CN116535321A - Method for preparing nonanediamine by hydrogenation of nonanedinitrile - Google Patents
Method for preparing nonanediamine by hydrogenation of nonanedinitrile Download PDFInfo
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- CN116535321A CN116535321A CN202210112136.6A CN202210112136A CN116535321A CN 116535321 A CN116535321 A CN 116535321A CN 202210112136 A CN202210112136 A CN 202210112136A CN 116535321 A CN116535321 A CN 116535321A
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- nondinitrile
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- 238000000034 method Methods 0.000 title claims abstract description 33
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 title claims abstract description 20
- QXOYPGTWWXJFDI-UHFFFAOYSA-N nonanedinitrile Chemical compound N#CCCCCCCCC#N QXOYPGTWWXJFDI-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 title description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007868 Raney catalyst Substances 0.000 claims description 6
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- HOKKHZGPKSLGJE-GSVOUGTGSA-N N-Methyl-D-aspartic acid Chemical compound CN[C@@H](C(O)=O)CC(O)=O HOKKHZGPKSLGJE-GSVOUGTGSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- -1 aliphatic diamine Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a novel method for preparing nonanediamine by hydrogenating nonanedinitrile, and relates to the technical field of catalytic hydrogenation. The new method for preparing the nonanediamine mainly comprises the steps of adopting a trickle bed reaction mode, introducing benzene solvent, and mixing with alcohol solvent to prepare a double-solvent system. By the two modes, the problem of rapid deactivation of the catalyst caused by poor solubility of impurities in a solvent and adsorption in a catalyst pore canal due to back mixing of materials in the original process is solved.
Description
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to a novel method for preparing nonanediamine by hydrogenating nonanedinitrile.
Background
The nonanediamine is C9 aliphatic diamine, the products of industrial production at present are all a mixture of two isomers of Nonanediamine (NMDA) and 2-methyl-1, 8-octanediamine (MODA), and the mixture is white solid. Nonylenediamine is mainly used as a raw material of heat-resistant polyamide resin (PA 9T), and is also used as a raw material of various fine chemicals and a raw material of polyamide and polyurethane because it has many reactive characteristics similar to ethylenediamine and hexamethylenediamine.
The existing methods for preparing the nonanediamine mainly comprise a butadiene method (US 4417079, US4510331, US4510331, JP 58167547) and a nonanedinitrile hydrogenation method (CN 106220513A, CN 102701991A). The butadiene method has longer process flow and low nonanediamine content, and the petroleum-based product is used as a raw material, so that the application of the product in the fields of medicines and foods is limited. The nondinitrile hydrogenation method mainly adopts a reaction kettle mode, the material back mixing is serious, the catalyst is severely crushed, the deactivation speed is high, and the intermittent reaction efficiency is low.
Therefore, development of a process for producing nonylenediamine which can be continuously produced and has stable operating conditions and can be operated for a long period of time is needed.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for preparing nonanediamine by hydrogenating nonanedinitrile, which is used for solving the problems that the existing reaction form adopted by the hydrogenation of nonanedinitrile has serious back mixing, the solubility of reaction impurities in a solvent is poor, the catalyst is deactivated rapidly, new catalyst is required to be added continuously, the deactivated catalyst is discharged, the cost is greatly increased, the solid waste is increased, and the reaction efficiency is restricted.
In order to achieve the aim of the invention, the invention provides a trickle bed reaction type catalytic hydrogenation system, and simultaneously introduces a double solvent system, so that the problem of dissolution of anti-mixing impurities is effectively solved, and the catalyst can not be deactivated in the long-time use process.
A method for preparing nonanediamine by hydrogenation of nonanedinitrile, which comprises the following steps:
s1: mixing the nonoxydinitrile with a solvent to form a nonoxydinitrile solution; the solvent includes benzene solvents and alcohol solvents;
s2: mixing the nonodinitrile solution and the cocatalyst to form a liquid raw material;
s3: the liquid raw material and the hydrogen gas pass through a catalyst bed layer of the trickle bed reactor from top to bottom to react to obtain the nonanediamine; the catalyst bed is filled with catalyst.
The invention provides a novel process for preparing nonanediamine by hydrogenating nonanedinitrile, which adopts a trickle bed as a reactor. Meanwhile, a second benzene solvent is introduced and mixed with an alcohol solvent to prepare a double solvent.
Step S1
The benzene solvent is not limited and may be benzene organic solvents known in the art capable of dissolving nondinitrile and hydrogenation products, including but not limited to toluene, benzene, ethylbenzene, cumene, xylenes, etc.
The alcohol solvent is not limited and may be an alcohol organic solvent capable of dissolving nondinitrile and hydrogenation products known in the art, including but not limited to methanol, ethanol, propanol, butanol, etc.
The mode of the combination of the benzene solvent and the alcohol solvent is not limited, and for example, the solvent may be a mixed solution of ethanol and toluene, a mixed solution of ethanol and xylene, a mixed solution of ethanol and toluene, a mixed solution of methanol and xylene, or the like.
By introducing benzene solvent, deamination and cyclization impurities generated by hydrogenation reaction can be better dissolved in the solvent, so that the catalyst is prevented from being coated on the catalyst to cause deactivation. The double-solvent system is adopted, so that the service life of the catalyst can be greatly prolonged, the dosage of the catalyst is reduced, and the reaction cost is saved.
In one embodiment, the benzene solvent to alcohol solvent mass ratio is (1-10): 10, e.g., 1:10, 1:5, 3:10, 2:5, 1:2, 3:5, 7:10, 4:5, 9:10, 1:1.
In one embodiment, the concentration of nonoxydinitrile in the nonoxydinitrile solution is 20% -50%, e.g., 20%, 25%, 30%, 35%, 40%, 45%, 50% by mass.
Step S2
The promoter is not limited and may be any promoter known in the art that can be used in the hydrogenation of nondinitriles, including but not limited to sodium hydroxide, potassium hydroxide, or calcium hydroxide, among others.
In one embodiment, the mass ratio of nondinitrile to promoter (e.g., sodium hydroxide) is (20-100): 1, e.g., 20:1, 40:1, 60:1, 80:1, 100:1.
In one embodiment, the mass concentration of promoter in the liquid feedstock is from 0.25% to 0.5%, such as 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, or 0.5%.
Step S3
The trickle bed reactor is a gas-liquid-solid three-phase catalytic reactor, and gas and liquid flow downwards through a solid catalyst bed in parallel. The liquid raw material and hydrogen of the invention react from top to bottom through the catalyst bed layer to obtain the nonanediamine.
In one embodiment, the molar ratio of hydrogen to nonyldinitrile is from 20 to 120, such as 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120.
The catalyst bed is filled with catalyst.
The catalyst is not limited and may be a hydrogenation catalyst known in the art to be capable of being used in the hydrogenation of nondinitriles. Preferably, the catalyst takes 3-8mm shaped Raney nickel or 3-5mm supported nickel as the catalyst, and the porosity of the catalyst is required to be more than 20 percent so as to ensure the trickle effect.
In one embodiment, the temperature of the reaction is from 70 ℃ to 100 ℃, such as 70 ℃, 80 ℃, 90 ℃, 100 ℃. The pressure of the reaction is 2MPa to 5MPa, for example 2MPa, 3MPa, 4MPa and 5MPa. Reaction space velocity of 0.1h -1 -1h -1 For example 0.1h -1 、0.2h -1 、0.5h -1 、0.6h -1 、0.8h -1 、1h -1 。
Space velocity refers to the amount of catalyst treated material per unit time per unit mass under specified conditions, in Kg/(m) 3 Catalyst h), which can be simplified as h -1 。
The process mainly adopts a new reactor form, and a double-solvent system is additionally used for solving the problem of higher catalyst deactivation rate. Raney nickel or supported nickel is used as catalyst to perform continuous reaction under certain reaction conditions. Compared with the existing reactor and fluidized bed reactor, the reactor can quickly generate products from raw materials, avoid side reactions, reduce reaction back mixing, quickly discharge generated substances out of a reaction system, and greatly reduce the probability of catalyst deactivation.
The technical scheme of the embodiment of the invention has the following beneficial effects:
(1) The invention obviously reduces the deactivation rate of the catalyst and improves the impurity resistance of the catalyst by using a double-solvent system, thereby enhancing the stability of the catalyst, prolonging the single-use time of the catalyst, reducing the replacement frequency of the catalyst, improving the production efficiency, shortening the reaction flow and having great practical industrial application value.
(2) According to the invention, a trickle bed is used as a reactor, a raw material nondinitrile solution is mixed with excessive hydrogen and then quickly passes through a catalyst bed layer of the reactor, so that complete conversion of nondinitrile is realized, meanwhile, the heat transfer effect of the excessive hydrogen is utilized, the temperature of the catalyst bed layer is controlled, the overhigh reaction temperature is avoided, and the conversion rate of the reaction reaches 100%. Meanwhile, the trickle bed is a plug flow type reactor (forward flow, liquid raw materials and hydrogen pass through from top to bottom), and the back mixing of a reaction system can be effectively restrained, so that the selectivity is over 98%, the hydrogen is recycled through a circulating compressor, and the process is simpler than the operation of a reaction kettle, solves the difficulty in the prior art, and reduces the production cost.
The present invention has been described in detail hereinabove, but the above embodiments are merely exemplary in nature and are not intended to limit the present invention. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or summary or the following examples.
Unless explicitly stated otherwise, numerical ranges throughout this application include any subrange therein and any numerical value incremented by the smallest subunit in which a given value is present. Unless explicitly stated otherwise, numerical values throughout this application represent approximate measures or limits to include minor deviations from the given value and ranges of embodiments having about the stated value and having the exact value noted. Except in the operating examples provided last, all numerical values of parameters (e.g., amounts or conditions) in this application (including the appended claims) are to be understood in all cases as modified by the term "about" whether or not "about" actually appears before the numerical value. "about" means that the recited value allows for slight imprecision (with some approximation to the exact value; approximately or reasonably close to the value; approximated). "about" as used herein at least means variations that can be produced by ordinary methods of measuring and using these parameters if the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" may include a change of less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, or less than or equal to 0.5%.
Detailed Description
The invention is further illustrated by the following examples, which are provided for illustrative purposes only and are not to be construed as limiting the scope of the invention as claimed.
Unless otherwise indicated, all materials, reagents, methods and the like used in the examples are those conventionally used in the art.
Trickle bed reactors were purchased from aerospace century star SRT-H1002BJ.
Examples
Example 1
A method for preparing nonanediamine by hydrogenation of nonanedinitrile, which comprises the following steps:
mixing a certain amount of nondinitrile, corresponding alcohols and benzene, adding an inorganic base cocatalyst, mixing, and dissolving to prepare a nondinitrile liquid raw material with a certain concentration; the liquid raw material passes through the catalyst bed layer of the trickle bed reactor from top to bottom through the metering pump according to the set flow and the hydrogen with the set flow, and hydrogenation reaction is carried out, so that hydrogenation reaction liquid is obtained.
The experimental evaluation device selects a trickle bed as a reactor, 3-5mm shaped Raney nickel as a catalyst, the reaction temperature is 80 ℃, the pressure is 2.5MPa, and the reaction airspeed is 0.5h -1 The molar ratio of the hydrogen to the nonodinitrile is 80:1, and the solvent is ethanol and methyl acetateThe mass ratio of the benzene mixed solution is 3:1, the mass concentration of the nondinitrile in the nondinitrile solution is 20wt%, the mass concentration of the sodium hydroxide in the liquid raw material is 0.5%, the continuous operation is carried out for 300 hours, the catalyst activity is basically unchanged, the average conversion rate is 99.9%, and the average selectivity is 99.2%.
Example 2
A method for preparing nonanediamine by hydrogenation of nonanedinitrile, which comprises the following steps:
mixing a certain amount of nondinitrile, corresponding alcohols and benzene, adding an inorganic base cocatalyst, mixing, and dissolving to prepare a nondinitrile liquid raw material with a certain concentration; the liquid raw material passes through the catalyst bed layer of the trickle bed reactor from top to bottom through the metering pump according to the set flow and the hydrogen with the set flow, and hydrogenation reaction is carried out, so that hydrogenation reaction liquid is obtained.
The experimental evaluation device selects a trickle bed as a reactor, 3-5mm shaped Raney nickel as a catalyst, the reaction temperature is 80 ℃, the pressure is 2.5MPa, and the reaction airspeed is 0.5h -1 The molar ratio of the hydrogen to the nondinitrile is 80:1, the solvent is ethanol and toluene mixed solution, the mass ratio is 3:1, the nondinitrile mass concentration in the nondinitrile solution is 10wt%, the sodium hydroxide mass concentration in the liquid raw material is 0.25%, the continuous operation is carried out for 300 hours, the catalyst activity is basically unchanged, the average conversion rate is 99.9%, and the average selectivity is 99.7%.
Example 3
A method for preparing nonanediamine by hydrogenation of nonanedinitrile, which comprises the following steps:
mixing a certain amount of nondinitrile, corresponding alcohols and benzene, adding an inorganic base cocatalyst, mixing, and dissolving to prepare a nondinitrile liquid raw material with a certain concentration; the liquid raw material passes through the catalyst bed layer of the trickle bed reactor from top to bottom through the metering pump according to the set flow and the hydrogen with the set flow, and hydrogenation reaction is carried out, so that hydrogenation reaction liquid is obtained.
The experimental evaluation device selects a trickle bed as a reactor, 3-5mm shaped Raney nickel as a catalyst, the reaction temperature is 80 ℃, the pressure is 2.5MPa, and the reaction airspeed is 0.5h -1 The molar ratio of the hydrogen to the nonyldinitrile is 80:1, the solvent is ethanol and toluene mixed solution, the mass ratio is 5:1, and the nonyldinitrile in the nonyldinitrile solution isThe mass concentration of nitrile is 20wt%, the mass concentration of sodium hydroxide in the liquid raw material is 0.5%, the continuous operation is carried out for 300 hours, the catalyst activity is slightly reduced, the average conversion rate is 99.0%, and the average selectivity is 97.4%.
Example 4
A method for preparing nonanediamine by hydrogenation of nonanedinitrile, which comprises the following steps:
mixing a certain amount of nondinitrile, corresponding alcohols and benzene, adding an inorganic base cocatalyst, mixing, and dissolving to prepare a nondinitrile liquid raw material with a certain concentration; the liquid raw material passes through the catalyst bed layer of the trickle bed reactor from top to bottom through the metering pump according to the set flow and the hydrogen with the set flow, and hydrogenation reaction is carried out, so that hydrogenation reaction liquid is obtained.
The experimental evaluation device selects a trickle bed as a reactor, 3mm shaped supported nickel-based catalyst is adopted, the reaction temperature is 80 ℃, the pressure is 2.5MPa, and the reaction airspeed is 0.5h -1 The molar ratio of the hydrogen to the nondinitrile is 80:1, the solvent is ethanol and toluene mixed solution, the mass ratio is 3:1, the nondinitrile mass concentration in the nondinitrile solution is 20wt%, the sodium hydroxide mass concentration in the liquid raw material is 0.5%, the continuous operation is carried out for 300 hours, the catalyst activity is basically unchanged, the average conversion rate is 99.9%, and the average selectivity is 98.5%.
Comparative example 1
The experimental evaluation device selects a reaction kettle as a reactor, the reaction temperature is 80 ℃, the pressure is 2.5MPa, the nonodinitrile is a catalyst, sodium hydroxide is a catalyst, ethanol is a solvent, the reaction is carried out for 4 hours under the condition that the catalyst is 10:1:0.25:50 (mass ratio), the catalyst is reused for 10 times, the average conversion rate of 10 times is 95.1%, and the average selectivity is 90.5%.
Comparative example 2
The experimental evaluation device selects a reaction kettle as a reactor, the reaction temperature is 80 ℃, the pressure is 2.5MPa, the nonodinitrile is a catalyst, sodium hydroxide is sodium hydroxide, ethanol is toluene is 10:1:0.25:37.5:12.5 (mass ratio), wherein the ethanol and the toluene are used as solvents, the reaction is carried out for 4 hours under the condition, the catalyst is repeatedly used for 10 times, the average conversion rate of 10 times is 97.6%, and the average selectivity is 93.4%.
It can be seen that although the comparative examples are different from the reaction forms of the examples of the present invention, both the conversion and selectivity values in the comparative examples are lower than those in the examples of the present invention, and the catalyst deactivation rate in the comparative examples is significantly higher than that in the examples of the present invention, and the overall production efficiency is much lower than that in the examples of the present invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. A method for preparing nonanediamine by hydrogenating nonanedinitrile, which is characterized by comprising the following steps:
mixing the nonoxydinitrile with a solvent to form a nonoxydinitrile solution; the solvent comprises benzene solvent and alcohol solvent;
mixing the nonodinitrile solution and the cocatalyst to form a liquid raw material;
the liquid raw material and the hydrogen gas pass through a catalyst bed layer of the trickle bed reactor from top to bottom to react to obtain the nonanediamine; the catalyst bed is filled with a catalyst.
2. The method according to claim 1, wherein the mass concentration of the nondinitrile in the nondinitrile solution is 20% -50%.
3. The method according to claim 1, wherein the benzene solvent is one or more of toluene, benzene, ethylbenzene, cumene or xylene;
the alcohol solvent is one or more of methanol, ethanol, propanol or butanol.
4. The method according to claim 3, wherein the mass ratio of the benzene-based solvent to the alcohol-based solvent is (1-10): 10.
5. The method of claim 1, wherein the promoter is one or more of sodium hydroxide, potassium hydroxide, or calcium hydroxide.
6. The method according to claim 5, wherein the mass concentration of the cocatalyst in the liquid feedstock is 0.25% -0.5%;
the mass ratio of the nondinitrile to the cocatalyst is (20-100): 1.
7. The process according to any one of claims 1 to 6, wherein the molar ratio of hydrogen to nonyldinitrile is from 20 to 120.
8. The method of any one of claims 1-6, wherein the catalyst is 3-8mm shaped raney nickel or 3-5mm supported nickel, and the catalyst porosity is greater than 20%.
9. The process according to any one of claims 1 to 6, wherein the reaction temperature is from 70℃to 100℃and the pressure is from 2MPa to 5MPa, and the reaction space velocity is 0.1h -1 -1h -1 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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