a silicon oxide carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 4
20%Co-5%Cu-1%Ru/SiO 2 Preparation of the catalyst
100g of base treatment (NaHCO) 3 -5-80-6), 99.0g of cobalt nitrate hexahydrate, 18.9g of copper nitrate trihydrate, and 2.0g of ruthenium chloride were dissolved in 300ml of water, and dissolved at 50 ℃ to prepare a dipping solution. And uniformly adding half of the impregnation liquid into a silicon oxide carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 5
10% Ni-10% by Re-2.5% by weight of B/Si. Al catalyst preparation
100g of the alkali-treated (ethylenediamine-5-150-6) silica-alumina carrier was prepared by dissolving 49.6g of nickel nitrate hexahydrate, 49.6g of cobalt nitrate hexahydrate, 3.6g of ammonium perrhenate, and 11.4g of boric acid in 300ml of water, and dissolving them at 50 ℃ to prepare a solution. And uniformly adding half of the impregnation liquid into a silicon-aluminum carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 6
25%Ni-3.6%Re-2%B/SiO 2 Preparation of the catalyst
100g of base treatment (NaHCO) 3 -5 to 120 to 5), 123.8g of nickel nitrate hexahydrate, 5.2g of ammonium perrhenate and 11.4g of boric acid were dissolved in 300ml of water at 50 ℃ to prepare a dipping solution. And uniformly adding half of the impregnation liquid into a silicon oxide carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 7
15%Ni-5%Re-0.5%Ru/Al 2 O 3 Preparation of the catalyst
100g of the alumina support after the alkali treatment (NaOH-5 to 150-6), 74.2g of nickel nitrate hexahydrate, 7.2g of ammonium perrhenate and 1.0g of ruthenium chloride were dissolved in 300ml of water, and the solution was dissolved at 50 ℃ to prepare an impregnation solution. And uniformly adding half of the impregnation liquid into an alumina carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 8
25%Co-5%Cu-2%B/Al 2 O 3 Preparation of the catalyst
100g of the alumina support after the alkali treatment (ethylenediamine-3-120-8), 123.8g of cobalt nitrate hexahydrate, 18.9g of copper nitrate trihydrate, and 11.4g of boric acid were dissolved in 300ml of water at 50 ℃ to prepare a soaking solution. And uniformly adding half of the impregnation liquid into an alumina carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 9
20%Ni-3.6%Re-0.1%Pd/SiO 2 Preparation of the catalyst
100g of the silica carrier after the alkali treatment (NaOH-8 to 120-5), 99.0g of nickel nitrate hexahydrate, 5.2g of ammonium perrhenate, and 0.17g of palladium chloride were dissolved in 300ml of water, and dissolved at 50 ℃ to prepare a dipping solution. And uniformly adding a half of the impregnation liquid into a silicon oxide carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4 hours, and then roasting in a muffle furnace at 500 ℃ for 6 hours. The above preparation process is repeated until the required loading amount is reached.
Example 10
15%Ni-5%Co-3 % Cu -0.1%Pt/Al 2 O 3 Preparation of the catalyst
100g of the alumina support after alkali treatment (NaOH-5 to 150-6) was dissolved in 300ml of water with 74.2g of nickel nitrate hexahydrate, 24.8g of cobalt nitrate hexahydrate, 11.3g of copper nitrate trihydrate, and 0.14g of platinum dichloride, and the resultant solution was dissolved at 50 ℃ to prepare a solution. And uniformly adding half of the impregnation liquid into an alumina carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
Example 11
25%Ni-4.5%Cr/SiO 2 Preparation of the catalyst
100g of base treatment (NaHCO) 3 -5-120-5), 123.8g of nickel nitrate hexahydrate and 20.6g of chromium nitrate in 300ml of water, and dissolving at 50 ℃ to prepare a dipping solution. And uniformly adding a half of the impregnation liquid into a silicon oxide carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4 hours, and then roasting in a muffle furnace at 500 ℃ for 6 hours. The above preparation process is repeated until the required loading amount is reached.
Comparative example 1
25% Co-5% Cu-2% B/non-alkali treated Al 2 O 3
Compared with example 8, the carrier alumina was not subjected to the alkali treatment process, and the rest was the same as example 8.
100g of alumina carrier, 123.8g of cobalt nitrate hexahydrate, 18.9g of copper nitrate trihydrate and 11.4g of boric acid were dissolved in 300ml of water at 50 ℃ to prepare an impregnation solution. And uniformly adding half of the impregnation liquid into an alumina carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. Repeating the above preparation process until the required loading amount is reached
Comparative example 2
20%Ni-3.6%Re-2%B/SiO 2 Preparation of the catalyst
The procedure of example 3 was repeated except that the carrier silica was not subjected to the alkali treatment as compared with example 3.
20% Ni-3.6% Re-2% by weight/non-alkali-treated SiO 2 Preparation of the catalyst
100g of silica carrier, 99.0g of nickel nitrate hexahydrate, 5.2g of ammonium perrhenate and 11.4g of boric acid were dissolved in 300ml of water at 50 ℃ to prepare a solution. And uniformly adding half of the impregnation liquid into a silicon oxide carrier, airing at normal temperature, placing in an oven for drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 500 ℃ for 6h. The above preparation process is repeated until the required loading amount is reached.
3. Evaluation of catalyst
The catalysts prepared in examples 1-11 and comparative examples 1 and 2 were placed at 325 ℃ at a space velocity of 2000h -1 And activating for 12 hours in the hydrogen flow. Cooling to 160 deg.C, mixing liquid ammonia and hexanediol, feeding into fixed bed reactor filled with catalyst, feeding hydrogen gas, and feeding H 2 The reaction was carried out at a/ammonia/hexanediol ratio of 0.1.
The evaluation results are shown in table 1.
TABLE 1 evaluation results of catalysts
As can be seen from Table 1, the conversion rate of hexanediol to hexamethylenediamine in the catalyst of the present invention was 63% or more, and the maximum conversion rate was 79.0%, except that in example 5, the conversion rate of hexanediol was less than 60%. Example 5 the low conversion should be due to the carrier being a mixed carrier.
As can be seen from Table 1, the loading of active ingredient was high, and both the conversion of hexanediol and the selectivity of hexamethylenediamine tended to increase.
In addition, comparative example 1 is different from example 8 only in that the catalyst carrier is not treated with alkali, but in the reaction for synthesizing hexamethylene diamine by catalyzing hexanediol, the conversion rate of example 8 is improved by 38.3% compared with comparative example 1, and the selectivity of hexamethylene diamine in example 8 is improved by 68.6% compared with comparative example 1.
Comparative example 1 compared with example 3, the difference is only that the catalyst carrier is not treated by alkali, but in the reaction for synthesizing hexamethylene diamine by catalyzing hexanediol, the conversion rate of example 3 is improved by 53.6% compared with comparative example 1, and the selectivity of hexamethylene diamine in example 3 is improved by 81.1% compared with comparative example 1.
It can be seen that the catalytic effect of the catalyst can be significantly improved by alkali treatment of the carrier, and the conversion rate of hexanediol and the selectivity of hexamethylenediamine are both significantly improved.
Claims (5)
1. A catalyst for synthesizing hexamethylene diamine comprises an active component, an auxiliary agent and a carrier; the active component is one or two of Ni or Co; the method is characterized in that: the auxiliary agent is one or more of Pd, pt, re, ru, cr, B, cu and Na; the carrier is one or more of aluminum oxide, silicon oxide and silicon-aluminum oxide which are subjected to alkali treatment;
preparing an aqueous solution with the mass percentage of 2-10% from alkali, placing the carrier in an alkali liquor, soaking for 1-10 h at 50-200 ℃, washing with water until the eluate is neutral, drying, and roasting for 2-10 h at 300-800 ℃;
the alkali is one or more of sodium hydroxide, ethylenediamine and sodium bicarbonate;
the active component accounts for 5-40% of the total mass of the catalyst;
the auxiliary agent accounts for 1-10% of the total mass of the catalyst;
the catalyst is used for catalyzing the amination of hexanediol under the hydrogen condition to prepare hexamethylene diamine.
2. The catalyst for the synthesis of hexamethylenediamine according to claim 1, wherein: the auxiliary agent is one or more of Pd, re, cr and B.
3. The process for preparing hexamethylene diamine by amination of hexanediol under the condition of hydrogen catalysis by the catalyst of claim 1, which is characterized in that: filling the activated catalyst into a trickle bed or fixed bed reactor, and preparing hexamethylene diamine by using hexanediol and ammonia as reactants under the conditions of temperature of 100 to 200 ℃, pressure of 5 to 13MPa and hydrogen presence; the ammonia-alcohol ratio is 2 to 20, and the hydrogen mole fraction is 1 to 30%.
4. A process for the amination of hexylene glycol to produce hexylene diamine in the presence of hydrogen according to claim 3, wherein: the hexanediol and the liquid ammonia are pumped into a trickle bed or fixed bed reactor by a high pressure pump.
5. A process for the amination of hexylene glycol to produce hexylene diamine in the presence of hydrogen according to claim 3, wherein: the activation temperature of the catalyst is 200 to 600 ℃, the pressure is 0.3 to 3MPa, and the space velocity is 100 to 2500h -1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010064037.6A CN111151256B (en) | 2020-01-20 | 2020-01-20 | Catalyst for synthesizing hexamethylene diamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010064037.6A CN111151256B (en) | 2020-01-20 | 2020-01-20 | Catalyst for synthesizing hexamethylene diamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111151256A CN111151256A (en) | 2020-05-15 |
| CN111151256B true CN111151256B (en) | 2023-03-24 |
Family
ID=70564417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010064037.6A Active CN111151256B (en) | 2020-01-20 | 2020-01-20 | Catalyst for synthesizing hexamethylene diamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111151256B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111604054B (en) * | 2020-06-10 | 2023-05-30 | 南京红宝丽醇胺化学有限公司 | Catalyst for synthesizing 2-aminopropanol, preparation method and use thereof |
| CN113797929A (en) * | 2020-06-17 | 2021-12-17 | 中国科学院过程工程研究所 | Solid catalyst for catalyzing synthesis of butanediamine, method for preparing butanediamine by using solid catalyst and system device |
| CN113713853B (en) * | 2021-09-16 | 2024-03-22 | 中触媒新材料股份有限公司 | Method for preparing aliphatic diamine from cyclic imine and catalyst used in method |
Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3591635A (en) * | 1968-09-25 | 1971-07-06 | Upjohn Co | Catalytic hydrogenation process for preparing di(4 - aminocyclohexyl) methane |
| US4409399A (en) * | 1981-12-09 | 1983-10-11 | Millmaster Onyx Group, Inc. | Process for producing aliphatic amines |
| JPH07101910A (en) * | 1993-04-27 | 1995-04-18 | Sumitomo Chem Co Ltd | Production of amines |
| US5488165A (en) * | 1990-04-10 | 1996-01-30 | Zeofuels Research (Proprietary) Limited | Process for the production of methyl amines |
| CN1179423A (en) * | 1996-09-23 | 1998-04-22 | 气体产品与化学公司 | Triethylenediamine synthesis with base-treated zeolits as catalysts |
| JP2000038369A (en) * | 1998-06-04 | 2000-02-08 | Bayer Ag | Production of various mixtures of cyclohexylamine and dicyclohexylamine |
| CN1467028A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing vinyl epoxide argentum catalyst |
| CN103357436A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Alkali treatment modification method of alumina carrier as well as preparation method and application of silver catalyst supported by alumina carrier |
| CN104001516A (en) * | 2014-05-29 | 2014-08-27 | 中国天辰工程有限公司 | Preparation method of catalyst for synthesizing hexanediamine by carrying out hydrogenation on hexane dinitrile |
| CN104262168A (en) * | 2014-09-22 | 2015-01-07 | 北京旭阳化工技术研究院有限公司 | Preparation method of hexamethylenediamine |
| CN105107496A (en) * | 2015-08-28 | 2015-12-02 | 陕西开达化工有限责任公司 | Ruthenium aluminium oxide catalyst and preparation method thereof |
| CN106807395A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of catalyst for synthesizing hexamethylene diamine |
| CN106807377A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of catalyst for synthesizing hexamethylene diamine |
| CN107159308A (en) * | 2017-06-22 | 2017-09-15 | 中国天辰工程有限公司 | A kind of Ni-based molecular sieve catalyst and preparation method thereof |
| CN107486208A (en) * | 2017-08-25 | 2017-12-19 | 湘潭大学 | A kind of preparation method and application of carbon nanotube loaded quaternary amorphous nickel-base catalyst |
| CN107899587A (en) * | 2017-11-22 | 2018-04-13 | 山东玉皇化工有限公司 | A kind of catalyst for fatty alcohol amination amine and preparation method thereof |
| CN107913694A (en) * | 2017-10-31 | 2018-04-17 | 山东玉皇化工有限公司 | A kind of modulating method of amination catalysis carrier and its application |
| WO2018121042A1 (en) * | 2016-12-27 | 2018-07-05 | 河南神马尼龙化工有限责任公司 | Production method for high-quality pure hexanediamine |
| CN109647419A (en) * | 2018-12-20 | 2019-04-19 | 大连理工大学 | A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, preparation method and application |
| CN111072489A (en) * | 2019-12-16 | 2020-04-28 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine from hexamethylene dialdehyde in fixed bed reactor |
| CN112898163A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing 1, 6-hexamethylene diamine by ammoniation of hexamethylene imine |
| CN114433090A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and carrier with function of catalytically synthesizing amine by taking alcohol as raw material, and preparation method and application thereof |
-
2020
- 2020-01-20 CN CN202010064037.6A patent/CN111151256B/en active Active
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3591635A (en) * | 1968-09-25 | 1971-07-06 | Upjohn Co | Catalytic hydrogenation process for preparing di(4 - aminocyclohexyl) methane |
| US4409399A (en) * | 1981-12-09 | 1983-10-11 | Millmaster Onyx Group, Inc. | Process for producing aliphatic amines |
| US5488165A (en) * | 1990-04-10 | 1996-01-30 | Zeofuels Research (Proprietary) Limited | Process for the production of methyl amines |
| JPH07101910A (en) * | 1993-04-27 | 1995-04-18 | Sumitomo Chem Co Ltd | Production of amines |
| CN1179423A (en) * | 1996-09-23 | 1998-04-22 | 气体产品与化学公司 | Triethylenediamine synthesis with base-treated zeolits as catalysts |
| JP2000038369A (en) * | 1998-06-04 | 2000-02-08 | Bayer Ag | Production of various mixtures of cyclohexylamine and dicyclohexylamine |
| CN1467028A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing vinyl epoxide argentum catalyst |
| CN103357436A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Alkali treatment modification method of alumina carrier as well as preparation method and application of silver catalyst supported by alumina carrier |
| CN104001516A (en) * | 2014-05-29 | 2014-08-27 | 中国天辰工程有限公司 | Preparation method of catalyst for synthesizing hexanediamine by carrying out hydrogenation on hexane dinitrile |
| CN104262168A (en) * | 2014-09-22 | 2015-01-07 | 北京旭阳化工技术研究院有限公司 | Preparation method of hexamethylenediamine |
| CN105107496A (en) * | 2015-08-28 | 2015-12-02 | 陕西开达化工有限责任公司 | Ruthenium aluminium oxide catalyst and preparation method thereof |
| CN106807395A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of catalyst for synthesizing hexamethylene diamine |
| CN106807377A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of catalyst for synthesizing hexamethylene diamine |
| WO2018121042A1 (en) * | 2016-12-27 | 2018-07-05 | 河南神马尼龙化工有限责任公司 | Production method for high-quality pure hexanediamine |
| CN107159308A (en) * | 2017-06-22 | 2017-09-15 | 中国天辰工程有限公司 | A kind of Ni-based molecular sieve catalyst and preparation method thereof |
| CN107486208A (en) * | 2017-08-25 | 2017-12-19 | 湘潭大学 | A kind of preparation method and application of carbon nanotube loaded quaternary amorphous nickel-base catalyst |
| CN107913694A (en) * | 2017-10-31 | 2018-04-17 | 山东玉皇化工有限公司 | A kind of modulating method of amination catalysis carrier and its application |
| CN107899587A (en) * | 2017-11-22 | 2018-04-13 | 山东玉皇化工有限公司 | A kind of catalyst for fatty alcohol amination amine and preparation method thereof |
| CN109647419A (en) * | 2018-12-20 | 2019-04-19 | 大连理工大学 | A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, preparation method and application |
| CN112898163A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing 1, 6-hexamethylene diamine by ammoniation of hexamethylene imine |
| CN111072489A (en) * | 2019-12-16 | 2020-04-28 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine from hexamethylene dialdehyde in fixed bed reactor |
| CN114433090A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and carrier with function of catalytically synthesizing amine by taking alcohol as raw material, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Gas-phase hydrogenation of adiponitrile with high selectivity to primary amine over supported Ni-B amorphous catalysts;HexingLi et al.;《Applied Catalysis A: General》;20010831;摘要，第2.1节，第3节 * |
| Reductive amination of 1,6-hexanediol with Ru/Al2O3 catalyst in;Yan Li et al.;《SCIENCE CHINA》;20170630;第920-926页 * |
| 腈选择性加氢制备胺类化合物的催化技术研究进展;王清涛等;《浙江化工》;20151231;第31-34页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111151256A (en) | 2020-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111151256B (en) | Catalyst for synthesizing hexamethylene diamine | |
| KR100420453B1 (en) | Raney Iron Catalyst and a Process for Hydrogenating Organic Compounds Using Said Catalyst | |
| CN107899587B (en) | Catalyst for amine production by fatty alcohol amination and preparation method thereof | |
| CN110551278B (en) | Supported catalyst and preparation method and application thereof | |
| CN112898558B (en) | Method for preparing polyether amine by hydroamination of polyether polyol | |
| JPS60261542A (en) | Reinforced nickel catalyst for amination | |
| CN101966456A (en) | Hydrogenation catalyst and preparation method of 4,4'-diamino-dicyclohexyl methane | |
| CN109574855B (en) | Method for continuously preparing pentamethyldiethylenetriamine and catalyst system used for method | |
| CN110961154B (en) | Hydrogenation catalyst and preparation method thereof, and method for preparing citronellal by hydrogenating citral | |
| CN106807377A (en) | A kind of catalyst for synthesizing hexamethylene diamine | |
| CN112705241A (en) | Ruthenium-based catalyst, preparation method and application thereof | |
| CN107540556B (en) | Preparation method of m-xylylenediamine | |
| CN112473663A (en) | Catalyst for preparing alicyclic amine from aromatic amine and preparation method and application thereof | |
| WO2023179110A1 (en) | Method for synthesizing polyethylene polyamine under catalysis | |
| CN110496645B (en) | Supported aminoalkyl ion liquid-metal catalyst and preparation and application thereof | |
| CN100465145C (en) | Process of preparing 1,4-cyclohexane dimethand | |
| CN109821572A (en) | Porous microsphere Polymer-supported metal catalyst and its preparation method and application | |
| CN102491904A (en) | Application of hydrogenation catalyst to preparation of 1,4-cyclohexanediamine | |
| CN110116004B (en) | Catalyst for synthesizing ethylene amine by reductive amination of monoethanolamine and liquid ammonia prepared from nitrate and preparation and use methods thereof | |
| CN110201671B (en) | Catalyst for synthesizing ethylene amine by monoethanolamine prepared by ammonia complex and reductive amination of liquid ammonia and preparation and use methods thereof | |
| CN114160127B (en) | Anti-deamination hydrogenation catalyst and preparation method and application thereof | |
| CN114436852A (en) | Method for preparing hexamethylene diamine by hydrogenation of adiponitrile | |
| CN114933535B (en) | Preparation method of membrane reactor and method for co-producing aniline and 4-aminodiphenylamine from nitrobenzene | |
| CN112774670A (en) | Application of rhodium monatomic catalyst in reaction for preparing m-chloroaniline through selective hydrogenation of m-chloronitrobenzene | |
| CN108084034A (en) | A kind of method that ethylene glycol carries out hydrogenating amination reaction under supercritical ammine state |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |