CN105536858B - A kind of preparation method of catalyst and a kind of preparation method of monoethanolamine - Google Patents
A kind of preparation method of catalyst and a kind of preparation method of monoethanolamine Download PDFInfo
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- CN105536858B CN105536858B CN201510933735.4A CN201510933735A CN105536858B CN 105536858 B CN105536858 B CN 105536858B CN 201510933735 A CN201510933735 A CN 201510933735A CN 105536858 B CN105536858 B CN 105536858B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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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
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The preparation method and a kind of preparation method of monoethanolamine of a kind of catalyst of the present invention, are related to catalyst and preparation method of a kind of ethylene glycol through the aminating reaction organic amine product in downstream directly processed.A kind of preparation method of catalyst, including hydrogen type molecular sieve is made through ion exchange in sodium form mordenite molecular sieve, then produced being mixed after hydrogen type molecular sieve progress acid modification with boehmite powder.The invention also discloses be used to above-mentioned catalyst be catalyzed ethylene glycol ammonification.The invention also discloses a kind of preparation method of monoethanolamine, including by ethylene glycol, monoethanolamine is made in ammonification under the catalysis of above-mentioned catalyst.Present invention process route is short, and product selectivity is higher, has larger economic advantages.
Description
Technical field
The present invention relates to catalyst and preparation method of a kind of ethylene glycol through the aminating reaction organic amine product in downstream directly processed.
Technical background
The most important purposes of ethanolamine product is production surfactant, is additionally operable to TEXTILE CHEMICALS, gas purification in addition
Agent, accelerator for cement slurry, petroleum additive, bating agent, lubricating oil corrosion inhibitor, soot prevention compound etc..Ethylenediamine product
It is mainly used in medicine intermediate；Cheland；Epoxy curing agent；Agriculture chemicals fungicide；Fiber surface activity agent etc..
At present, the production of monoethanolamine is mainly by oxirane and ammonia reaction generation monoethanolamine, diethanol amine and three second
The mixture of hydramine, the ratio of three kinds of monoethanolamines of generation is mainly by oxirane and the ratio-dependent of ammonia.And oxirane master
If it is made by ethene through epoxidation reaction, therefore it is complex and rely on oxirane serious ask process route to be present
Topic.
Ethylenediamine production method mainly has two kinds, first, dichloroethane law, the method corrosivity is strong, a large amount of NaCl of by-product, dirty
Dye problem is serious；Second, monoethanolamine ammoniation process, the basic three wastes of the method, there is stronger competitiveness, but the process route still according to
Rely in ethylene industry.
Recently as the maturation of coal-ethylene glycol technology, ethylene glycol production capacity increases sharply, from raw material ethylene glycol through
The organic amine product in the downstreams such as one-step synthesis method monoethanolamine, not only process route is simple, and cost of material relative moderate, while suitable
The trend of current China's Development of Coal Chemical Industry is answered.
Patent 201010124753.5 discloses one kind using copper as active component, using titanium oxide, zinc oxide, zirconium oxide to help
The catalyst of agent, diamine through amination is hydrogenated for ethylene glycol, at 275 DEG C, ethylene glycol air speed is 0.5h-1, ethylene glycol reforming rate
Reach 60%, ethylenediamine yield reaches 32.2%.
Siegfried Winderl et al. disclose a kind of preparation method of sintering type metal catalyst, and cobalt salt is existed
1100 DEG C are sintered to form metal oxide, and ethylene glycol is used for after reducing in a hydrogen atmosphere and reacts ethylenediamine processed with ammonia,
180 DEG C, under 300atm, obtain 90% ethylene glycol reforming rate and 78% ethylenediamine yield.
Pt-Ru-Co/Al is used in patent 201310674922.62O3It is anti-that catalyst is used for ethylene glycol ammonification monoethanolamine
Should, ethylene glycol reforming rate reaches 65%, and monoethanolamine yield reaches 34%.
The production of monoethanolamine at present depends on ethene and oxirane, and the production of ethylenediamine again relies on monoethanolamine, work
Skill route is more complicated and strong to feed ethylene and oxirane dependence.
The content of the invention
It is an object of the invention to overcome deficiency and defect existing for prior art route, there is provided one kind prepares raw catelyst
Method, and obtained catalyst is used for ethylene glycol ammonification.
In addition, present invention also offers a kind of synthetic method of the organic amine product in the downstream such as new synthesizing ethanolamine.
The preparation method of catalyst of the present invention, it is that Hydrogen is made through ion exchange in sodium form mordenite molecular sieve
Molecular sieve, then produced being mixed after hydrogen type molecular sieve progress acid modification with boehmite powder.
Wherein described sodium form mordenite molecular sieve can use commercially available prod, can also directly prepare.Such as：Using
Hydrothermal synthesis method is made, and silica alumina ratio is 10 ~ 25.
It is highly preferred that the mass fraction of aluminum oxide is 10% ~ 20% in resulting catalyst.
Or it is highly preferred that it is to use ion-exchange and infusion process that described hydrogen type molecular sieve, which is modified,.When using ion
During exchange process, modifying agent used in the modification of described hydrogen type molecular sieve is ammonium salt, organic monoacid or alkali metal salt.Such as dilute nitre
Acid, ammonium chloride, ammonium fluoride, citric acid or sodium nitrate.Such as 0.5 ~ 2mol/L acid solution is prepared, by liquid-solid ratio 1.5 ~ 3:1
Ratio carries out ion exchange.
When using infusion process, modifying agent used in the modification of described hydrogen type molecular sieve is rare earth ion, alkaline-earth metal
Or phosphate.Such as diammonium hydrogen phosphate, lanthanum nitrate, cerous nitrate, magnesium nitrate or the sour calcium of pin.Such as by liquid-solid ratio 1.3 ~ 1.8:1 ratio
Example dipping, 60 ~ 90 DEG C of dipping temperature, dip time 6 ~ 12h, P2O5、La3+、Ce3+、Mg2+Or Ca2+Load capacity be 0.5% ~ 2%.
Or it is further preferred that hydrogen type molecular sieve is made through ion exchange in described sodium form mordenite molecular sieve is
Refer to：By sodium form modenite use 1 ~ 2mol/L ammonium nitrate, ammonium chloride, ammonium acetate and ammonium citrate in any one progress from
Son exchanges, and ion-exchange temperature is 80 ~ 110 DEG C, 8 ~ 16h of time, exchanges after completing through 100 ~ 120 DEG C of dryings, 500 ~ 600 DEG C of roastings
It is fired into hydrogen type molecular sieve.
In a specific embodiment, " hydrogen type molecular sieve is modified to be mixed with boehmite powder " of the present invention
Concrete operations are：By the modified hydrogen molecular sieve that upper step obtains in 100 ~ 120 DEG C of dry 8 ~ 12h, afterwards with boehmite powder
Mixed, add appropriate nitric acid and do binding agent, kneading extruded moulding.In 100 ~ 120 DEG C of 6 ~ 10h of drying process after shaping, it
After 200 ~ 250 DEG C of 1 ~ 2h of low-temperature bake, catalyst is made then at 400 ~ 500 DEG C of 4 ~ 6h of high-temperature roasting.
Present invention also offers be used to catalyst made from the above method be catalyzed ethylene glycol ammonification.
The preparation method of monoethanolamine of the present invention, be by ethylene glycol catalyst made from the above method catalysis
Monoethanolamine is made in the lower ammonification of effect.
Preferably, ammonia alcohol mol ratio is 10, and temperature is 300 DEG C, system pressure 12MPa during aminating reaction, and ethylene glycol is empty
Fast 0.3h-1。
The present invention has following advantage：
1）Ethanolamine product is directly made through aminating reaction in ethylene glycol of the present invention, and raw material ethylene glycol price is relatively low, technique road
Line is short, has larger economic advantages.
2）Catalyst of the present invention is used for ethylene glycol aminating reaction, and product selectivity is higher, is 0.3h in air speed-1, ethylene glycol
Conversion ratio reaches 56%, and monoethanolamine and ethylenediamine overall selectivity reach 67%, and the selectivity of wherein monoethanolamine reaches 43%.
Embodiment
Evaluating catalyst of the present invention uses fixed-bed reactor, stainless steel reaction bore 8mm, loaded catalyst
10mL.System is boosted using nitrogen first, reactor and preheater are heated to after reaching specified pressure
Reaction temperature is specified, stopping is passed through nitrogen, and switching is passed through raw materials ammonia and ethylene glycol, and liquefied ammonia and ethylene glycol are accurate using measuring pump
Metering.
Stable reaction 8h sampling analyses, analyzed with Agilent 7890A chromatographs.
Evaluating catalyst condition：280 ~ 330 DEG C, 8 ~ 15MPa of reaction pressure of reaction temperature, raw material ammonia and ethylene glycol mol ratio
For 10 ~ 15:1, ethylene glycol air speed is 0.2 ~ 0.5h-1。
Embodiment 1
1.1 catalyst preparation
（1）Ion exchange is carried out to the sodium form modenite of preparation with 1mol/L ammonium nitrate solution, constant 90 DEG C of temperature,
Ion-exchange time 10h, 4 filterings of deionized water rinsing after the completion of exchange, Hydrogen point is made through 110 DEG C of dryings, 500 DEG C of roastings
Son sieve；
（2）Weigh 100g h-mordenites, the h-mordenite prepared with 1mol/L ammonium chloride solution to step 1
It is modified, 70 DEG C of ion-exchange temperature, swap time 8h, is filtered after the completion of exchange, in 110 DEG C of dry 8h；
（3）20g boehmite powder is weighed, is well mixed with the modified molecular screen that step 2 is dried to obtain, adds appropriate nitre
Sour kneading is uniform, afterwards extruded moulding, the catalyst after shaping in 110 DEG C of dry 10h, after 250 DEG C of low-temperature bake 2h, then
It is warming up to 450 DEG C of high-temperature roasting 4h and amination catalyst is made.
1.2 appreciation condition
Above-mentioned catalyst is used for ethylene glycol ammonification.Wherein 300 DEG C of aminating reaction temperature, ammonia alcohol mol ratio are 10, system
Pressure 12MPa, ethylene glycol air speed 0.3h-1。
Ethylene glycol reforming rate reaches 47%, and monoethanolamine is selectively 45.3%, and ethylenediamine is selectively 18.7%.
Embodiment 2
2.1 catalyst preparation
（1）The preparation method of h-mordenite is the same as described in step 1 in embodiment 1；
（2）100g h-mordenites are weighed, 2.1320g diammonium hydrogen phosphates is weighed, is added to complete in 140mL deionized waters
Fully dissolved, modenite is added in the ammonium dibasic phosphate solution prepared, in 80 DEG C stirring dipping 8h, dipping complete after
120 DEG C of dry 10h；
（3）23g boehmite powder is weighed, is well mixed with the phosphorus modified molecular sieves that step 2 is dried to obtain, addition is appropriate
Nitric acid kneading is uniform, afterwards extruded moulding, the catalyst after shaping in 110 DEG C of dry 8h, after 220 DEG C of low-temperature bake 2h,
480 DEG C of high-temperature roasting 4h are warming up to again, and amination catalyst is made.
2.2 appreciation condition
Above-mentioned catalyst is used for ethylene glycol ammonification.Wherein 320 DEG C of aminating reaction temperature, ammonia alcohol mol ratio are 15, system
Pressure 15MPa, ethylene glycol air speed 0.3h-1。
Ethylene glycol reforming rate reaches 56%, and monoethanolamine selectively reaches 39.5%, and ethylenediamine is selectively 27.6%.
Embodiment 3
3.1 catalyst preparation
（1）The preparation method of h-mordenite is the same as described in step 1 in embodiment 1；
（2）100g h-mordenites are weighed, weigh 4.6785gLa (NO3)3·6H2O, it is added to 145mL deionized waters
In be completely dissolved, modenite is added in the lanthanum nitrate hexahydrate prepared, in 90 DEG C stirring dipping 8h, dipping complete after
110 DEG C of dry 8h；
（3）25g boehmite powder is weighed, is well mixed with the lanthanum modified molecular screen that step 2 is dried to obtain, addition is appropriate
Nitric acid kneading is uniform, afterwards extruded moulding, the catalyst after shaping in 110 DEG C of dry 10h, after 250 DEG C of low-temperature bake 1h,
500 DEG C of high-temperature roasting 4h are warming up to again, and amination catalyst is made.
3.2 appreciation condition
Above-mentioned catalyst is used for ethylene glycol ammonification.Wherein 320 DEG C of aminating reaction temperature, ammonia alcohol mol ratio are 15, system
Pressure 13MPa, ethylene glycol air speed 0.3h-1。
Ethylene glycol reforming rate reaches 58%, and monoethanolamine selectively reaches 42.6%, and ethylenediamine is selectively 21.3%.
Embodiment 4
4.1 catalyst preparation
（1）The preparation method of h-mordenite is the same as described in step 1 in embodiment 1；
（2）100g h-mordenites are weighed, weigh 3.5422gCa (NO3)2·4H2O, it is added to 140mL deionized waters
In be completely dissolved, modenite is added in the calcium nitrate solution prepared, in 80 DEG C stirring dipping 8h, dipping complete after
110 DEG C of dry 8h；
（3）20g boehmite powder is weighed, is well mixed with the calcium oxide modified molecular screen that step 2 is dried to obtain, is added
Appropriate nitric acid kneading is uniform, afterwards extruded moulding, the catalyst after shaping in 110 DEG C of drys 10h, after 230 DEG C of low temperature roastings
2h is burnt, then is warming up to 500 DEG C of high-temperature roasting 6h and amination catalyst is made.
4.2 appreciation condition
Above-mentioned catalyst is used for ethylene glycol ammonification.Wherein 330 DEG C of aminating reaction temperature, ammonia alcohol mol ratio are 13, system
Pressure 15MPa, ethylene glycol air speed 0.3h-1。
Ethylene glycol reforming rate reaches 54%, and monoethanolamine selectively reaches 40.2%, and ethylenediamine is selectively 26.4%.
Claims (6)
1. the purposes that catalyst is prepared into monoethanolamine for being catalyzed ethylene glycol ammonification, wherein the preparation method of the catalyst is
Hydrogen type molecular sieve is made through ion exchange in sodium form mordenite molecular sieve, then by hydrogen type molecular sieve carry out after acid modification with plan
Boehmite powder, which mixes, to be produced.
2. the purposes of catalyst as claimed in claim 1, it is characterised in that the quality of aluminum oxide point in obtained catalyst
Number is 10% ~ 20%.
3. the purposes of catalyst as claimed in claim 2, it is characterised in that it is to use ion that described hydrogen type molecular sieve, which is modified,
Exchange process, used modifying agent are ammonium salt, organic monoacid or alkali metal salt.
4. the purposes of catalyst as claimed in claim 2, it is characterised in that it is using dipping that described hydrogen type molecular sieve, which is modified,
Method, modifying agent used in the modification of described hydrogen type molecular sieve is rare earth ion, alkaline-earth metal or phosphate.
5. the purposes of the catalyst as described in claim 1-3 Arbitrary Terms, it is characterised in that described sodium form modenite molecule
Sieve is made hydrogen type molecular sieve through ion exchange and referred to：By sodium form modenite using 1 ~ 2mol/L ammonium nitrate, ammonium chloride, ammonium acetate
Ion exchange is carried out with any one in ammonium citrate, ion-exchange temperature is 80 ~ 110 DEG C, 8 ~ 16h of time, exchanges and completes
Hydrogen type molecular sieve is made by 100 ~ 120 DEG C of dryings, 500 ~ 600 DEG C of roastings.
6. the purposes of the catalyst as described in claim 1-4 Arbitrary Terms, it is characterised in that in described ethylene glycol ammonifying process
Ammonia alcohol mol ratio is 10, and temperature is 300 DEG C, system pressure 12MPa during aminating reaction, ethylene glycol air speed 0.3h-1。
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927132B (en) * | 2017-05-26 | 2020-11-24 | 中国科学院大连化学物理研究所 | Bifunctional catalyst and method for preparing ethylene by carbon monoxide hydrogenation |
| CN107737605B (en) * | 2017-09-30 | 2020-06-09 | 宝鸡文理学院 | Catalyst for selectively synthesizing 4-methyl-2, 6-di-tert-butylphenol and application thereof |
| 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 |
| CN114433088B (en) * | 2020-10-30 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst and carrier with function of catalyzing hydro-ammonification of alcohol to generate organic amine, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4254061A (en) * | 1979-09-11 | 1981-03-03 | E. I. Du Pont De Nemours And Company | Preparation of monomethylamine |
| US4918233A (en) * | 1986-07-08 | 1990-04-17 | Air Products And Chemicals, Inc. | Production of ethylenediamine from monoethanolamine and ammonia |
| CN1351904A (en) * | 2000-11-15 | 2002-06-05 | 北京燕山石油化工公司研究院 | Zeolite catalyst and process for preparing 4-tert butyl catechol |
| CN102189002A (en) * | 2010-03-04 | 2011-09-21 | 中国石油化工股份有限公司 | Pseudo-boehmite and molecular sieve composition and carrier prepared from same |
| CN103664649A (en) * | 2013-12-10 | 2014-03-26 | 陕西省石油化工规划设计院 | Method for preparing monoethanolamine from ethylene glycol |
-
2015
- 2015-12-15 CN CN201510933735.4A patent/CN105536858B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4254061A (en) * | 1979-09-11 | 1981-03-03 | E. I. Du Pont De Nemours And Company | Preparation of monomethylamine |
| US4918233A (en) * | 1986-07-08 | 1990-04-17 | Air Products And Chemicals, Inc. | Production of ethylenediamine from monoethanolamine and ammonia |
| CN1351904A (en) * | 2000-11-15 | 2002-06-05 | 北京燕山石油化工公司研究院 | Zeolite catalyst and process for preparing 4-tert butyl catechol |
| CN102189002A (en) * | 2010-03-04 | 2011-09-21 | 中国石油化工股份有限公司 | Pseudo-boehmite and molecular sieve composition and carrier prepared from same |
| CN103664649A (en) * | 2013-12-10 | 2014-03-26 | 陕西省石油化工规划设计院 | Method for preparing monoethanolamine from ethylene glycol |
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