CN101885686B - Method for producing ethanolamine - Google Patents
Method for producing ethanolamine Download PDFInfo
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- CN101885686B CN101885686B CN2009100572368A CN200910057236A CN101885686B CN 101885686 B CN101885686 B CN 101885686B CN 2009100572368 A CN2009100572368 A CN 2009100572368A CN 200910057236 A CN200910057236 A CN 200910057236A CN 101885686 B CN101885686 B CN 101885686B
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- thanomin
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Abstract
The invention relates to a method for producing ethanolamine, mainly solving the technical problem of high reaction temperature and high system pressure in the prior art. The technical problem is well solved by using a technical scheme in which ethylene oxide and ammonia are used as raw materials and ZSM-5 is taken as a catalyst for reaction to produce ethanolamine under the conditions that the mole ratio of ammonia to ethylene oxide is 0.5-15, the reaction temperature is 50-100 DEG C, the system pressure is 4-12 MPa, and liquid-phase space velocity is 0.5-4h<-1>. The method can be used in the industrial production of the ethanolamine.
Description
Technical field
The present invention relates to a kind of method for the production of thanomin.
Background technology
Alcohol amine compound comprises Monoethanolamine MEA BASF (MEA), diethanolamine (DEA) and trolamine (TEA), because the alcohol amine compound end group is respectively hydroxyl and amido, has the chemical property of alcohols and aminated compounds.Bifunctional makes it become important organic intermediate, and purposes is very extensive.Thanomin is to produce the important basic materials of product such as tensio-active agent, medicine, urethane auxiliary agent, rubber processing aids, deicing fluid auxiliary agent.What the production of thanomin was mainly adopted at present is the oxyethane ammonolysis process.Since Knorr (Knorr L.Chem.Bev., 1897,30:909-911; Chem.Bev., 1899, found first since the Ammonia Process synthesizing ethanolamine that 32:729-731) research of synthesizing ethanolamine attracts more research interest.The researchist of Shell (ReynhartA F A, Beverwijk.US 2186392,1940) company finds, when add ammonium salt in system after, can improve the selectivity of thanomin, and the output of thanomin is directly proportional with the ammonium salt that adds.BASF (Frauenkron M, M ü ller U, Harder W, Unger J, Melder J P, Meier A, Himmel W.US 7119231.2006) company adopts the ammoniacal liquor of high density as reaction raw materials, ammonia concn about 90wt%, NH
3/ EO ratio between 20～25, although the productive rate of MEA reaches more than the 70wt%, the NH in the system
3Excessive far away, increase production cost, and still contained more water in the reactive system.Vamling (Vamling L, Cider L., Ind.Eng.Chem.Prod.Res.Dev.1986, (25): 424-430) etc. employing liquefied ammonia is raw material, take strong-acid ion exchange resin as catalyzer, under high-speed, the productive rate of MEA reaches more than the 70wt%, because ion exchange resin thermally-stabilised not high, and this reaction is strong exothermal reaction, so the application of ion exchange resin is limited by very large.Texcao (Grice N J, Knifton J F.US 4939301.1990; Johnson F L.US 4438281.1984) company adopts Al
2O
3-SiO
2And on montmorillonite the catalyzer such as carried heteropoly acid, yet the activity of catalyzer is not high, the transformation efficiency less than 90% of EO and product do not had selectivity.NipponShokubai (Tsuneki H, Moriya A, Baba H.US 6169207.2001; Moriya A, Tsuneki H.EP0652207.1995; Moriya A, Tsuneki H.US 5880058.1999; Tsuneki H, Moriya A, Baba H.A EP0941986.1999; Tsuneki H, Kirishiki M, Arita Y, Hashimoto Y, Oku T, Shindou H, Urano Y, Morishita F.US 6559342.2003; Tsuneki H.US 6455016.2002) zeolite of company's employing La modification is catalyzer, when La mass loading amount is 10%, and NH
3During/EO=8, the weight selectivity of DEA is about 48%, with the MEA in the product, EO, NH
3After the circulation, the weight selectivity of DEA reaches about 80%, and the charge capacity of La is too high according to a certain percentage, and the Nippon Shokubai researchist of company thinks that La can improve NH
3With the reactive behavior of EO, but this does not explain selectivity rising of DEA, and the said firm does not report the content of amidogen ether in the product yet.
Summary of the invention
Technical problem to be solved by this invention is to have the technical problem that temperature of reaction is high, reaction pressure is high and the oxyethane low conversion rate is low with the thanomin selectivity in the prior art, and a kind of method for the production of thanomin newly is provided.The method has the advantage that temperature of reaction is low, reaction pressure low and the oxyethane transformation efficiency is high and the thanomin selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for the production of thanomin, take ammonia and oxyethane as raw material, nitrogen is reaction medium, the mol ratio of ammonia and oxyethane is 0.5～15, be 50～100 ℃ in temperature of reaction, reaction pressure is 4～12MPa, and the liquid phase air speed is 0.5～4h
-1Under the condition, raw material contacts with catalyzer, and reaction generates thanomin, and wherein used catalyzer comprises following component in weight fraction: a) 40～100 parts of SiO
2/ Al
2O
3Mol ratio is 10～500 ZSM-5 molecular sieve, and wherein the particle diameter of ZSM-5 molecular sieve is 1～5 μ m; B) 0～60 part of binding agent.
In the technique scheme, reaction raw materials ammonia and oxyethane preferred version are for being liquid state; Ammonia and oxyethane mol ratio preferable range are 3～12, and more preferably scope is 6～9; The temperature of reaction preferable range is 60～90 ℃ when raw material and catalyzer contact reacts; The reaction pressure preferable range is 5～10MPa when raw material and catalyzer contact reacts, and more preferably scope is 6～8MPa; Liquid phase air speed preferable range is 1.0～3h when raw material and catalyzer contact reacts
-1, more preferably scope is 1.5～2h
-1The SiO of ZSM-5 molecular sieve
2/ Al
2O
3The mol ratio preferable range is 10～300; The particle diameter preferable range is 1～3 μ m; The binding agent preferred version is selected from aluminum oxide, silicon sol or pseudo-boehmite; When consumption of binder was 0, molecular sieve adopted the ZSM-5 molecular sieve of binder free.In the catalyst preparation process, preferred version is that ZSM-5 molecular sieve carries out finishing with tetraethoxy-silicane.
The present invention proposes a kind of method that prior art is produced thanomin that is different from, obtain a kind of SiO by above-mentioned technical scheme
2/ Al
2O
3Mol ratio is 10～500, and specific surface area is at 200～400 meters
2/ gram, particle diameter is at the catalyzer of 1～5 μ m.Because catalyzer has suitable acidity, do not need to add any metallic element and non-metallic element, just the reaction of ammonia and oxyethane had very high catalytic activity, the transformation efficiency of oxyethane significantly raises, reduce significantly temperature of reaction, fundamentally reduced the system pressure of system.
Catalyzer of the present invention has good acidity distribution, can weaken the etherification reaction degree again in the amination of catalytic epoxyethane liquid phase; So do not have the carbon distribution problem because temperature of reaction is low, and the regeneration of catalyzer is simple.Catalyzer of the present invention is when being used for above-mentioned oxyethane liquid phase amination catalysis, at NH
3/ EO=5 moles/mole, temperature of reaction are that 80 ℃, reaction pressure are that 7.2 MPas, liquid phase air speed are 0.5～4 hour
-1Condition under, the one way weight selectivity sum of monoethanolamine and diethanolamine reaches 93%, the weight content of amidogen ether is below 0.5%, the transformation efficiency of oxyethane can reach more than 98%, has obtained preferably technique effect.
The invention will be further elaborated below by embodiment, but these embodiment in no case are construed as limiting scope of the present invention.
Embodiment
[embodiment 1]
The 187g silicon sol is mixed with the 200mL deionized water, stirred 10 minutes under room temperature, the quadrol of measuring thereafter 5.6mL adds in the above-mentioned mixing solutions, and at room temperature stirs 0.5 hour; According to SiO
2/ Al
2O
3The ratio of=25 (mol ratios) takes by weighing Al
2(SO
4)
318H
2O joins in the above-mentioned mixing solutions, and violent stirring 0.5 hour, will obtain the colloid of white thickness.Add 8gNaOH in the body colloid, regulation system pH value to 13～14, and continue to stir after 1 hour and transfer to crystallizing kettle were in 180 ℃ of constant temperature 36 hours.With the product deionized water wash after the crystallization, and in 100 ℃ of oven dry, resulting molecular sieve places retort furnace after will drying, roasting in air atmosphere, air velocity is 100 ml/min, speed with 15 ℃/min is warming up to 600 ℃, and this roasting temperature 6 hours, obtains thus molecular sieve presoma I.The cyclohexane solution constant temperature that molecular sieve presoma I is placed tetraethoxy-silicane is after 12 hours, and filtration, washing, roasting obtain molecular sieve presoma II.The molecular sieve presoma II of aequum, an amount of nitric acid that gets are mixed with the binding agent aluminum oxide powder of aequum, and adding makes the presoma III of catalyzer in the sesbania powder of weight fraction 0.1～5%.With catalyst precursor III extruded moulding, drying and in 450～650 ℃ of roastings 0.5～24 hour gets the catalyzer finished product.
Get the 10mL molecular sieve catalyst and place reactor, and whether the resistance to air loss of checking system is intact; Then with intrasystem air with N
2Displacement is replaced and is filled with high pressure nitrogen to 6～10MPa in the backward system, and is heated to 50～100 ℃, treats after the homo(io)thermism, according to NH
3The ratio of/EO=6 (mol ratio) passes into ammonia and oxyethane.
[embodiment 2～15]
Get each Step By Condition Kaolinite Preparation of Catalyst and examination catalyzer according to embodiment 1, the only kind of feed change, crystallization condition, roasting condition, proportioning raw materials, the synthesis condition such as surface treatment and shaping of catalyst factor whether, and synthesis condition listed in form 1; Under same examination condition, the resulting catalyzer of different synthetic methods is checked and rated, appraisal result is listed in the form 2.
[embodiment 16～28]
According to each Step By Condition Kaolinite Preparation of Catalyst of embodiment 1 and examination catalyzer, only change the processing parameters such as mol ratio, temperature of reaction, system pressure, air speed of ammonia and oxyethane in the examination condition, list in the form 3.
Claims (5)
1. method for the production of thanomin, take ammonia and oxyethane as raw material, nitrogen is reaction medium, and the mol ratio of ammonia and oxyethane is 3～12, is 60～90 ℃ in temperature of reaction, and reaction pressure is 6～8MPa, and the liquid phase air speed is 1～3h
-1Under the condition, raw material contacts with catalyzer, and reaction generates thanomin, and wherein used catalyzer comprises following component in weight fraction:
A) 40～100 parts of SiO
2/ Al
2O
3Mol ratio is 10～500 ZSM-5 molecular sieve, and wherein the particle diameter of ZSM-5 molecular sieve is 1～5 μ m, and specific surface area is at 200～400 meters
2/ gram;
B) 0～60 part of binding agent.
2. described method for the production of thanomin according to claim 1 is characterized in that ammonia and oxyethane mol ratio are 6～9.
3. described method for the production of thanomin according to claim 1, the liquid phase air speed is 1.5～2h when it is characterized in that raw material and catalyzer contact reacts
-1
4. described method for the production of thanomin according to claim 1 is characterized in that the SiO of ZSM-5 molecular sieve
2/ Al
2O
3Mol ratio is 10～300; Particle diameter is 1～3 μ m; Binding agent is selected from aluminum oxide, silicon sol or pseudo-boehmite; When consumption of binder was 0, molecular sieve adopted the ZSM-5 molecular sieve of binder free.
5. described method for the production of thanomin according to claim 1 is characterized in that in the catalyst preparation process, ZSM-5 molecular sieve carries out finishing with tetraethoxy-silicane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100572368A CN101885686B (en) | 2009-05-13 | 2009-05-13 | Method for producing ethanolamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100572368A CN101885686B (en) | 2009-05-13 | 2009-05-13 | Method for producing ethanolamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101885686A CN101885686A (en) | 2010-11-17 |
| CN101885686B true CN101885686B (en) | 2013-04-03 |
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|---|---|---|---|
| CN2009100572368A Active CN101885686B (en) | 2009-05-13 | 2009-05-13 | Method for producing ethanolamine |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746165B (en) * | 2011-04-20 | 2013-12-25 | 中国石油化工股份有限公司 | Production method of ethanolamine |
| CN102746164B (en) * | 2011-04-20 | 2014-03-26 | 中国石油化工股份有限公司 | Production method of ethanolamine |
| CN102746166B (en) * | 2011-04-20 | 2013-12-25 | 中国石油化工股份有限公司 | Production method of ethanolamine |
| CN102746167B (en) * | 2011-04-20 | 2013-12-25 | 中国石油化工股份有限公司 | Method for production of monoethanolamine and diethanolamine |
| CN102744096B (en) * | 2011-04-20 | 2016-01-13 | 中国石油化工股份有限公司 | For the production of the molecular sieve catalyst of diethanol amine |
| CN107774343B (en) * | 2016-08-30 | 2021-12-28 | 中国石油化工股份有限公司 | Catalyst regeneration process |
| CN107778186A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | Catalyst Production and process of regenerating |
| CN110586175B (en) * | 2018-06-12 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for increasing production of monoethanolamine and diethanolamine |
| CN110586168B (en) * | 2018-06-12 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for preparing monoethanolamine and diethanolamine |
| CN110586169B (en) * | 2018-06-12 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for synthesizing monoethanolamine and diethanolamine |
| CN110590578B (en) * | 2018-06-12 | 2021-11-30 | 中国石油化工股份有限公司 | Method for preparing monoethanolamine and diethanolamine |
| CN110639600B (en) * | 2018-06-27 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst rich in monoethanolamine and diethanolamine |
| CN110639605B (en) * | 2018-06-27 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for increasing production of monoethanolamine and diethanolamine |
| CN110639601B (en) * | 2018-06-27 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for synthesizing monoethanolamine and diethanolamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273235A (en) * | 1999-04-09 | 2000-11-15 | 株式会社日本触媒 | Reaction device for preparing alkanolamine and preparing method using the device |
| CN1297884A (en) * | 1999-11-26 | 2001-06-06 | 株式会社日本触媒 | Process and apparatus for producing alkane hydramine |
-
2009
- 2009-05-13 CN CN2009100572368A patent/CN101885686B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273235A (en) * | 1999-04-09 | 2000-11-15 | 株式会社日本触媒 | Reaction device for preparing alkanolamine and preparing method using the device |
| CN1297884A (en) * | 1999-11-26 | 2001-06-06 | 株式会社日本触媒 | Process and apparatus for producing alkane hydramine |
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|---|---|
| CN101885686A (en) | 2010-11-17 |
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