CN102744096B - For the production of the molecular sieve catalyst of diethanol amine - Google Patents
For the production of the molecular sieve catalyst of diethanol amine Download PDFInfo
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- CN102744096B CN102744096B CN201110100027.4A CN201110100027A CN102744096B CN 102744096 B CN102744096 B CN 102744096B CN 201110100027 A CN201110100027 A CN 201110100027A CN 102744096 B CN102744096 B CN 102744096B
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Abstract
The present invention relates to a kind of molecular sieve catalyst for the production of diethanol amine, mainly solve diethanol amine one way in prior art selective low, the technical problem of poor catalyst stability.The present invention, by adopting with weight parts, comprises following component: a) 40 ~ 99.9 parts of SiO
2/ Al
2o
3mol ratio is the ZSM-5 zeolite molecular sieve of 10 ~ 500,0 ~ 50 part of binding agent, when wherein binding agent is 0, adopts binder free catalyst, its compression strength be greater than 40 newton/; B) 0.1 ~ 10 part is selected from the technical scheme of at least two oxides in Fe, Ca, La, Ni, Mg, Ba or P, preferably resolves this problem, can be applied to the industrial production of diethanol amine.
Description
Technical field
The present invention relates to a kind of molecular sieve catalyst for the production of diethanol amine.
Background technology
Alcohol amine compound comprises monoethanolamine (MEA), diethanol amine (DEA) and triethanolamine (TEA), because alcohol amine compound end group is respectively hydroxyl and amido, there is the chemical property of alcohols and aminated compounds.Difunctional becomes important organic intermediate, and purposes widely.Monoethanolamine produces the important basic material of the products such as surfactant, medicine, polyurethane auxiliary agent, rubber processing aids, anti-icing fluid auxiliary agent.What the production of current monoethanolamine mainly adopted is oxirane ammonolysis process.Since Knorr (KnorrL.Chem.Bev., 1897,30:909-911; Chem.Bev., 1899,32:729-731) since Late Cambrian Ammonia Process synthesizing ethanolamine, the research of synthesizing ethanolamine attracts more to study interest.The researcher of Shell (ReynhartAFA, Beverwijk.US2186392,1940) company finds, after add ammonium salt in system, can improve the selective of monoethanolamine, and the output of monoethanolamine is directly proportional with the ammonium salt added.BASF (FrauenkronM, M ü llerU, HarderW, UngerJ, MelderJP, MeierA, HimmelW.US7119231.2006) company adopts the ammoniacal liquor of high concentration as reaction raw materials, and ammonia concn is at about 90wt%, NH
3/ EO ratio is between 20 ~ 25, although the productive rate of MEA reaches more than 70wt%, and the NH in system
3excessive far away, add production cost, and still containing more water in reaction system.Vamling (VamlingL, CiderL., Ind.Eng.ChemProd.Res.Dev.1986,: 424-430) etc. (25) adopting liquefied ammonia to be raw material, take strong-acid ion exchange resin as catalyst, under high-speed, the productive rate of MEA reaches more than 70wt%, not thermally-stabilised not high due to ion exchange resin, and this reaction is strong exothermal reaction, so the application of ion exchange resin is limited by very large.Texcao (GriceNJ, KniftonJF.US4939301.1990; JohnsonFL.US4438281.1984) company adopts Al
2o
3-SiO
2and on montmorillonite the catalyst such as carried heteropoly acid, but the activity of catalyst is not high, and the conversion ratio of EO is less than 90% and do not have selective to product.NipponShokubai (TsunekiH, MoriyaA, BabaH.US6169207.2001; MoriyaA, TsunekiH.EP0652207.1995; MoriyaA, TsunekiH.US5880058.1999; TsunekiH, MoriyaA, BabaH.AEP0941986.1999; TsunekiH, KirishikiM, AritaY, HashimotoY, OkuT, ShindouH, UranoY, MorishitaF.US6559342.2003; TsunekiH.US6455016.2002) company adopts the zeolite of La modification to be catalyst, NH
3during/EO=5, the one way weight selectivities of DEA about 48%, by MEA, EO, NH in product
3according to a certain percentage after circulation, the weight selectivities of DEA reaches about 80%, however Japan petroleum engineering can will report, when catalyst for the production of time, the selective decline of diethanol amine within 10 days, needs again to regenerate that just can to reach higher diethanol amine selective.
Summary of the invention
Technical problem to be solved by this invention there is the selective low problem with poor catalyst stability of diethanol amine one way in prior art, provides a kind of molecular sieve catalyst for the production of diethanol amine newly.This catalyst has higher diethanol amine one way selective and good catalyst stability when producing for the production of diethanol amine.
For solving the problems of the technologies described above, one of the technical solution used in the present invention is as follows: a kind of molecular sieve catalyst for the production of diethanol amine, with weight parts, comprises following component: a) 40 ~ 99.9 parts of SiO
2/ Al
2o
3mol ratio is the ZSM-5 zeolite molecular sieve of 10 ~ 500; B) 10 ~ 50 parts of binding agents; C) 0.1 ~ 10 part is selected from the oxide of at least two kinds of elements in Fe, Ca, La, Ni, Mg, Ba or P.
In technique scheme, with weight parts, the consumption being selected from the oxide of at least two kinds of elements in Fe, Ca, La, Ni, Mg, Ba or P is 0.1 ~ 5 part.
For solving technique scheme, the technical solution used in the present invention two as follows: a kind of molecular sieve catalyst for the production of diethanol amine, with weight parts, comprises following component: a) 40 ~ 99.9 parts of SiO
2/ Al
2o
3mol ratio is the adhesiveless ZSM-5 zeolite molecular sieve of 10 ~ 500; B) 0.1 ~ 10 part is selected from the oxide of at least two kinds of elements in Fe, Ca, La, Ni, Mg, Ba or P; Wherein the compression strength of catalyst be greater than 40 newton/.
In technique scheme, with weight parts, the consumption being selected from the oxide of at least two kinds of elements in Fe, Ca, La, Ni, Mg, Ba or P is 0.1 ~ 5 part.
The preparation method of the adhesiveless ZSM-5 zeolite molecular sieve adopted in the present invention is as follows: to be selected from least one in aluminum sulfate, sodium aluminate, macropore clay or boehmite for aluminium source, with the one in Ludox, ethyl orthosilicate or sodium metasilicate for silicon source, with ethylenediamine, triethylamine or hydroxyl-tetraethyl amine for directed agents, wherein SiO
2/ Al
2o
3/ water/directed agents=10 ~ 500/1/150 ~ 200/1 ~ 10, by extrusion after raw material mixing, constant temperature 12 ~ 120 hours at 100 ~ 250 DEG C, obtains adhesiveless ZSM-5 zeolite molecular sieve through washing, roasting.By adding salt or the oxide of required element on adhesiveless ZSM-5 zeolite molecular sieve, obtain adhesiveless ZSM-5 zeolite molecular sieve catalyst through roasting.
When the present invention adopts containing binder catalyst, the number that binding agent accounts for catalyst total amount is 10 ~ 50 parts, its preparation method is as follows: to be selected from one in aluminum sulfate, sodium aluminate or boehmite for aluminium source, with the one in Ludox, ethyl orthosilicate or sodium metasilicate for silicon source, with NaOH and sulfuric acid for pH controls reagent, with ethylenediamine, triethylamine or hydroxyl-tetraethyl amine for directed agents, wherein SiO
2/ Al
2o
3/ water/directed agents=10 ~ 550/1/150 ~ 200/1 ~ 10, at 100 ~ 250 DEG C, crystallization 12 ~ 120 hours, ZSM-5 zeolite molecular sieve source powder is obtained through washing, roasting, aluminium oxide is added or boehmite is binding agent according to 10 ~ 50 parts of catalyst total amount, extruded moulding obtains the ZSM-5 zeolite molecular sieve catalyst precursor containing binding agent, by adding salt or the oxide of required element on ZSM-5 zeolite molecular sieve catalyst precursor, obtain adhesiveless ZSM-5 zeolite molecular sieve catalyst through roasting.
The method that above-mentioned element adds catalyst can be that original position adds, exchange process or direct impregnation load; Above-mentioned element is raw materials used is selected from lanthanum nitrate or lanthana, ferric nitrate or iron oxide, phosphoric acid or phosphorous oxide etc.
Because catalyst has suitable acidity, to ammonia (NH3) and the reaction of oxirane (EO), there is very high catalytic activity, and the alkalescence of catalyst accelerates product from its surface desorption, the mesoporous pore volume of higher catalyst is conducive to the diffusion of product and raw material, improves the stability of catalyst.
A kind of SiO is obtained by above-mentioned technical scheme
2/ Al
2o
3mol ratio is 10 ~ 500, and specific area is at 200 ~ 400 meters
2/ gram, particle diameter is at the catalyst of 0.1 ~ 5 μm, and the mesoporous pore volume of catalyst is at 0.08 ~ 0.30cm
3/ g; Adopt catalyst of the present invention, during for oxirane and ammonia react, inlet temperature 60 ~ 120 DEG C, under system pressure 6 ~ 15.0MPa condition, its reaction result is, the selective of diethanol amine (DEA) reaches 55%, catalyst was through examination in 500 hours, and the activity of catalyst is unchanged, the larger change of selective nothing of diethanol amine, exceed international similar catalyst 240 hours stability and selective, achieve good technique effect.
Below by embodiment, the invention will be further elaborated, but these embodiments are in no case construed as limiting scope of the present invention.
Detailed description of the invention
[embodiment 1]
187g Ludox is mixed with the ethylenediamine of 5.6mL, and at room temperature stirs 0.5 hour; According to SiO
2/ Al
2o
3the ratio of=25 (mol ratios) takes thin aluminium water stone, joins in said mixture, and strong agitation 0.5 hour, add the La (NO of 5% thereafter
3)
3with H
3pO
4, by said mixture extruded moulding, and by product in 180 DEG C of constant temperature 36 hours.Product after crystallization is spent deionized water, and in 100 DEG C of oven dry, Muffle furnace is placed in by drying the rear molecular sieve obtained, roasting in air atmosphere, air velocity is 100 ml/min, with the ramp to 600 DEG C of 15 DEG C/min, and roasting 6 hours at this temperature, obtain molecular sieve precursor I thus.In 550 DEG C of roastings after molecular sieve precursor I and ammonium nitrate solution being exchanged, obtain adhesiveless ZSM-5 zeolite molecular sieve catalyst finished product.
Get 10mL molecular sieve catalyst and be placed in reactor, and whether the air-tightness of checking system is intact; Then by intrasystem air with N
2displacement, is replaced in backward system and is filled with high pressure nitrogen to 6 ~ 10MPa, and be heated to 50 ~ 100 DEG C, after treating temperature constant, according to NH
3the ratio of/EO=6 (mol ratio) passes into ammonia and oxirane.
[embodiment 2] ~ [embodiment 10]
According to each Step By Condition Kaolinite Preparation of Catalyst of embodiment 1, only feed change silica and alumina ratio, add the kind of directed agents, the kind of addition element and content, and synthesis condition is listed in form 1.
[embodiment 11]
Mixed with 200mL deionized water by 187g Ludox, in stirred at ambient temperature 10 minutes, the ethylenediamine measuring 5.6mL thereafter added in above-mentioned mixed solution, and at room temperature stirred 0.5 hour; According to SiO
2/ Al
2o
3the ratio of=25 (mol ratios) takes Al
2(SO
4)
318H
2o, joins in above-mentioned mixed solution, and strong agitation 0.5 hour, will the colloid of thick white be obtained.In body colloid, add 8gNaOH, regulation system pH value to 13 ~ 14, in above-mentioned mixed liquor, add the La (NO of 5%
3)
3with H
3pO
4, and continue stirring and transfer to crystallizing kettle after 1 hour, in 180 DEG C of constant temperature 36 hours.Product after crystallization is spent deionized water, and in 100 DEG C of oven dry, Muffle furnace is placed in by drying the rear molecular sieve obtained, roasting in air atmosphere, air velocity is 100 ml/min, with the ramp to 600 DEG C of 15 DEG C/min, and roasting 6 hours at this temperature, obtain molecular sieve precursor I thus.80 parts of molecular sieve precursor I, appropriate nitric acid are mixed with the binding agent alumina powder of 20 parts, and adds the sesbania powder in weight fraction 0.1 ~ 5%, obtains the presoma II of catalyst.By catalyst precursor II extruded moulding, drying also in 450 ~ 650 DEG C of roastings 0.5 ~ 24 hour, obtains finished catalyst.
[embodiment 12] ~ [embodiment 20]
According to embodiment 1 each Step By Condition Kaolinite Preparation of Catalyst, only the silica of feed change and alumina ratio, binding agent content, add the kind of directed agents and the kind of addition element and content, and synthesis condition is listed in form 1.
[embodiment 21] ~ [embodiment 25]
According to embodiment 1 each Step By Condition Kaolinite Preparation of Catalyst and to catalyst and examination catalyst, only change the mol ratio of ammonia and oxirane in examination condition, reaction temperature, system pressure, air speed, and the technological parameter such as reaction time, list in form 2.
[embodiment 26] ~ [embodiment 30]
According to embodiment 11 each Step By Condition Kaolinite Preparation of Catalyst and to catalyst and examination catalyst, only change the mol ratio of ammonia and oxirane in examination condition, reaction temperature, system pressure, air speed, and the technological parameter such as reaction time, list in form 2.
[comparative example 1]
The catalyst data that comparative example 1 is reported for NipponShokubai company, lists in form 3.
Form 1
Form 2
Form 3
Claims (4)
1. for the production of a molecular sieve catalyst for diethanol amine, with weight parts, comprise following component: a) 40 ~ 99.9 parts of SiO
2/ Al
2o
3mol ratio is the ZSM-5 zeolite molecular sieve of 10 ~ 500; B) 10 ~ 50 parts of binding agents; C) 0.1 ~ 10 part is selected from the oxide of at least two kinds of elements in La and P.
2. the molecular sieve catalyst for the production of diethanol amine according to claim 1, is characterized in that with weight parts, and the consumption being selected from the oxide of at least two kinds of elements in La and P is 0.1 ~ 5 part.
3. for the production of a molecular sieve catalyst for diethanol amine, with weight parts, comprise following component: a) 40 ~ 99.9 parts of S1O
2/ Al
2o
3mol ratio is the adhesiveless ZSM-5 zeolite molecular sieve of 10 ~ 500; B) 0.1 ~ 10 part is selected from the oxide of at least two kinds of elements in La and P; Wherein the compression strength of catalyst be greater than 40 newton/.
4. the molecular sieve catalyst for the production of diethanol amine according to claim 3, is characterized in that with weight parts, and the consumption being selected from the oxide of at least two kinds of elements in La and P is 0.1 ~ 5 part.
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| CN201110100027.4A CN102744096B (en) | 2011-04-20 | 2011-04-20 | For the production of the molecular sieve catalyst of diethanol amine |
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| CN102744096B true CN102744096B (en) | 2016-01-13 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107512729B (en) * | 2016-06-18 | 2020-04-17 | 中国石油化工股份有限公司 | Preparation method of binder-free ZSM-5 molecular sieve |
| CN106631836A (en) * | 2016-11-17 | 2017-05-10 | 北京德博莱化工产品销售有限公司 | Preparation method of novel isopropanolamine |
| 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 |
| CN110590579B (en) * | 2018-06-12 | 2021-11-30 | 中国石油化工股份有限公司 | Method for synthesizing monoethanolamine and diethanolamine |
| CN110590580B (en) * | 2018-06-12 | 2021-11-30 | 中国石油化工股份有限公司 | Preparation method of monoethanolamine and diethanolamine |
| CN110586171B (en) * | 2018-06-12 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for producing monoethanolamine and diethanolamine |
| CN110590572B (en) * | 2018-06-12 | 2021-11-30 | 中国石油化工股份有限公司 | Method for producing 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 |
| CN110639602B (en) * | 2018-06-27 | 2022-07-08 | 中国石油化工股份有限公司 | Catalyst for producing 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 |
| CN110642728B (en) * | 2018-06-27 | 2022-10-11 | 中国石油化工股份有限公司 | Method for rich production of monoethanolamine and diethanolamine |
| CN110642727B (en) * | 2018-06-27 | 2022-09-06 | 中国石油化工股份有限公司 | Method for increasing production of monoethanolamine and diethanolamine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106377A (en) * | 1993-11-02 | 1995-08-09 | 株式会社日本触媒 | Process for preparation for alkanolamine, catalyst used in process for preparation of catalyst |
| CN101884934A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Zeolite catalyst for producing ethanolamine and preparation method thereof |
| CN101885686A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for producing ethanolamine |
-
2011
- 2011-04-20 CN CN201110100027.4A patent/CN102744096B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106377A (en) * | 1993-11-02 | 1995-08-09 | 株式会社日本触媒 | Process for preparation for alkanolamine, catalyst used in process for preparation of catalyst |
| CN101884934A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Zeolite catalyst for producing ethanolamine and preparation method thereof |
| CN101885686A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for producing ethanolamine |
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