CN101037389A - Method for preparing organic amine by directly aminating low-carbon olefin - Google Patents

Method for preparing organic amine by directly aminating low-carbon olefin Download PDF

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CN101037389A
CN101037389A CN 200710040057 CN200710040057A CN101037389A CN 101037389 A CN101037389 A CN 101037389A CN 200710040057 CN200710040057 CN 200710040057 CN 200710040057 A CN200710040057 A CN 200710040057A CN 101037389 A CN101037389 A CN 101037389A
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organic amine
low
reaction
ammonia
reactor
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金杏妹
马云飞
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The invention discloses a method for directly amination to produce organic amine by the lower olefins including following steps: continuously feeding the lower olefins and ammonia into the reactor having the catalyzer for an amination reaction, collecting the reaction product, i.e. target organic amine. The catalyzer components and weight percentage comprises: molecular screen of 55-89%; binder of 10-44% which is selected from Al2O3; modified element of 1-10% which is selected from rare earth element, transition metal or alkaline earth metal element. The olefin percent conversion is more than 10%, and the amide selectivity is more than 99%. The inventive operation method benefits much to the catalytic properties. Compared to the current technology, the invention provides the catalyzer with a high activity, a reaction product with a good selectivity and an organic amine with a good quality.

Description

Method by the direct amination system organic amine of low-carbon alkene
Technical field
The invention belongs to a kind of preparation method of organic amine, being specifically related to by low-carbon alkene is raw material, prepares the method for organic amine in the presence of modified molecular sieve catalyst with ammonia react.
Background technology
The synthetic method of organic aminated substance is a lot, as tert-butylalcohol hydrolysis method, the direct amination method of the trimethyl carbinol, Ritter reaction, alkene prussic acid method and alkene one acetonitrile direct hydrolysis method.Above-mentioned technology will be used mineral acid, not only causes equipment corrosion, and it is serious also to have an environmental pollution, shortcoming such as energy loss is big.Therefore optimal approach is to synthesize amine by alkene and ammonia direct reaction.
R-CH＝CH 2+NH 3→R-CH(NH 2)-CH 3
Early 1980s, U.S. Air Products and chemical Inc has reported with rare-earth metal La or H at US 430725 +The silicoaluminate of exchange, Y zeolite are as catalyzer, and in 270～310 ℃ of reactions down of temperature, transformation efficiency is 6.1%, and selectivity can reach 100%.
BASF AG is at DE19526502, EP0752410 is reported in 270 ℃, 28Mpa, with MCM-22 after handling through multistep, PSH-3, SSZ-25 is a catalyzer, the TERTIARY BUTYL AMINE yield of isobutene aminating reaches 20.5%, at DE19545875, EP0778259, EP0785185, EP0786449, DE19530177 is to beta-zeolite, SSZ-26, SSZ-33, SSZ-37, the aluminate or phosphate that tool is zeolite structured, the amination performance of hexagon faujusite is studied, the catalytic performance of finding the β zeolite is better, the direct aminating TERTIARY BUTYL AMINE yield of iso-butylene can reach 22.67% under above-mentioned reaction conditions, although the BASF operational path makes the TERTIARY BUTYL AMINE yield that large increase arranged, but reaction pressure and temperature of reaction are higher, production unit is had high requirements, and power consumption is big.
Japanese Mitsui Toatsu company successively was reported in SiO at JP77459, JP82864, JP139156 in 1992 2The TiO of content 〉=80% 2, ZrO 2, Al 2O 3, MgO, InO, oxide compounds such as MoO exist down, or in the presence of aluminosilicophosphate or containing metal aluminate or phosphate, at 10Mpa, 200 ℃ of reactions, the selectivity 96% of generation TERTIARY BUTYL AMINE, transformation efficiency reaches 19%.The reaction pressure of isobutene aminating is significantly decreased, but in this technological process owing to use H 3PO 4Serious to equipment corrosion.
China PetroChemical Corporation reports with heteropolyacid-zeolite-A l at calendar year 2001 Chinese patent CN1289761A 2O 3For the solid acid of active ingredient is a catalyzer, 250～400 ℃ of temperature, pressure 3.0～24.0Mpa, alkene feed weight air speed 0.5～5.0h -1, under the reaction conditions of the mol ratio 0.5～10: 1 of ammonia and alkene, the alkene per pass conversion is more than 10%.
Reported method among the previously disclosed patent CN 1436768A of applicant through the direct amination system TERTIARY BUTYL AMINE of the catalytic iso-butylene of the Si-Al molecular sieve of rare earth exchanged modification.150～280 ℃ of temperature of reaction, reaction pressure normal pressure or 0.05～0.5Mpa, the mol ratio of iso-butylene and ammonia is 1: 0.5～1: 2, iso-butylene air speed 260～409h -1Condition under, isobutene conversion reaches 3.8%, the subject matter of this method is that reaction conversion ratio is too low, is difficult to realize industrialization.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of method by the direct amination system organic amine of low-carbon alkene, to overcome said process high temperature, high pressure, environmental pollution, equipment corrosion, and defective such as reaction conversion ratio is low.
Method of the present invention comprises the steps:
Low-carbon alkene and ammonia are fed reactor packed with catalyst continuously carry out amination reaction, temperature of reaction is 150～340 ℃, is preferably 200～310 ℃, reaction pressure is 0.1～10.0MPa, best 0.2～8.0Mpa, collecting reaction product is the target product organic amine;
The general structure of said organic amine is as follows:
RCH(NH 2)R 1
R in the formula 1Be H or CH 3, preferably TERTIARY BUTYL AMINE, ethamine, propylamine or n-Butyl Amine 99 etc.;
R is C nH 2n, n=1-5;
Said low-carbon alkene is the normal olefine of 2～6 carbon atoms or isomeric olefine or its mixture of 2～6 carbon atoms, preferred iso-butylene;
The mol ratio of low-carbon alkene and ammonia is 1: 0.5～1: 4, best 1: 1～4.0;
In the reactor, the low-carbon alkene air speed is 100～1000h -1, best 200～800h -1
Can be to feed ammonia or alkene and ammonia earlier simultaneously to enter beds by reactor head, the gas of reactor outlet, after the organic amine product was removed in separation, unreacted lower boiling reactant circulated with the unstripped gas that replenishes and enters reactor;
Said is the Si-Al molecular sieve-Al that contains rare earth element with catalyzer 2O 3Catalyzer, wherein each component has different functions, and component and weight percent content comprise:
Molecular sieve 55-89%, preferably 70-85%
Cakingagent 10-44%, preferably 15-30%
Modifying element 1～10%
A kind of in H β, Nu-, MCM-, ZSM-5, ZSM-11 or mordenite of said molecular screening, the Si/Al mol ratio of molecular sieve is preferably 10～250;
Cakingagent is selected from Al 2O 3, preferably select γ-Al for use 2O 3
Said modifying element is selected from rare earth element, transition metal or alkali earth metal
Said rare earth element is selected from one or more among La, Ce, Pr or the Sr;
Said transition metal or alkali earth metal are selected from one or more among Cu, Mn, Co, K, P, Mg, Zn or the W;
The modification Si-Al molecular sieve Preparation of catalysts method that Preparation of catalysts can adopt the present technique field to be familiar with, as open reported method in the katalysis basic science press (2005), following catalyst preparation process is that the contriver recommends:
(1) the former powder of Si-Al molecular sieve being added weight concentration is 0.5%～3.5% NH 4In the Cl aqueous solution, keeping liquid-solid ratio is 6: 1～10: 1, at 80 ℃ of left and right sides reflux condensation modes, exchange, the exchange after scouring to do not have chlorion exist, 110 ℃ of dryings, exchange secondary repeatedly; 400～600 ℃ of thermal treatments 4～10 hours, get the former powder of H-type Si-Al molecular sieve then.
(2) the former powder of above-mentioned H-type Si-Al molecular sieve impregnated in nitrate or the carbonate aqueous solution that weight concentration is 5～30% modifying element, excess solution dipping 6 hours, the elimination surplus solution, room temperature ageing 12 hours is then 400～500 ℃ of thermal treatments 4～10 hours;
(3) with the modification Si-Al molecular sieve and the tackiness agent mixed grinding of step (2), the interpolation weight percent is 2～10% HNO 3The aqueous solution grinds, and extruded moulding is dry, 400～700 ℃ of roastings 4～10 hours, said catalyzer.
Compared with prior art, distinguishing feature of the present invention is: this process engineering does not use mineral acid to avoid equipment corrosion and environmental pollution; Because this process engineering adopts direct amination process, has avoided the polystep reaction energy consumption big, the shortcoming of technical process complexity; Because process of the present invention adopts the molecular sieve catalyst through modification, has avoided the polymerization of alkene, has improved reaction preference; Because molecular sieve catalyst of the present invention is through rare earth element or transition metal modification, improved catalytic performance, process of the present invention can be carried out under lower temperature of reaction and reaction pressure, and the selectivity ratios prior art of conversion of olefines rate and aminate increases, and catalyst life is long.
Embodiment
To come below that the invention will be further described by some embodiment:
Embodiment (1～10)
Catalyzer of the present invention can prepare by the following method:
1. with 90 ml concns the NH of 0.3mol/mL with the former powder of 10 gram Si-Al molecular sieves 4The Cl aqueous solution refluxed 5 hours about 80 ℃, carried out ion-exchange, washing, 110 ℃ of oven dry, then 400 ℃ of roastings 6 hours, got the former powder of H-type Si-Al molecular sieve.
2. the 10 former powder of H-type Si-Al molecular sieve that make of gram steps 1 be impregnated in the nitrate or carbonate solution of modifying element, ageing is after 12 hours, in 110 ℃ of dryings 2 hours, and 400 ℃ of roastings 6 hours, the modification Si-Al molecular sieve.
3. the 7 gram modification Si-Al molecular sieves that step 2 made and 3 gram tackiness agent γ-Al 2O 3Mix, grind evenly, then Dropwise 5 milliliter 5% (wt) HNO slowly 3The aqueous solution is ground to the mud shape, extruded moulding, forming composition drying, 600 ℃ of roastings 4 hours, modification Si-Al molecular sieve catalyzer, wherein the Si/Al mol ratio is 10;
4. the preparation of TERTIARY BUTYL AMINE: the different modification Si-Al molecular sieves that 2 gram steps 3 are made are seated in the fixed-bed reactor with 50 purpose granularities, under 250 ℃, use nitrogen purging 2 hours, make catalyst activation; Make liquefied olefines and liquefied ammonia enter the vaporizing chamber vaporization respectively then and mix, the reaction mixture gas after the vaporization enters fixed-bed reactor, and fixed-bed reactor are long 50cm, external diameter 1.4cm, and the stainless steel tube of internal diameter 1.0cm places process furnace;
Be 210 ℃ in temperature of reaction respectively, reaction pressure is 0.1Mpa, and iso-butylene and ammonia raw materials components mole ratio are 1: 1, and the iso-butylene air speed is 225h -1Down reaction of reaction conditions, experimental result sees Table 1.
Table 1:
Modifying element Modifying element content (wt.%) Isobutene conversion (%) TERTIARY BUTYL AMINE selectivity (%)
Embodiment 1 Ce 1 1.52 ＞99
Embodiment 2 Ce 2 1.63 ＞99
Embodiment 3 Ce 3 1.50 ＞99
Embodiment 4 Mo 2 1.40 ＞99
Embodiment 5 Pr 2 1.63 ＞99
Embodiment 6 Pr 3 1.94 ＞99
Embodiment 7 Pr 4 1.69 ＞99
Embodiment 8 H 2 1.46 ＞99
Embodiment 9 Nd 2 1.71 ＞99
Embodiment 10 P 2 1.29 ＞99
Embodiment 11～13
According to the method for embodiment 6, the employing iso-butylene is a raw material, and molecular screening is from mordenite, and wherein the Si/Al mol ratio is 250; Changing temperature of reaction is 200 ℃, 220 ℃, 230 ℃, the results are shown in table 2.
Table 2:
Temperature of reaction (℃) Isobutene conversion (%) TERTIARY BUTYL AMINE selectivity (%)
Embodiment 11 200 1.31 ＞99
Embodiment 12 220 1.68 ＞99
Embodiment 13 230 1.55 ＞99
Embodiment 14～16
Peace just changes reaction and is 1.2MPa, 1.6MPa, 2.0MPa according to the method for embodiment 6, and reaction result is listed in table 3.
Table 3:
Reaction pressure (MPa) Temperature of reaction (℃) Isobutene conversion (%) TERTIARY BUTYL AMINE selectivity (%)
Embodiment 14 1.2 240 6.21 ＞99
Embodiment 15 1.6 250 8.03 ＞99
Embodiment 16 2.0 250 10.21 ＞99
Embodiment 17～18
The method of peace photograph embodiment 6 just changes iso-butylene and the ammonia raw materials components mole ratio is 1.0: 2.0,1.0: 2.5, and reaction result is listed in table 4.
Table 4:
Iso-butylene: ammonia is than (mol) Isobutene conversion (%) TERTIARY BUTYL AMINE selectivity (%)
Embodiment 17 1.0∶2.0 2.17 ＞99
Embodiment 18 1.0∶2.5 1.59 ＞99
Embodiment 19～21
Peace just changes the raw material feeding manner according to the method for embodiment 6, and reaction result is listed in table 5.
Table 5:
Feeding manner Isobutene conversion (%)
Embodiment 19 Feed iso-butylene earlier, feed the gas mixture of ammonia and alkene again 1.02
Embodiment 20 Feed ammonia and iso-butylene simultaneously 1.48
Embodiment 21 Feed ammonia earlier, feed the gas mixture of ammonia and alkene again 1.94

Claims (10)

1. the method by the direct amination system organic amine of low-carbon alkene is characterized in that, comprises the steps: low-carbon alkene and ammonia successive feeding reactor packed with catalyst are carried out amination reaction, and collecting reaction product is the target product organic amine;
Said catalyst component and weight percent content comprise:
Molecular sieve 55-89%, cakingagent 10-44%, modifying element 1～10%;
Cakingagent is selected from Al 2O 3
Said modifying element is selected from rare earth element, transition metal or alkali earth metal
Said rare earth element is selected from one or more among La, Ce, Pr or the Sr;
Said transition metal or alkali earth metal are selected from one or more among Cu, Mn, Co, K, P, Mg, Zn or the W.
2. method according to claim 1 is characterized in that, temperature of reaction is 150～340 ℃, and reaction pressure is 0.1～10.0Mpa.
3. method according to claim 1 is characterized in that, the general structure of said organic amine is as follows: RCH (NH 2) R 1
R in the formula 1Be H or CH 3R is C nH 2n, n=1-5;
Said low-carbon alkene is normal olefine or 2～6 isomeric olefines or its mixture of 2～6 carbon atoms; The mol ratio of low-carbon alkene and ammonia is 1: 0.5～1: 4.
4. method according to claim 3 is characterized in that, low-carbon alkene is a TERTIARY BUTYL AMINE.
5. method according to claim 1 is characterized in that cakingagent is selected from γ-Al 2O 3
6. method according to claim 1 is characterized in that, catalyzer, and component and weight percent content comprise: molecular sieve 70-84%, cakingagent 15-29%, modifying element 1～10%.
7. method according to claim 1 is characterized in that, a kind of in H β, Nu-, MCM-, ZSM-5, ZSM-11 or mordenite of said molecular screening, and the Si/Al mol ratio of molecular sieve is 10～250.
8. method according to claim 2 is characterized in that, in the reactor, the low-carbon alkene air speed is 100～1000h -1
9. according to each described method of claim 1～8, it is characterized in that, feed ammonia or alkene and ammonia earlier and simultaneously enter beds by reactor head.
10. method according to claim 9 is characterized in that, the gas of reactor outlet, and after the organic amine product was removed in separation, unreacted lower boiling reactant circulated with the unstripped gas that replenishes and enters reactor.
CN 200710040057 2007-04-26 2007-04-26 Method for preparing organic amine by directly aminating low-carbon olefin Pending CN101037389A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101869836B (en) * 2009-04-27 2011-12-28 中国石油化工股份有限公司 Catalyst for preparing low-grade aliphatic amine and preparation method and application thereof
CN105457673A (en) * 2016-01-12 2016-04-06 西安近代化学研究所 Amination catalyst and preparation method thereof
CN106040289A (en) * 2016-06-03 2016-10-26 中国科学院大连化学物理研究所 Preparation method of catalyst applied to tert-butylamine production through direct amination of isobutene and application
CN107486236A (en) * 2016-06-13 2017-12-19 中国科学院大连化学物理研究所 A kind of catalyst for producing the propylamine of 2 methyl 2 and its preparation method and application
CN107899605A (en) * 2017-11-22 2018-04-13 山东玉皇化工有限公司 It is a kind of to be used to catalyze and synthesize catalyst of tert-butylamine and preparation method thereof
CN111056948A (en) * 2019-12-16 2020-04-24 中国科学院大连化学物理研究所 Process for preparing hexamethylenediamine
CN111068741A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for synthesizing low-carbon olefin by one-step method and application thereof
CN115254181A (en) * 2022-09-28 2022-11-01 淄博鲁华泓锦新材料集团股份有限公司 Catalyst for producing tert-butylamine and preparation method and application thereof

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101869836B (en) * 2009-04-27 2011-12-28 中国石油化工股份有限公司 Catalyst for preparing low-grade aliphatic amine and preparation method and application thereof
CN105457673A (en) * 2016-01-12 2016-04-06 西安近代化学研究所 Amination catalyst and preparation method thereof
CN105457673B (en) * 2016-01-12 2018-07-31 西安近代化学研究所 A kind of amination catalysis and preparation method thereof
CN106040289B (en) * 2016-06-03 2018-06-08 中国科学院大连化学物理研究所 A kind of preparation method and application of isobutene direct aminatin production tert-butylamine catalyst
CN106040289A (en) * 2016-06-03 2016-10-26 中国科学院大连化学物理研究所 Preparation method of catalyst applied to tert-butylamine production through direct amination of isobutene and application
CN107486236A (en) * 2016-06-13 2017-12-19 中国科学院大连化学物理研究所 A kind of catalyst for producing the propylamine of 2 methyl 2 and its preparation method and application
CN107486236B (en) * 2016-06-13 2020-04-14 中国科学院大连化学物理研究所 Catalyst for producing 2-methyl-2-propylamine and preparation method and application thereof
CN107899605A (en) * 2017-11-22 2018-04-13 山东玉皇化工有限公司 It is a kind of to be used to catalyze and synthesize catalyst of tert-butylamine and preparation method thereof
CN111068741A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for synthesizing low-carbon olefin by one-step method and application thereof
CN111068741B (en) * 2018-10-18 2023-04-07 中国石油化工股份有限公司 Catalyst for synthesizing low-carbon olefin by one-step method and application thereof
CN111056948A (en) * 2019-12-16 2020-04-24 中国科学院大连化学物理研究所 Process for preparing hexamethylenediamine
CN115254181A (en) * 2022-09-28 2022-11-01 淄博鲁华泓锦新材料集团股份有限公司 Catalyst for producing tert-butylamine and preparation method and application thereof
CN115254181B (en) * 2022-09-28 2023-01-06 淄博鲁华泓锦新材料集团股份有限公司 Method for producing tert-butylamine

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