CN114436859A - Method for preparing sec-butylamine through etherified C4 - Google Patents
Method for preparing sec-butylamine through etherified C4 Download PDFInfo
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- CN114436859A CN114436859A CN202011205038.4A CN202011205038A CN114436859A CN 114436859 A CN114436859 A CN 114436859A CN 202011205038 A CN202011205038 A CN 202011205038A CN 114436859 A CN114436859 A CN 114436859A
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- butylamine
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- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 230000009471 action Effects 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000006266 etherification reaction Methods 0.000 claims description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000001282 iso-butane Substances 0.000 claims description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 7
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 5
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 3
- 229960000583 acetic acid Drugs 0.000 description 31
- 239000000203 mixture Substances 0.000 description 13
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000005913 hydroamination reaction Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100001223 noncarcinogenic Toxicity 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 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
- C07C209/46—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 carboxylic acids or esters thereof in presence of ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a method for preparing sec-butylamine through etherified C4. The method comprises the following steps: (1) carrying out a first reaction on acetic acid and etherified C4 under the action of a first catalyst to obtain a first stream containing sec-butyl acetate; (2) and uniformly mixing the first stream with hydrogen and ammonia, and then carrying out a second reaction under the action of a second catalyst to obtain a second stream containing sec-butylamine. The method has simple process, good conversion rate and target product selectivity, is easy to realize industrial application, and is an effective way for reasonably utilizing the C4 and acetic acid resources after the ether is removed.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for preparing sec-butylamine through etherified C4.
Background
Sec-butylamine is a colorless, ammonia-flavored volatile liquid, is dissolved in water, ethanol, diethyl ether, acetone and the like, has a mildew-proof and sterilization effect, is recommended by the health organization and the food organization of the United nations as a low-toxicity, non-malformation and non-carcinogenic excellent preservative in the early 80 th century, and the demand of the preservative is continuously increased in recent years.
The main sources of the C4 mixture are a catalytic cracking unit and an ethylene cracking unit, the mixed C4 component after etherification with methanol is called as post-etherification C4, and the main components of the post-etherification C4 are butylene, isobutane, n-butane, cis-2-butylene, trans-2-butylene and the like. For years, the C4 resource is not reasonably utilized in China, and a large amount of etherified C4 resource in China is combusted and used as civil fuel. In recent years, due to large-scale development and utilization of natural gas, the etherified C4 is gradually replaced by pipeline natural gas in the field of civil fuels, the market share is gradually reduced, the etherified C4 resource is reasonably used, and the high-added-value chemical product prepared by the etherified C4 resource has good social value.
Meanwhile, with the development of the technology for preparing methanol from coal in China, the yield of a methanol carbonylation acetic acid preparation device can be rapidly increased, the total global acetic acid yield in 2015 is close to 2000 kilotons, wherein the acetic acid productivity of seranies, BP, Jiangsusoprop, Shanghai friendship and Shandong Yan mines is more than 100 kilotons, and the domestic acetic acid productivity is seriously surplus.
Therefore, the C4 resource after acetic acid and ether are reasonably utilized, and the high value-added product is prepared by using the resource, so that the method has good social value and market prospect.
The prior patent only discloses a preparation method of single ethylamine or single sec-butylamine, and does not disclose a technical route for preparing sec-butylamine from C4 after acetic acid and ether.
Disclosure of Invention
The invention aims to solve the problems and provide a method for preparing sec-butylamine starting from C4 after etherification.
In order to achieve the above object, the present invention provides a process for preparing sec-butylamine through post-ether C4, comprising the steps of:
(1) carrying out a first reaction on acetic acid and etherified C4 under the action of a first catalyst to obtain a first stream containing sec-butyl acetate;
(2) and uniformly mixing the first stream with hydrogen and ammonia, and then carrying out a second reaction under the action of a second catalyst to obtain a second stream containing sec-butylamine.
In a particular embodiment, the process for the preparation of sec-butylamine by post-ether C4, according to the present invention, comprises the following steps:
(1) uniformly mixing acetic acid and C4 after ether treatment in a first mixer, then feeding the mixture into a first reactor, filling a first catalyst into the first reactor, and performing esterification reaction (namely a first reaction) under the action of the first catalyst to obtain a first stream containing sec-butyl acetate;
(2) uniformly mixing the first stream with hydrogen and ammonia in a second mixer, then feeding the mixture into a second reactor, and carrying out hydroamination (namely, carrying out a second reaction) under the action of a second catalyst to obtain a second stream containing sec-butylamine;
(3) and separating components in the second stream, such as gas-liquid separation, to obtain the sec-butylamine.
Wherein, the first reactor can be selected from but not limited to a tubular reactor, a tank reactor and a tower reactor, and is preferably a tubular reactor. Usually, the first catalyst is filled in the middle position in the first reactor, and ceramic rings are used for filling other parts.
Wherein, the second reactor can be selected from but not limited to a tubular reactor, a tank reactor and a tower reactor, and is preferably a tubular reactor. Usually, the second catalyst is filled in the middle position in the second reactor, and ceramic rings are used for filling other parts.
In a particular embodiment, according to the present invention, said first stream comprises, in addition to sec-butyl acetate, isobutane, n-butane, small amounts of n-butenes, small amounts of cis-2-butene and trans-2-butene.
According to the invention, in a particular embodiment, said second stream comprises, in addition to sec-butylamine: ethylamine, isobutane, n-butane, hydrogen, ammonia, ethanol, sec-butanol and sec-butyl acetate.
In a specific embodiment, after the gas-liquid separation of the second stream, the main components of the liquid-phase product include sec-butylamine, ethylamine, a small amount of sec-butyl acetate, and a small amount of ethanol and sec-butanol.
According to the invention, the post-ether C4 is an post-ether C4 containing an olefin, and the inclusion of an olefin in the post-ether C4 is common knowledge in the art.
Preferably, the post-etherification C4 includes n-butene, isobutane, n-butane, cis-2-butene, and trans-2-butene.
Preferably, the molar content of the olefin in the post-etherification C4 is 40 to 60 percent.
Preferably, the first catalyst is at least one selected from the group consisting of zeolites, molecular sieves, and acidic resins; more preferably, the first catalyst is a zeolite and/or an acidic resin.
Preferably, the second catalyst is a cobalt-based catalyst taking an inorganic oxide as a carrier; further preferably, the mass content of cobalt in the second catalyst is 10% -35% in a metal element state; further preferably, the inorganic oxide is alumina and/or silica, more preferably alumina.
According to the invention, the first catalyst and the second catalyst are used only by meeting the operation requirements of the process, and do not need to be used for a specific production process.
Preferably, in step (1), the molar ratio of the acetic acid to the olefin in C4 after etherification is (0.8-0.95): 1. under the proportion, the olefin in C4 is slightly excessive after the etherification, so that the complete conversion of acetic acid can be realized, and the phenomenon that the acetic acid is remained in the first stream and reacts with the ammonia added later to generate salt is avoided.
Preferably, in the step (2), the mole ratio of the sec-butyl acetate to the hydrogen and the ammonia is 1: (3-15): (2-25); further preferably, the mole ratio of the sec-butyl acetate to the hydrogen and the ammonia is 1: (5-10): (4-15). Under the proportion of the hydrogen, the ammonia and the sec-butyl acetate, the second catalyst has excellent activity and sec-butylamine selectivity.
Preferably, the temperature of the first reaction is 80-100 ℃, and the pressure is 1.0-3.0 MPa; further preferably, the temperature of the first reaction is 85-100 ℃ and the pressure is 1.5-2.5 MPa. Under the temperature and the pressure, the acetic acid reacts with the olefin in the ether-back carbon four under the catalytic action of the catalyst to generate the sec-butyl acetate, and the catalytic activity is better; meanwhile, the reaction temperature is lower, and side reactions can be greatly reduced. Preferably, the temperature of the second reaction is 150-220 ℃, and the pressure is 1.0-2.5 MPa; further preferably, the temperature of the second reaction is 160-200 ℃ and the pressure is 1.3-2.5 MPa. Under the temperature and the pressure, the catalyst for the ammoniation reaction has higher activity, high selectivity of sec-butylamine and reduced occurrence probability of side reaction.
Preferably, in the step (1), the liquid hourly space velocity of the acetic acid is 0.1-1.5 h-1(ii) a Further preferably, the liquid hourly space velocity of the acetic acid is 0.2-1 h-1。
The invention has the beneficial effects that:
the method for preparing sec-butylamine by C4 after etherification only needs two reaction processes, firstly, the olefin component in C4 after etherification and acetic acid are esterified to generate sec-butyl acetate, then the sec-butyl acetate is subjected to one-step hydroamination to generate sec-butylamine, and partial ethylamine is coproduced.
The separation process is simple, the sec-butylamine and ethylamine products can be obtained only by simple separation, the method is suitable for industrial application, and the phenomena of surplus acetic acid production capacity and unreasonable utilization of C4 after ether treatment can be solved to a certain extent.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 shows a flow diagram of a process for preparing sec-butylamine through post-ether C4 according to one embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
This example provides a process for the preparation of sec-butylamine via post-ethereal C4.
As the first catalyst, a macroporous sulfonic acid type cation exchange resin available from Deng Ming Zhu specialty resins, Inc. was used.
The second catalyst was prepared as follows:
(1) and (3) carrier molding: 300g of alumina powder was mixed with 6g of sesbania powder in a kneader. Adding 270mL of water, kneading for 20min, extruding into 3mm thick clover shape with a bar extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain the alumina carrier.
(2) Loading active components: 188.1g of Co (NO) are taken3)2·6H2O (technical grade, purity 98%), 54.31g of Zn (NO)3)2·6H2Dissolving O (analytically pure) into 180mL of solution with water, and loading the solution on 100g of the obtained carrier by a spray immersion method in two times; after each spray-impregnation, the catalyst was dried at 120 ℃ for 4 hours and then calcined at 390 ℃ for 4 hours to obtain the catalyst in the oxidized state.
(3) Reduction of the oxidation state of the catalyst: and (3) reducing the oxidation-state catalyst obtained in the step (2) by using a mixed gas of 25 vol% of hydrogen and 75 vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the temperature stays for 4 hours when being heated to 170 ℃, then the reduction heating rate is 10 ℃/h, the temperature is heated to 450 ℃, the temperature stays for 8 hours, and then the temperature is reduced to room temperature, so that a second catalyst is obtained, wherein the mass content of cobalt in the second catalyst is 25%.
Reaction raw materials: the acetic acid is glacial acetic acid with purity of more than 99.5%; the hydrogen is steel cylinder hydrogen with the purity of more than 99 percent; the ammonia is steel cylinder liquid ammonia with the purity of more than 99 percent; the composition (molar composition) of the post-etherification C4 fraction was: 17.2 percent of n-butane, 33.2 percent of isobutane, 18.8 percent of n-butene, 16.8 percent of cis-2-butene and 13.5 percent of trans-2-butene.
The reaction steps are as follows: the first reactor and the second reactor both adopt fixed bed tubular reactors, 100mL of first catalyst is filled in the middle position in the first reactor, and other positions are filled by ceramic rings; the middle position in the second reactor is filled with 100mL of second catalyst, and other parts are filled with ceramic rings.
Fig. 1 shows a flow diagram of a process for preparing sec-butylamine through post-ether C4 according to one embodiment of the present invention. Referring to fig. 1, the process for preparing sec-butylamine by post-ethereal C4 comprises the following steps:
(1) uniformly mixing acetic acid and C4 after ether treatment in a first mixer, then feeding the mixture into a first reactor, filling a first catalyst into the first reactor, and performing esterification reaction (namely a first reaction) under the action of the first catalyst to obtain a first stream containing sec-butyl acetate;
(2) uniformly mixing the first stream with hydrogen and ammonia in a second mixer, then feeding the mixture into a second reactor, and carrying out hydroamination (namely, carrying out a second reaction) under the action of a second catalyst to obtain a second stream containing sec-butylamine;
(3) and carrying out gas-liquid separation on the second flow to obtain the sec-butylamine in a liquid-phase product.
Wherein, acetic acid: the olefins in the post-ethereal C4 component (molar ratio) was 0.9: 1; the mole ratio of sec-butyl acetate to hydrogen in the first stream is 1: 5, the molar ratio of sec-butyl acetate to ammonia in the first stream is 1: 10; the reaction temperature in the first reactor is 85 ℃, and the reaction pressure is 1.8 MPa; the reaction temperature in the second reactor is 180 ℃, and the reaction pressure is 1.7 MPa; the liquid hourly space velocity of the acetic acid is 0.8h-1。
The results of the important composition of the first stream and the second stream are shown in table 1:
TABLE 1
As can be seen from Table 1, the first step of esterification reaction of acetic acid and olefin in C4 after etherification, the acetic acid conversion rate is 99.98%, and the sec-butyl acetate selectivity is 99.96%. And in the second step, sec-butyl acetate is directly subjected to hydroamination, the conversion rate of the sec-butyl acetate is 93.4%, and the selectivity of sec-butylamine is 96.0%.
Example 2
This example provides a process for the preparation of sec-butylamine via post-ethereal C4.
As the first catalyst, a macroporous sulfonic acid type cation exchange resin available from Deng-Dong-Ming-Zhu specialty resins, Inc. was used.
The second catalyst was prepared as follows:
(1) and (3) carrier molding: 300g of alumina powder was mixed with 6g of sesbania powder in a kneader. Adding 270mL of water, kneading for 20min, extruding into 3mm thick clover shape with a bar extruder, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain the alumina carrier.
(2) Loading active components: 271.4g of Co (NO) was taken3)2·6H2Dissolving O (industrial grade, purity 98%) into 176mL of solution with water, and loading the solution on 100g of the obtained carrier by a spray immersion method in two times; after each spray-impregnation, the catalyst was dried at 120 ℃ for 4 hours and then calcined at 400 ℃ for 4 hours to obtain the catalyst in the oxidized state. (3) Reduction of the oxidation state of the catalyst: and (3) reducing the oxidation-state catalyst obtained in the step (2) by using a mixed gas of 25 vol% of hydrogen and 75 vol% of nitrogen, wherein the reduction heating rate is 10 ℃/h, the temperature stays for 4 hours when being heated to 170 ℃, then the reduction heating rate is 10 ℃/h, the temperature is heated to 450 ℃, the temperature stays for 8 hours, and then the temperature is reduced to room temperature, so that a second catalyst is obtained, wherein the mass content of cobalt in the second catalyst is 35%.
Reaction raw materials: the acetic acid is glacial acetic acid with purity of more than 99.5%; the hydrogen is steel cylinder hydrogen with the purity of more than 99 percent; the ammonia is steel cylinder liquid ammonia with the purity of more than 99 percent; the composition (molar composition) of the post-etherification C4 fraction was: n-butane 18.1%, isobutane 30.9%, n-butene 19.8%, cis-2-butene 18.4%, trans-2-butene 12.7%.
The reaction steps are as follows: the first reactor and the second reactor both adopt fixed bed tubular reactors, 100mL of first catalyst is filled in the middle position in the first reactor, and other positions are filled by ceramic rings; the middle position in the second reactor is filled with 100mL of second catalyst, and other parts are filled with ceramic rings.
The method for preparing sec-butylamine through C4 after etherification comprises the following steps:
(1) uniformly mixing acetic acid and C4 after ether treatment in a first mixer, then feeding the mixture into a first reactor, filling a first catalyst into the first reactor, and performing esterification reaction (namely a first reaction) under the action of the first catalyst to obtain a first stream containing sec-butyl acetate;
(2) uniformly mixing the first stream with hydrogen and ammonia in a second mixer, then feeding the mixture into a second reactor, and carrying out hydroamination (namely, carrying out a second reaction) under the action of a second catalyst to obtain a second stream containing sec-butylamine;
(3) and carrying out gas-liquid separation on the second flow to obtain the sec-butylamine in a liquid-phase product. Wherein, acetic acid: olefins in post-ethereal C4 component (molar ratio) 0.85: 1; the mole ratio of sec-butyl acetate to hydrogen in the first stream is 1: 9, the molar ratio of sec-butyl acetate to ammonia in the first stream is 1: 18; the reaction temperature in the first reactor is 95 ℃, and the reaction pressure is 2.3 MPa; the reaction temperature in the second reactor is 200 ℃, and the reaction pressure is 2.2 MPa; the liquid hourly space velocity of the acetic acid is 0.4h-1。
The results of the important composition of the first stream and the second stream are shown in table 2:
TABLE 2
As can be seen from Table 2, the first step of esterification reaction of acetic acid and olefin in C4 after etherification, the acetic acid conversion rate is 99.95%, and the sec-butyl acetate selectivity is 99.97%. And in the second step, sec-butyl acetate is directly subjected to hydroamination, the conversion rate of the sec-butyl acetate is 93.7%, and the selectivity of sec-butylamine is 95.5%.
The embodiment shows that the method for preparing sec-butyl alcohol has high selectivity on sec-butyl amine, good sec-butyl alcohol conversion rate, capacity of co-producing ethylamine, good market prospect and high added value, and can effectively utilize C4 and acetic acid resources after ether production.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A process for preparing sec-butylamine through post-etheric C4, characterized in that it comprises the steps of:
(1) carrying out a first reaction on acetic acid and etherified C4 under the action of a first catalyst to obtain a first stream containing sec-butyl acetate;
(2) and uniformly mixing the first stream with hydrogen and ammonia, and then carrying out a second reaction under the action of a second catalyst to obtain a second stream containing sec-butylamine.
2. The process of claim 1, wherein the post-ethereal C4 comprises n-butene, isobutane, n-butane, cis-2-butene, and trans-2-butene.
3. The process of claim 1, wherein the post-etherification C4 has a molar olefin content of 40% to 60%.
4. The process of claim 1, wherein the first catalyst is selected from at least one of a zeolite, a molecular sieve, and an acidic resin;
preferably, the first catalyst is a zeolite and/or an acidic resin.
5. The process of claim 1, wherein the second catalyst is a cobalt-based catalyst supported on an inorganic oxide;
preferably, the mass content of cobalt in the second catalyst is 10-35% in the form of metal element;
preferably, the inorganic oxide is alumina and/or silica, more preferably alumina.
6. The process of claim 1, wherein in step (1), the molar ratio of the acetic acid to the olefin in post-ether C4 is (0.8-0.95): 1.
7. the process of claim 1, wherein in the step (2), the mole ratio of the sec-butyl acetate to the hydrogen and the ammonia is 1: (3-15): (2-25);
preferably, the mole ratio of the sec-butyl acetate to the hydrogen and the ammonia is 1: (5-10): (4-15).
8. The process according to claim 1, wherein the temperature of the first reaction is 80-100 ℃ and the pressure is 1.0-3.0 MPa;
preferably, the temperature of the first reaction is 85-100 ℃ and the pressure is 1.5-2.5 MPa.
9. The method as claimed in claim 1, wherein the temperature of the second reaction is 150 ℃ and 220 ℃, and the pressure is 1.0-2.5 MPa;
preferably, the temperature of the second reaction is 160-200 ℃, and the pressure is 1.3-2.5 MPa.
10. The method according to claim 1, wherein in the step (1), the liquid hourly volume space velocity of the acetic acid is 0.1-1.5 h-1；
Preferably, the liquid hourly volume space velocity of the acetic acid is 0.2-1 h-1。
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| GB421718A (en) * | 1933-04-26 | 1934-12-27 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of amines and amides |
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