CN1289761A - Process for direct amination of olefine - Google Patents

Process for direct amination of olefine Download PDF

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Publication number
CN1289761A
CN1289761A CN 99113283 CN99113283A CN1289761A CN 1289761 A CN1289761 A CN 1289761A CN 99113283 CN99113283 CN 99113283 CN 99113283 A CN99113283 A CN 99113283A CN 1289761 A CN1289761 A CN 1289761A
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Prior art keywords
alkene
amination method
zeolite
reaction
heteropolyacid
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CN 99113283
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CN1102574C (en
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勾连科
霍稳周
于镝明
许波
姜晓晖
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Abstract

A process for direct amination of olefine features that under the existance of solid acid catalyst whose active component is heteropoly acid-zeolite-Al2O3, ammonia and olefine in mole ratio of (0.5-10):1 take part in reaction at 250-400 deg.C and 3-24 MPa. Its advantages are high one-pass transform rate (10% or more) of olefine, high efficiency and long service life of catalyst.

Description

A kind of processing method of direct amination of olefine
The present invention relates to a kind of with alkene be raw material in the presence of ammonia and solid acid catalyst, ammonification prepares the method for amine.
The synthetic method of aminate mainly contains following several:
1) hydrolysis method: with low-carbon alcohol, urea is route, through the synthetic aminate of hydrolysis.Though this method has characteristics such as technology is simple, raw material is easy to get, but no matter be calcium hydroxide hydrolysis method or sodium hydroxide hydrolysis method, perhaps need be in hydrolysis under the hot conditions, perhaps use high boiling solvent (ethylene glycol or ethylene glycol ethyl ether), and the recovery of high temperature production technology and high boiling solvent still there is certain technical difficulty at present.This explained hereafter cost is higher in addition.
In 1983 German Patent EP68219 and DE3124654 have delivered the technology that N-tert-butylamides hydrolysis method prepares TERTIARY BUTYL AMINE: the basic hydrolysis of N-tert-butylamides can prepare toluylic acid and TERTIARY BUTYL AMINE simultaneously.People's such as Irie Japanese Patent JP61103858 has also reported hydrolysis method technology.RNH 2(R=C 4～22Tertiary alkyl) can be by { MeCH (OH) CONHR} prepares, simultaneously common property lactic acid at 130～220 ℃ of following alkaline hydrolysis tertiary alkyl lactic amides.
Recently people such as army of kingdom has reported that in the fifth phase in 1996 " chemical industry Technological Economy " tert-butylalcohol water medium causticization hydrolysis method synthesizes the TERTIARY BUTYL AMINE technology.This synthesis technique substitutes high boiling solvent with water, obtains content and is 〉=95% TERTIARY BUTYL AMINE.It is said that this technology can make the production cost of TERTIARY BUTYL AMINE reduce to 2.78 ten thousand yuan/ton.But the above technology is the batch process process, is difficult for carrying out large-scale industrial production.
2) low-carbon alkene, prussic acid method: early eighties U.S. Rohm and Haas Company (US) Independenec Mall West, Philadelphia, Pennsy Lvania 1 adopts iso-butylene/prussic acid legal system to be equipped with TERTIARY BUTYL AMINE, this method is alkene and prussic acid and sulfuric acid reaction, generate vitriol and obtain corresponding aminate with the ammonia neutralization then, simultaneously by-product hydrogen sulfate amine.
In 1982 German Patent 50869,50870,50871,50868 has been reported the technology of handling preparation amine such as branched-chain alkene and alcohol with HCN, and the tertiary alkyl ester of primary alconol or secondary alcohol can get uncle's N-alkanamine or cycloalkanes amine and brothers alkyl formate with the strong acid treatment of HCN and≤2mol.The subject matter that this technological process exists is to use HCN, and is unfavorable to environment and production.
3) olefin catalytic ammoniation process: early eighties United States Patent (USP) 4375002 has been developed zeolite catalysis NH 3Reaction process with alkene.Can obtain the highly selective amine product by following improvement: (1) uses enough temperature and pressures to generate the amine product, but can not cause olefinic polymerization; (2) use a kind of crystalline silica-aluminate as catalyzer.N (ethene): n (NH 3)=3: 2,386 ℃ of temperature, pressure 20.67MPa uses the reaction of catalyst S K-500 (pelleted La exchanging zeolite Y) Study on Catalytic Amination of Alcohols, obtains conversion of ethylene 13.2% and EtNH 2Selectivity 79%.This technological process has had certain improvement to the polymerization of alkene, but still have the part olefinic polymerization under 386 ℃ high temperature, makes EtNH 2Selectivity on the low side.
Japanese Patent JP04139156 had reported with C in 9 years 4～8Iso-butylene or tertiary alkanol and NH 3Catalyzed reaction prepares TERTIARY BUTYL AMINE technology.Aluminosilicophosphate or metallic aluminate are housed, by handling C in the reactor 4～8Iso-butylene or tertiary alkanol and NH 3Can prepare TERTIARY BUTYL AMINE.Containing (Si 0.05Al 0.45P 0.5) add iso-butylene and NH in the reactor of catalyzer 3, be that 9.7MPa can obtain Me with pressure at 270 ℃ 3CNH 2, selectivity 96%, isobutene conversion 17%.TERTIARY BUTYL AMINE is at H 3PO 4And/or the phosphoric acid salt existence down, by handling iso-butylene or Me 3COH and NH 3Prepare.Iso-butylene and NH 3Mixture enter H be housed 3PO 4Reactor in, under 270 ℃ and 9.8MPa condition, obtain TERTIARY BUTYL AMINE, selectivity 97%, isobutene conversion 18%.Use H in this technological process 3PO 4Cause equipment corrosion serious.
German Patent 4206992 had also been reported iso-butylene and NH under zeolite or an acidic catalyst effect in 9 years 3The prepared in reaction TERTIARY BUTYL AMINE.Catalyzer operation lifetime 〉=100h is with the catalyzer duration of contact of 10～30mol/kgcath preferably, selectivity 〉=99.8%.In the reactor that H type ZSM catalyzer is housed, NH 3: iso-butylene feeds with mol ratio 2: 1, and under 25MPa and 300 ℃ of conditions, isobutene conversion is 11.6%.This process characteristic is to have improved transformation efficiency and selectivity, but reaction pressure and temperature of reaction are higher, make troubles to suitability for industrialized production.
Developing a kind of dealuminium Y type beta stone (LZY-72) with the ammonium ion exchange in 9 years in the EP587424 patent is used at 280 ℃ of catalyzing N H 3With isobutene reaction, obtain TERTIARY BUTYL AMINE, isobutene conversion is 7.7%, TERTIARY BUTYL AMINE selectivity 〉=99%, this patent does not disclose reaction pressure.
European patent EP 310527 also reported in the presence of catalyzer, can be by alkene and corresponding alcohol and NH 3Prepared in reaction amine.Iso-butylene 56g, NH 390g, (NH 4) 2SO 4The mixture of 20g is at 360gH 2Stir among the O,, can get the 25.6g TERTIARY BUTYL AMINE at 250 ℃ of reaction 10h.At (NH 4) 2SO 4There is down the trimethyl carbinol (Me 3COH) and NH 3Reaction obtains TERTIARY BUTYL AMINE under 240 ℃, and trimethyl carbinol transformation efficiency 30%, this process characteristic are that reaction conditions relaxes, and the problem of existence is periodical operation.
The processing method that the purpose of this invention is to provide a kind of successive direct amination of olefine, high temperature, high pressure and the serious equipment corrosion problem of above-mentioned technological process have been overcome, under lower temperature and pressure, can obtain the selectivity of higher olefin conversion and purpose product.
Technical scheme of the present invention is as described below:
Use contains the zeolite-A l of heteropolyacid 2O 3Catalyzer uses alkene and ammonia as reaction raw materials, 250～400 ℃ of temperature of reaction, and reaction pressure 3.0～24.0MPa, ammonia/alkene (mol) suitable in the reactive system is 0.5～10: 1, the heavy air speed of alkene charging is 0.5～5.0h -1
Above-mentioned alkene and ammonia can adopt the mode of charging to enter reactor from the top together, and maintain reaction under the gas phase state.Preferred reaction conditions is: ammonia/alkene (mol) 1～5: 1, alkene feed weight air speed 1～3h -1(w), 260～350 ℃ of temperature of reaction, reaction pressure 4.0～12.0MPa.
The above-mentioned solid acid catalyst that contains heteropolyacid is a benchmark with the weight percent, contains:
1) zeolite 30%～90%, and preferably 50%～70%, zeolite can be one or more in USY, REUSY, H β, ZSM, NTY, SSY, the mordenite, the SiO of zeolite 2/ Al 2O 3Mol ratio is preferably 20～100.
2) heteropolyacid content 0.01%～10%, is preferably 0.5%～6%, and heteropolyacid can be H 2SO 4, H 3PO 4, 20MoO 32H 3PO 448H 2O, H 2[P (W 2O 7) 5.5(Mo 2O 3) 0.5], H 4[Si (W 3O 10) 4], 20WO 32H 3PO 425H 2O, H 4S[Si (W3O 14) 4] and its esters such as Cu 1.5HS[Si (W 3O 14) 4], AlHS[Si (W 3O 14) 4], Zn 1.5HS[Si (W 3O 14) 4], Na 3HS[Si (W 3O 14) 4], FeHS[Si (W 3O 14) 4] in one or more, be preferably silicotungstic acid or phospho-wolframic acid.
3) γ-Al 2O 310%～70%, preferably 30%～50%.
This catalyzer can prepare by the following method:
(1) with zeolite and γ-Al 2O 3Precursor, water and aqueous nitric acid (concentration is 10%～20%) or phosphate aqueous solution (concentration 10%～15%), add-on is nitric acid or phosphoric acid and γ-Al 2O 3Mol ratio be 0.1～0.5, mix then pinch, moulding, airing at room temperature; (preferably using deionized water and concentration is 10%～15% aqueous nitric acid); (2) the shaping thing that obtains of step (1) was 100～170 ℃ of dryings 4～16 hours; (3) exsiccant shaping thing roasting 5～12 hours under 400～700 ℃ of conditions makes the carrier of catalyzer of the present invention; (4) carrier that step (3) is made floods with the aqueous solution that contains heteropolyacid, and dry then, roasting promptly get catalyzer of the present invention.
Raw material olefin of the present invention can be the normal olefine or the isomeric olefine of 2～6 carbon atoms, purity 〉=95%, and ammonia can use industrial seconds, ammonia content 〉=99.5%.
Alkene amination reaction detailed process of the present invention is as follows:
Raw material olefin and ammonia enter process furnace after squeezing into interchanger and reactor discharging heat exchange by volume pump, alkene and ammonia enter reactor after the process furnace heating, the material that comes out from reactor is through entering separator after by the water cooler cooling after interchanger and raw material olefin and the ammonia heat exchange, separator is normal temperature, normal pressure, its liquid phase is aminate and a spot of other components after separating, and enters storage tank; Gas phase enters drying tower, and dry back alkene and ammonia recycle through recycle compressor.
Compared with prior art, outstanding feature of the present invention is: do not use sulfuric acid or phosphoric acid to avoid equipment corrosion in technological process of the present invention, owing to adopted the high activated catalyst that contains heteropolyacid in the technology of the present invention, process reaction condition therefore of the present invention relaxes, avoided the polymerization of alkene, production cost is low, and catalyst life is long, is easy to carry out large-scale industrial production.
Embodiment 1
With 250ml (200g) granularity 10～26 orders, containing silicotungstic acid is the H β zeolite-A l of 3% (weight) 2O 3(wherein zeolite content is 70% (weight) to catalyzer, γ-Al 2O 3Be 30% (weight)), in the stainless steel reactor of pack into internal diameter 25mm, long 1.5m, (weight space velocity is 1.0h to iso-butylene with 330ml/h -1) input speed enter reactor head, ammonia/alkene (mol) is 2.0, reaction pressure is 6.0MPa, 280 ℃ of temperature of reaction.From the effusive material of reactor bottom after interchanger and raw material olefin and ammonia heat exchange, by entering separator after the water cooler cooling, wherein pressure is normal pressure, temperature is a normal temperature, liquid portion in the separator enters storage tank, and vapour phase partly enters the drying tower of gac, and dried alkene and ammonia recycle through recycle compressor, it forms liquid portion in the storage tank by gas chromatographic analysis, and table 1 is 500 hours result of running.
Embodiment 2～4
According to the method for embodiment 1, just change temperature of reaction and be 260 ℃, 320 ℃, 380 ℃ and the results are shown in table 2.
Table 1:
Runtime (h) Isobutyl alkene per pass conversion (%) The selectivity of TERTIARY BUTYL AMINE (%)
50 13．0 93
100 12．5 94
150 12．0 94
200 12．0 95
250 11．5 96
300 11．8 95
350 12．0 97
400 12．4 98
450 10．5 99
500 12．1 98
Table 2:
Embodiment Reaction conditions Iso-butylene per pass conversion (%) TERTIARY BUTYL AMINE selectivity (%)
Reaction pressure MPa Temperature of reaction ℃ Ammonia alkene compares mol
????2 ????6．0 ????260 ????2．0 ????12．5 ????96
????3 ????6．0 ????320 ????2．0 ????14．5 ????95．5
?4 ????6．0 ????380 ????2．0 ????16．5 ????89
Embodiment 5
With 25ml (20g) granularity 10～26 purpose H β zeolite-A l 2O 3(wherein phospho-wolframic acid is 4% (w) to catalyzer, and zeolite content is 60% (w), γ-Al 2O 3Content is 40% (w)) in the stainless steel reactor of pack into internal diameter 12mm, long 650m, (weight space velocity is 1.0h to iso-butylene with 33ml/h -1) input speed enter reactor head, ammonia/alkene (mol) is 1.5: 1, reaction pressure is 8.0MPa, 280 ℃ of temperature of reaction.From the effusive material of reactor bottom after interchanger and raw material olefin and ammonia heat exchange, by entering separator after the water cooler cooling, wherein pressure is normal pressure, temperature is a normal temperature, liquid portion in the separator enters storage tank, and gas phase partly enters the drying tower of gac, and dried alkene and ammonia recycle through recycle compressor, it forms liquid portion in the storage tank by gas chromatographic analysis, and table 3 is 300 hours result of running.
Table 3:
Runtime (h) Isobutyl alkene per pass conversion (%) The selectivity of TERTIARY BUTYL AMINE (%)
50 15．0 93
100 13．5 96
150 12．0 97
200 12．0 95
250 11．5 98
300 12．5 97
Embodiment 6～8
According to the method for embodiment 5, just changing reaction pressure is that 4.0MPa, 12.0MPa, 16.0MPa the results are shown in table 4.
Table 4:
Embodiment Reaction conditions Iso-butylene per pass conversion (%) TERTIARY BUTYL AMINE selectivity (%)
Reaction pressure MPa Temperature of reaction ℃ Ammonia alkene compares mol
????2 ????4．0 ????280 ????1．5 ????10．5 ????96
????3 ????12．0 ????280 ????1．5 ????15．5 ????95
?4 ????16．0 ????280 ????1．5 ????18．0 ????93

Claims (18)

1. alkene amination method, in the presence of solid acid catalyst, with alkene and ammonia is raw material, synthetic aminate, it is characterized in that using the solid acid catalyst that contains heteropolyacid and zeolite, 250～400 ℃ of temperature of reaction, reaction pressure 3.0～24.0MPa, alkene feed weight air speed 0.5～5.0h -1, the mol ratio of ammonia and alkene is 0.5～10 in the reactive system: 1.
2. alkene amination method according to claim 1 is characterized in that described solid acid catalyst, is benchmark with the weight percent, comprises zeolite 30%～90%, heteropolyacid 0.01%～10%, γ-Al 2O 310%～70%.
3. alkene amination method according to claim 1 is characterized in that described reaction carries out under gas phase state.
4. alkene amination method according to claim 1 is characterized in that described temperature of reaction is 260～350 ℃.
5. method according to claim 1 is characterized in that described reaction pressure is 4.0～12.0MPa.
6. alkene amination method according to claim 1 is characterized in that described alkene feed weight air speed 1.0～3.h -1
7. alkene amination method according to claim 1, the mol ratio that it is characterized in that described ammonia and alkene is 1～5: 1.
8. alkene amination method according to claim 1 and 2 is characterized in that described zeolite is one or more in USY, REUSY, H β, ZSM, NTY, SSY, the mordenite.
9. alkene amination method according to claim 1 and 2 is characterized in that described heteropolyacid is H SO 4, H 3PO 4, 20Mo 32H 3PO 448H 2O, H 2[P (W 2O 7) 5.5(Mo 2O 3) 0.5], H 4[Si (W 3O 10)], 20WO 32H 3PO 425H 2O, H 4S[Si (W 3O 14) 4] and corresponding salt in one or more.
10. alkene amination method according to claim 1 and 2 is characterized in that described zeolite content is 50%～70%.
11. alkene amination method according to claim 1 and 2, the content that it is characterized in that described heteropolyacid is 0.5%～6%.
12. alkene amination method according to claim 1 and 2 is characterized in that described γ-Al 2O 3Content is 30%～50%.
13. alkene amination method according to claim 1 and 2 is characterized in that described zeolite silica alumina ratio is 20～100.
14. alkene amination method according to claim 1 and 2 is characterized in that described heteropolyacid is a silicotungstic acid.
15. alkene amination method according to claim 1 and 2 is characterized in that described heteropolyacid is a phospho-wolframic acid.
16. alkene amination method according to claim 1 and 2 is characterized in that described zeolite is REUSY.
17. alkene amination method according to claim 1 and 2 is characterized in that described zeolite is a H β zeolite.
18. alkene amination method according to claim 1 is characterized in that described olefin feedstock is the normal olefine or the isomeric olefine of 2～6 carbon atoms.
CN 99113283 1999-09-29 1999-09-29 Process for direct amination of olefine Expired - Lifetime CN1102574C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100013A (en) * 2018-10-27 2020-05-05 中国石油化工股份有限公司 Method for preparing tert-butylamine
CN111825555A (en) * 2019-04-17 2020-10-27 中国石油化工股份有限公司 Method for preparing tert-butylamine by using MTBE as raw material
CN111825556A (en) * 2019-04-17 2020-10-27 中国石油化工股份有限公司 Preparation method of tert-butylamine
CN112742454A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Preparation method of supported heteropolyacid catalyst
CN114436853A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Method for preparing tert-butylamine by amination of isobutene
CN114436854A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Method for preparing tert-butylamine from isobutene
CN114436856A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Method for preparing tert-butylamine through isobutene amination
CN114436855A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Method for preparing tert-butylamine from isobutene

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100013A (en) * 2018-10-27 2020-05-05 中国石油化工股份有限公司 Method for preparing tert-butylamine
CN111100013B (en) * 2018-10-27 2023-03-07 中国石油化工股份有限公司 Method for preparing tert-butylamine
CN111825556B (en) * 2019-04-17 2022-09-09 中国石油化工股份有限公司 Preparation method of tert-butylamine
CN111825555A (en) * 2019-04-17 2020-10-27 中国石油化工股份有限公司 Method for preparing tert-butylamine by using MTBE as raw material
CN111825556A (en) * 2019-04-17 2020-10-27 中国石油化工股份有限公司 Preparation method of tert-butylamine
CN111825555B (en) * 2019-04-17 2023-02-03 中国石油化工股份有限公司 Method for preparing tert-butylamine by using MTBE as raw material
CN112742454A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Preparation method of supported heteropolyacid catalyst
CN112742454B (en) * 2019-10-31 2022-08-12 中国石油化工股份有限公司 Preparation method of supported heteropoly acid catalyst
CN114436855A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Method for preparing tert-butylamine from isobutene
CN114436856A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Method for preparing tert-butylamine through isobutene amination
CN114436854A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Method for preparing tert-butylamine from isobutene
CN114436853A (en) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 Method for preparing tert-butylamine by amination of isobutene
CN114436854B (en) * 2020-10-31 2024-02-13 中国石油化工股份有限公司 Method for preparing tert-butylamine from isobutene

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