CN101879456A - Process for preparing acrylic aldehyde by using selective glycerol dehydration and preparation method of catalyst thereof - Google Patents
Process for preparing acrylic aldehyde by using selective glycerol dehydration and preparation method of catalyst thereof Download PDFInfo
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- CN101879456A CN101879456A CN 201010213226 CN201010213226A CN101879456A CN 101879456 A CN101879456 A CN 101879456A CN 201010213226 CN201010213226 CN 201010213226 CN 201010213226 A CN201010213226 A CN 201010213226A CN 101879456 A CN101879456 A CN 101879456A
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Abstract
The invention discloses a process for preparing acrylic aldehyde by using selective glycerol dehydration and a preparation method of a catalyst thereof. Heteropolyacid/a carrier is disclosed in the expression of the catalyst, wherein the heteropolyacid is one of silicotungstic acid, phosphotungstic acid and phosphomolybdic acid, and the carrier is one of activated aluminium oxide, kieselguhr, activated carbon, rutile type titanium dioxide and kaoline. The catalyst is prepared by using a constant-pore volume dipping method. When the catalyst is used in a fixed-bed miniature reaction device, the transformation rate of glycerol is 13.5%-80.6%, and the selectivity of the acrylic aldehyde is 49.0%-90.5%. When used for carrying out the process for preparing acrylic aldehyde by using glycerol dehydration, the catalyst has the advantages of high catalyst activity, high reaction speed, high selectivity for the acrylic aldehyde and the like, and the main byproduct is hydroxyl acetone.
Description
Technical field
The present invention relates to technology and Preparation of catalysts method thereof that a kind of selective glycerol dehydration prepares methacrylaldehyde.
Background technology
Methacrylaldehyde is a kind of important organic chemical industry's product and the important intermediate of preparation fine chemical product, has widely in industries such as feedstuff industry, papermaking and water treatment, oil exploitation and medical treatment and uses.The concrete application of methacrylaldehyde comprises as producing the required D of animal feed additive, L-methionine, as effective bactericide of oilfield injection water in effective disinfectant of industrial circulating cooling water, the petroleum industry etc.Methacrylaldehyde is the simplest unsaturated aldehyde, because it has two reactive functional groups, can be converted into multiple high added value downstream product.
The industrialized producing technology of methacrylaldehyde mainly comprises condensation method and oxidizing process.Formaldehyde-acetaldehyde vapour phase condensation method is to realize the methacrylaldehyde preparation method of suitability for industrialized production the earliest.Degussa company adopts the impregnated silica gel of sodium metasilicate as catalyst, and formaldehyde and acetaldehyde are at 300～320 ℃ of catalyst layers that pass through down in the tubular reactor, and yield is about 65%, and this method is for realizing the methacrylaldehyde preparation method of suitability for industrialized production the earliest.Usefulness formalins such as Ai and the aldol condensation legal system of ethanol under 240～320 ℃ are equipped with methacrylaldehyde, and promptly with silica gel load different metal oxide and metal phosphate catalytic reaction, but yield is not good.The propylene catalytic oxidation is one of main path of synthesis of acrolein, and 80% methacrylaldehyde output in the world is provided.This process route is a kind of to be to be that intermediate product is produced acrylic acid with the methacrylaldehyde, and another kind is to prepare methacrylaldehyde with the propylene for the raw material selective oxidation.The oxidation of propane method is because the raw material cheapness cause people's research interest, but propane itself is saturated little molecule alkane, and stable in properties synthesizes methacrylaldehyde with it and need overcome thermodynamic limitation, and how the method improves the methacrylaldehyde yield, still has to be solved.
The increasing the weight of of exhausted day by day and environmental pollution along with the non-renewable fossil energy of containing on the earth, above-mentioned method with petrochemical industry path of preparing methacrylaldehyde will be subjected to severe challenge, and the regenerative resource of selecting to clean has become the emphasis of present energy research.Glycerine can be obtained by a plurality of living beings approach, have nontoxic, sustainability generates and advantage such as degradability.The polyfunctional group structure and the performance of glycerine itself make it can be converted into the high oxycompound of various added values.
As far back as nineteen twenty-eight, reported glycerine among the patent US 1672378 under 180 ℃, be that catalyst makes methacrylaldehyde with diatomite.Method described in the patent WO 2008052993 is based on the ZSM-5 molecular sieve and makees catalyst, in moving bed and fixed bed, carry out the reaction that the glycerine gas-phase dehydration prepares methacrylaldehyde, when glycerol concentration in the raw material when 20% rises to 85%, the feed stock conversion fluctuation is little, but the yield of methacrylaldehyde rises to 62% from 55%.This result and patent 200710041507 described reaction results are inconsistent, may be relevant with reaction process and catalyst.Patent US 5387720 reports are catalyst with the solid phosphoric acid, 10～40% glycerine water solution enters fixed bed reactors after vaporization catalytic bed.Preferred reaction conditions is to carry out gas-phase reaction under 250～340 ℃, and glycerol conversion yield is 100%, and the methacrylaldehyde selectivity is 70.5%, and main accessory substance is a hydroxypropanone-.
Selective glycerol dehydration prepares methacrylaldehyde and prepares methacrylaldehyde with existing petrochemical industry path and compare, and its feature of environmental protection and recyclability have clear superiority, are the industrial manufacture processes with broad prospect of application.
Summary of the invention
The object of the present invention is to provide a kind of selective glycerol dehydration to prepare the technology and the method for preparing catalyst of methacrylaldehyde.The expression formula of this catalyst is heteropoly acid/carrier, wherein said heteropoly acid is a kind of in silico-tungstic acid, phosphotungstic acid, the phosphomolybdic acid, described carrier is a kind of in activated alumina, diatomite, active carbon, rutile titanium dioxide, the kaolin, the preparation of pore volume impregnation methods such as employing, step and condition are as follows:
(1) take by weighing a certain amount of heteropoly acid and carrier respectively, making both mass ratioes is 1: 4～1: 19, and promptly activity component load quantity is 5～20% in the catalyst; Heteropoly acid is dissolved in the distilled water, makes the volume of its aqueous solution equal the pore volume of carrier;
(2) carrier is flooded 4～5h in the heteropoly acid aqueous solution, again this catalyst is dried 10～12h down at 120～140 ℃, stir once every 15～20min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier;
(3) with cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, rescreen that to be divided into 20～40 orders standby.
A kind of selective glycerol dehydration involved in the present invention prepares the following program of process using of methacrylaldehyde to carry out: be reflected in the fixed bed reactors and carry out, the catalyst of catalytic amount is placed the reactor middle part, be that 10～20% glycerine water solution pumps in the reactor after vaporization with mass concentration, the liquid air speed is 1.2h-1, raw material contacts under 220～300 ℃ with catalyst, the reaction of generation gas-phase dehydration prepares methacrylaldehyde.With the cooled with liquid nitrogen gas-liquid separator and collect product, product carries out quantitative and qualitative analysis by gas chromatograph and mass spectrograph.
Adopt catalyst of the present invention, carry out the technology that dehydrating glycerin prepares methacrylaldehyde, its outstanding advantage is:
(1) catalyst activity height, reaction rate fast, to methacrylaldehyde selectivity height, main accessory substance is a hydroxypropanone-.
(2) reaction raw materials concentration range of choice wide (10～20%), the glycerine that can directly adopt the living beings path to obtain is avoided glycerine is purified the energy consumption that causes.
(3) the dehydrating glycerin reaction belongs to the green chemical industry process of environment-friendly type, and production cost is low, and environmental pollution is little.
(4) glycerol conversion yield and methacrylaldehyde selectivity height can reach 69.7% and 90.5% respectively.
Concrete exemplifying embodiment
Embodiment 1
Take by weighing a certain amount of silico-tungstic acid and activated alumina respectively, making both mass ratioes is 1: 4, and promptly activity component load quantity is 20% in the catalyst.Silico-tungstic acid is dissolved in the distilled water, makes the volume of its aqueous solution equal the pore volume of activated alumina.Activated alumina is flooded 4h in silicon tungsten acid solution, again this catalyst is dried 10h down at 120 ℃, stir once every 15min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier.Cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, is rescreened that to be divided into 20～40 orders standby.With prepared catalyst called after silico-tungstic acid-activated alumina-20.
Glycerine water solution with 20% is raw material carries out glycerine in fixed-bed micro-reactor selectively dewatering reaction, use the no pulse measuring pump that glycerine water solution is sent into reactor continuously, reactor is that (Φ 10mm * 23cm), the liquid air speed is 1.2h to stainless-steel pipe
-1, silico-tungstic acid-activated alumina-20 is 5mL, the dehydration temperature is 300 ℃.Final glycerol conversion yield is 69.7%, and the methacrylaldehyde selectivity is 90.5%.
Exemplifying embodiment 2
Take by weighing a certain amount of phosphotungstic acid and active carbon respectively, making both mass ratioes is 1: 4, and promptly activity component load quantity is 20% in the catalyst.Phosphotungstic acid is dissolved in the distilled water, makes the volume of its aqueous solution equal the pore volume of active carbon.Active carbon is flooded 5h in phosphotungstic acid aqueous solution, again this catalyst is dried 12h down at 130 ℃, stir once every 20min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier.Cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, is rescreened that to be divided into 20～40 orders standby.With prepared catalyst called after phosphotungstic acid-active carbon-20.
Glycerine water solution with 20% is raw material carries out glycerine in fixed-bed micro-reactor selectively dewatering reaction, use the no pulse measuring pump that glycerine water solution is sent into reactor continuously, reactor is that (Φ 10mm * 23cm), the liquid air speed is 1.2h to stainless-steel pipe
-1, phosphotungstic acid-active carbon-20 is 5mL, the dehydration temperature is 300 ℃.Final glycerol conversion yield is 80.6%, and the methacrylaldehyde selectivity is 68.8%.
Exemplifying embodiment 3
Take by weighing a certain amount of phosphomolybdic acid and diatomite respectively, making both mass ratioes is 1: 19, and promptly activity component load quantity is 5% in the catalyst.Phosphomolybdic acid is dissolved in the distilled water, makes the volume of its aqueous solution equal diatomaceous pore volume.Diatomite is flooded 4.5h in the phosphomolybdic acid aqueous solution, again this catalyst is dried 11h down at 140 ℃, stir once every 20min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier.Cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, is rescreened that to be divided into 20～40 orders standby.With prepared catalyst called after phosphomolybdic acid-diatomite-5.
Glycerine water solution with 10% is raw material carries out glycerine in fixed-bed micro-reactor selectively dewatering reaction, use the no pulse measuring pump that glycerine water solution is sent into reactor continuously, reactor is that (Φ 10mm * 23cm), the liquid air speed is 1.2h to stainless-steel pipe
-1, phosphomolybdic acid-diatomite-5 is 5mL, the dehydration temperature is 220 ℃.Final glycerol conversion yield is 13.5%, and the methacrylaldehyde selectivity is 49.0%.
Exemplifying embodiment 4
Take by weighing a certain amount of silico-tungstic acid and rutile titanium dioxide respectively, making both mass ratioes is 1: 9, and promptly activity component load quantity is 10% in the catalyst.Silico-tungstic acid is dissolved in the distilled water, makes the volume of its aqueous solution equal the pore volume of rutile titanium dioxide.Rutile titanium dioxide is flooded 4h in silicon tungsten acid solution, again this catalyst is dried 11h down at 140 ℃, stir once every 15min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier.Cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, is rescreened that to be divided into 20～40 orders standby.With prepared catalyst called after silico-tungstic acid-rutile titanium dioxide-10.
Glycerine water solution with 10% is raw material carries out glycerine in fixed-bed micro-reactor selectively dewatering reaction, use the no pulse measuring pump that glycerine water solution is sent into reactor continuously, reactor is that (Φ 10mm * 23cm), the liquid air speed is 1.2h to stainless-steel pipe
-1, silico-tungstic acid-rutile titanium dioxide-10 is 5mL, the dehydration temperature is 280 ℃.Final glycerol conversion yield is 18.3%, and the methacrylaldehyde selectivity is 50.5%.
Exemplifying embodiment 5
Take by weighing a certain amount of phosphotungstic acid and kaolin respectively, making both mass ratioes is 1: 5, and promptly activity component load quantity is 20% in the catalyst.Phosphotungstic acid is dissolved in the distilled water, makes the volume of its aqueous solution equal kaolinic pore volume.Kaolin is flooded 4h in phosphotungstic acid aqueous solution, again this catalyst is dried 11h down at 140 ℃, stir once every 15min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier.Cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, is rescreened that to be divided into 20～40 orders standby.With prepared catalyst called after phosphotungstic acid-kaolin-20.
Glycerine water solution with 10% is raw material carries out glycerine in fixed-bed micro-reactor selectively dewatering reaction, use the no pulse measuring pump that glycerine water solution is sent into reactor continuously, reactor is that (Φ 10mm * 23cm), the liquid air speed is 1.2h to stainless-steel pipe
-1, phosphotungstic acid-kaolin-20 is 5mL, the dehydration temperature is 280 ℃.Final glycerol conversion yield is 17.5%, and the methacrylaldehyde selectivity is 54.5%.
Exemplifying embodiment 6
Take by weighing a certain amount of silico-tungstic acid and activated alumina respectively, making both mass ratioes is 1: 4, and promptly activity component load quantity is 20% in the catalyst.Silico-tungstic acid is dissolved in the distilled water, makes the volume of its aqueous solution equal the pore volume of activated alumina.Activated alumina is flooded 4h in silicon tungsten acid solution, again this catalyst is dried 10h down at 120 ℃, stir once every 15min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier.Cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, is rescreened that to be divided into 20～40 orders standby.With prepared catalyst called after silico-tungstic acid-activated alumina-20.
Glycerine water solution with 20% is raw material carries out glycerine in fixed-bed micro-reactor selectively dewatering reaction, use the no pulse measuring pump that glycerine water solution is sent into reactor continuously, reactor is that (Φ 10mm * 23cm), the liquid air speed is 1.2h to stainless-steel pipe
-1, silico-tungstic acid-activated alumina-20 is 5mL, the dehydration temperature is 220 ℃.Final glycerol conversion yield is 57.5%, and the methacrylaldehyde selectivity is 79.2%.
Exemplifying embodiment 7
Take by weighing a certain amount of silico-tungstic acid and activated alumina respectively, making both mass ratioes is 1: 9, and promptly activity component load quantity is 10% in the catalyst.Silico-tungstic acid is dissolved in the distilled water, makes the volume of its aqueous solution equal the pore volume of activated alumina.Activated alumina is flooded 4h in silicon tungsten acid solution, again this catalyst is dried 10h down at 130 ℃, stir once every 15min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier.Cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, is rescreened that to be divided into 20～40 orders standby.With prepared catalyst called after silico-tungstic acid-activated alumina-10.
Glycerine water solution with 20% is raw material carries out glycerine in fixed-bed micro-reactor selectively dewatering reaction, use the no pulse measuring pump that glycerine water solution is sent into reactor continuously, reactor is that (Φ 10mm * 23cm), the liquid air speed is 1.2h to stainless-steel pipe
-1, silico-tungstic acid-activated alumina-20 is 5mL, the dehydration temperature is 300 ℃.Final glycerol conversion yield is 55.4%, and the methacrylaldehyde selectivity is 72.3%.
Claims (2)
1. selective glycerol dehydration prepares the Preparation of catalysts method of methacrylaldehyde, the expression formula of this catalyst is heteropoly acid/carrier, it is characterized in that wherein said heteropoly acid is a kind of in silico-tungstic acid, phosphotungstic acid, the phosphomolybdic acid, described carrier is a kind of in activated alumina, diatomite, active carbon, rutile titanium dioxide, the kaolin, the preparation of pore volume impregnation methods such as employing, step and condition are as follows:
(1) take by weighing a certain amount of heteropoly acid and carrier respectively, making both mass ratioes is 1: 4～1: 19, and promptly activity component load quantity is 5～20% in the catalyst; Heteropoly acid is dissolved in the distilled water, makes the volume of its aqueous solution equal the pore volume of carrier;
(2) carrier is flooded 4～5h in the heteropoly acid aqueous solution, again this catalyst is dried 10～12h down at 120～140 ℃, stir once every 15～20min in dipping process and the drying course, the catalyst after the oven dry is cooled to room temperature in drier;
(3) with cooled catalyst at 220 ℃ of following roasting 4h, to catalyst compressing tablet, the pulverizing after the roasting, rescreen that to be divided into 20～40 orders standby.
2. the application rights following program of process using that requires 1 described catalyst selective glycerol dehydration to prepare methacrylaldehyde is carried out: be reflected in the fixed bed reactors and carry out, the catalyst of catalytic amount is placed the reactor middle part, be that 10～20% glycerine water solution pumps in the reactor after vaporization with mass concentration, the liquid air speed is 1.2h
-1, raw material contacts under 220～300 ℃ with catalyst, and the gas-phase dehydration reaction takes place, and prepares methacrylaldehyde.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718637A (en) * | 2012-06-28 | 2012-10-10 | 南京理工大学常熟研究院有限公司 | Method of prolonging service life of catalyst in dehydration of glycerol for production of acrolein |
| CN102992980A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Method for preparing acrolein |
| CN104918908A (en) * | 2012-10-30 | 2015-09-16 | 安迪苏法国联合股份有限公司 | Method for preparing acrolein from glycerol |
| CN112517031A (en) * | 2020-12-14 | 2021-03-19 | 江苏索普工程科技有限公司 | Acrylic acid catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080898A (en) * | 1997-07-23 | 2000-06-27 | Shell Oil Company | Hydrogenolysis of glycerol |
| CN101417928A (en) * | 2008-12-09 | 2009-04-29 | 江苏工业学院 | Method for preparing acrylic aldehyde by biological glycerol dehydration |
-
2010
- 2010-06-29 CN CN 201010213226 patent/CN101879456A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080898A (en) * | 1997-07-23 | 2000-06-27 | Shell Oil Company | Hydrogenolysis of glycerol |
| CN101417928A (en) * | 2008-12-09 | 2009-04-29 | 江苏工业学院 | Method for preparing acrylic aldehyde by biological glycerol dehydration |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992980A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Method for preparing acrolein |
| CN102718637A (en) * | 2012-06-28 | 2012-10-10 | 南京理工大学常熟研究院有限公司 | Method of prolonging service life of catalyst in dehydration of glycerol for production of acrolein |
| CN102718637B (en) * | 2012-06-28 | 2014-04-30 | 南京理工大学常熟研究院有限公司 | Method of prolonging service life of catalyst in dehydration of glycerol for production of acrolein |
| CN104918908A (en) * | 2012-10-30 | 2015-09-16 | 安迪苏法国联合股份有限公司 | Method for preparing acrolein from glycerol |
| CN112517031A (en) * | 2020-12-14 | 2021-03-19 | 江苏索普工程科技有限公司 | Acrylic acid catalyst and preparation method and application thereof |
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