CN101070276B - Process for preparing acrolein by glycerin dewatering - Google Patents
Process for preparing acrolein by glycerin dewatering Download PDFInfo
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- CN101070276B CN101070276B CN200710041507A CN200710041507A CN101070276B CN 101070276 B CN101070276 B CN 101070276B CN 200710041507 A CN200710041507 A CN 200710041507A CN 200710041507 A CN200710041507 A CN 200710041507A CN 101070276 B CN101070276 B CN 101070276B
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Abstract
This invention relates to acidity zeolite catalyst used for glycerol dehydration to perpare acrolein and the reaction craft. Glycerine directly dehydrate to generate acrolein under the condition ofacidity zeolite catalyst, 200 to 500deg temperature, 0.001 to 3.0MPa pressure and 0.1 to 100.0h - 1 liquid airspeed, at the same time produce byproduct pyruvic alcohol. The raw material raw glycerinecould be mixed liquor of water solution, alcosol, fatty acid ester solution at any ratio.
Description
Technical field
The present invention relates to a kind of method of preparing acrolein by dehydrating glycerin, specifically, is to be catalyzer with the acid zeolite, at 200～500 ℃ of temperature, pressure 0.001～3.0MPa and liquid air speed 0.1～100.0h
-1Reaction conditions under, glycerine directly dewaters and generates the method for propenal.
Background technology
Propenal is important fine-chemical intermediate, is mainly used in to produce agricultural chemical insecticide Provado, medical antitumour drug dibromopropanal, fodder additives methionine(Met), sterilant glutaraldehyde; Propenal can be produced vinylformic acid through oxidation, further acrylic ester synthesizing; Synthesize 1, ammediol through the hydration reduction; Can produce propyl alcohol through reduction, be the important intermediate of synthetic perfume and medical thiosinamine, different sulphur hydracid allyl ester.
Industrial propenal is mainly made by propylene oxidation, is to produce acrylic acid intermediate.Exhausted day by day along with chemical industry energy such as oil, price increase enjoys favor as the biofuel of the alternative energy.Yield of biodiesel significantly increases, but the outlet of its by product raw glycerine has become the important factor that hinders the biofuel development.Therefore, it is significant to develop the chemical utilization of biological raw glycerine.
As everyone knows, glycerine can dewater under the effect of acid catalyst and generates propenal.Liquid acid catalyst mainly adopts H
2SO
4Solution is with H
2SO
4Solution be catalyzer also be initial laboratory by the used catalyzer of glycerine acrolein, most of reaction is all carried out in liquid-phase system.People (J.Supercrit.Fluids such as B ü hler, 2002,22:37～53) having reported under 622～748K, 25～45MPa, the residence time 16～100s condition, is that solvent carries out the dehydrating glycerin reaction with the pure water, and glycerol conversion yield and propenal selectivity only are 31% and 37%.People such as Ramayya (Fuel, 1987,66:1364～1371) have reported under 300～350 ℃, 34.5MPa, 16～39s condition, added H in reaction systems
2SO
4, then glycerol conversion yield and propenal selectivity reach 40% and 80%.(carry out the dehydrating glycerin reaction under 573～663K, 25～35MPa, 10～60s) conditions, glycerol conversion yield and propenal selectivity are 50% and 75% to people (Green Chem, 2006,8:214～220) such as Ott in 2006 at nearly supercritical water.2007, people such as Watanabe studied nearly supercritical water (temperature of reaction, H under 573～673K, 25～34.5MPa) states
2SO
4Concentration, glycerol concentration and pressure show the glycerine of high density, the H of high density to the influence of dehydrating glycerin reaction
2SO
4And higher temperature and pressure helps the generation of propenal.Under supercritical water state (673K, 34.5MPa), glycerol conversion yield can reach 90%, and the propenal selectivity is about 80%.But, with H
2SO
4Be catalyzer, expect higher transformation efficiency and propenal selectivity, reaction must be selected high temperature, high pressure, the reaction down of nearly supercritical water state.But under such reaction conditions, water itself is just very serious to the corrosion of equipment, adds strong acid and has more increased the weight of the corrosive degree, and reactor can only adopt expensive corrosion resistant material, and this will inevitably increase facility investment.On the other hand, because of sulfuric acid is corrodibility strong acid, glycerine is done the time spent coking with it under hot conditions serious, greatly reduces reaction yield undoubtedly.Thereby a lot of research institutions are devoted to develop equipment corrosion less solid acid or bisalt catalyzer are replaced sulfuric acid.
FR 695931 had reported once that phosphoric acid salt such as tertiary iron phosphate, Trilithium phosphate loaded on the float stone, more than 300 ℃, especially carry out the reaction of glycerine gas-phase dehydration under 400～420 ℃ of conditions, the highest yield of propenal can be up to 75～80%, but report according to Degussa company (US 5426249 and CN1034803C), this result can not repeat, in fact, the propenal productive rate only is 1～3% in the time of 300 ℃, even at 400 ℃, the propenal yield only is 30～35% also, mainly generates by products such as vinyl carbinol, acetaldehyde and propionic aldehyde.Degussa company has reported aluminum oxide, the catalyzer such as HZSM-5, HY of phosphoric acid load in patent US 5426249 and CN 1034803C, about 71% the time when the propenal selectivity, glycerol conversion yield has only 19%, and transformation efficiency is low.Though WO 087084A2 in 2006 have also reported the aluminum oxide of phosphoric acid load, the highest yield of its propenal has only 54.5%, and this patent has also been reported oxide compound and loaded catalyst such as ZrO
2/ SO
4, Nafion/SiO
2, ZrO
2/ PO
4, ZrO
2/ WO
3, zirconium sulfate etc., but the propenal yield is generally lower, and hydroxy acetone content is higher in the product.
The present invention is by adopting suitable zeolite molecular sieve solid acid catalyst, under the reaction conditions of gentleness, employing glycerine is raw material, especially adopting biological raw glycerine is raw material, can high-activity high-selectivity ground synthesis of acrolein, overcome above-mentioned patent to adopt liquid acid such as sulfuric acid be catalyzer the heavy corrosion that equipment is brought and needed to use the shortcoming of extreme harsh reaction conditions (supercritical water state), and overcome the deficiency that glycerol conversion yield is not high, the propenal selectivity is low and by product hydroxyketone content is high that adopts phosphoric acid salt loaded catalyst etc.
Summary of the invention
The method that the purpose of this invention is to provide a kind of acidic zeolite catalyst and preparing acrolein by dehydrating glycerin with catalyst thereof.200～500 ℃ of temperature of reaction, preferred 240～360 ℃; Reaction pressure 0.001～3.0MPa, preferred 0.1～1.0MPa; Liquid hourly space velocity 0.1～100.0h
-1, preferred 0.5～20.0h
1Down, dehydrating glycerin generates propenal, simultaneously by-product small amount of hydroxyl groups acetone.
Wherein, zeolite be the aperture greater than
The Hydrogen acid zeolite, comprise X, Y, M, β, ZSM-8, ZSM-10, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-22, MCM-36, MCM-49, MCM-56, MCM-68, ITQ1, ITQ2, SSZ-25, PSH-3, SAPO-11 or SAPO-34 acid zeolite; The Si/Al atomic ratio is 5～500, preferred 10～120; H
+Exchange degree is greater than 70%, and preferred 90%.The preparation process of acidic zeolite catalyst is: will via the hydrothermal crystallization method synthetic and in 450～550 ℃ of following air atmospheres the zeolite powder after the roasting, under 75～95 ℃, exchange with ammonium nitrate solution, obtain the acid zeolite powder through suction filtration, washing, drying and roasting, obtain the acidic zeolite catalyst finished product through moulding again.
Reaction raw materials is aqueous glycerin solution, alcoholic solution, the fatty acid ester solution of content 1～80wt% or they are with arbitrary proportion blended mixing solutions, the mixing solutions of the mixing solutions of the aqueous glycerin solution of preferred content 5～40wt%, methanol solution, water and fatty acid ester or water and methyl alcohol and fatty acid ester.Fixed-bed reactor or fluidized-bed reactor are adopted in the reaction of acid zeolite catalyzed preparing acrolein by dehydrating glycerin.
The present invention adopt the aperture greater than
Acid zeolite as catalyzer, can under lower temperature of reaction, obtain the propenal of higher yields, the content of by product pyruvic alcohol is low in the product.
The present invention has following characteristics:
(1) reaction conditions gentleness, speed of reaction is fast, catalyst activity and selectivity height.
(2) the product system is separated simply, the renewable use of catalyzer and little to equipment corrosion.
(3) raw material raw glycerine wide material sources and inexpensive, the production cost of propenal is low.
(4) the dehydrating glycerin reaction belongs to the green chemical industry process of environment-friendly type.
Embodiment
To be specified with embodiment below, but content of the present invention be not confined to for the category of embodiment.
Embodiment 1
Silicate zeolite MCM-49 adopts hydrothermal crystallization method synthetic, and former powder exchanges 6h with the 2mol/L ammonium nitrate solution down at 85 ℃, and suction filtration and washing repeat 3 times.The filter cake that obtains obtains the H-MCM-49 zeolite of Si/Al=25 at 120 ℃ of dryings, 540 ℃ of roasting 3h, then through compressing tablet, pulverize and sieve, obtain 40～60 purpose zeolite catalyst particles.
The catalyzer of packing in fixed bed continuous flow reaction unit is sent into the raw material aqueous glycerin solution in the reactor respectively continuously with pump, and temperature of reaction is that 360 ℃, glycerine are that the aqueous solution, the reaction pressure of 20wt% is that normal pressure, liquid hourly space velocity are 1.7h
-1, reaction result such as table 1.
Table 1
Embodiment 2-5
Catalyzer and reaction conditions only change temperature of reaction, reaction result such as table 2 with embodiment 1.
Table 2
Embodiment 6-7
Catalyzer and reaction conditions only change liquid hourly space velocity, reaction result such as table 3 with embodiment 1.
Table 3
Embodiment 8-10
Catalyzer and reaction conditions only change glycerol concentration in the aqueous solution, reaction result such as table 4 with embodiment 4.
Table 4
Embodiment 11-12
Catalyzer and reaction conditions only change reaction pressure, reaction result such as table 5 with embodiment 4.
Table 5
Embodiment 13-18
Reaction conditions adopts different zeolite catalysts to carry out dehydrating glycerin reaction, result such as table 6 with embodiment 1.
Claims (6)
1. the method for a preparing acrolein by dehydrating glycerin, it is characterized in that this method be with Si/Al atomic ratio 5～500 and aperture greater than
Acid zeolite be catalyzer, at 200～500 ℃ of temperature, pressure 0.001～3.0MPa and liquid air speed 0.1～100.0h
-1Condition under, the glycerine generation propenal that directly dewaters; Acid zeolite is 10～120 and H for the Si/Al atomic ratio
+Exchange degree is greater than 70% X, Y, M, β, ZSM-8, ZSM-10, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-22, MCM-36, MCM-49, MCM-56, MCM-68, ITQ1, ITQ2, SSZ-25, PSH-3, SAPO-11 or SAPO-34 acid zeolite.
2. the method for preparing acrolein by dehydrating glycerin according to claim 1, it is characterized in that the acid zeolite preparation process is: will via the hydrothermal crystallization method synthetic and in 450～550 ℃ of following air atmospheres the zeolite powder after the roasting, under 75～95 ℃, exchange with ammonium nitrate solution, obtain the acid zeolite powder through suction filtration, washing, drying and roasting, obtain the acidic zeolite catalyst finished product through moulding again.
3. the method for preparing acrolein by dehydrating glycerin according to claim 1 is characterized in that reaction raw materials is that glycerol content is the aqueous glycerin solution of 1～80wt%.
4. the method for preparing acrolein by dehydrating glycerin according to claim 3 is characterized in that reaction raw materials is that glycerol content is the aqueous glycerin solution of 5～40wt%.
5. the method for preparing acrolein by dehydrating glycerin according to claim 1 is characterized in that the dehydrating glycerin reaction conditions is: 240～400 ℃ of temperature, pressure 0.01～1.0MPa, liquid air speed 0.5～20.0h
-1
6. the method for preparing acrolein by dehydrating glycerin according to claim 1 is characterized in that fixed-bed reactor or fluidized-bed reactor are adopted in the reaction of acid zeolite catalyzed preparing acrolein by dehydrating glycerin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710041507A CN101070276B (en) | 2007-05-31 | 2007-05-31 | Process for preparing acrolein by glycerin dewatering |
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| CN200710041507A CN101070276B (en) | 2007-05-31 | 2007-05-31 | Process for preparing acrolein by glycerin dewatering |
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| CN101070276B true CN101070276B (en) | 2010-05-19 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008038273A1 (en) | 2008-08-18 | 2010-03-04 | Evonik Stockhausen Gmbh | Producing acrylic acid, useful as superabsorbent, comprises dehydrating glycerol in presence of dehydration catalysts to obtain gaseous acrolein phase and oxidizing acrolein in presence of oxidation catalyst to gaseous acrylic acid phase |
| CN101417928B (en) * | 2008-12-09 | 2012-05-30 | 江苏工业学院 | Method for preparing acrylic aldehyde by biological glycerol dehydration |
| DE102009027420A1 (en) | 2009-07-02 | 2011-01-05 | Evonik Degussa Gmbh | Preparation of acrolein or aqueous acrolein solution comprises dehydration of a cyclic acetal of glycerol in the presence of a solid catalyst comprising acidic oxides or mixed oxides, natural or synthetic silicate materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034803C (en) * | 1992-11-14 | 1997-05-07 | 底古萨股份公司 | Process for the preparation of acrolein |
| WO2006087084A2 (en) * | 2005-02-15 | 2006-08-24 | Arkema France | Process for dehydrating glycerol to acrolein |
-
2007
- 2007-05-31 CN CN200710041507A patent/CN101070276B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034803C (en) * | 1992-11-14 | 1997-05-07 | 底古萨股份公司 | Process for the preparation of acrolein |
| WO2006087084A2 (en) * | 2005-02-15 | 2006-08-24 | Arkema France | Process for dehydrating glycerol to acrolein |
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Effective date of registration: 20170208 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |
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