CN101417928A - Method for preparing acrylic aldehyde by biological glycerol dehydration - Google Patents
Method for preparing acrylic aldehyde by biological glycerol dehydration Download PDFInfo
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- CN101417928A CN101417928A CNA2008102431552A CN200810243155A CN101417928A CN 101417928 A CN101417928 A CN 101417928A CN A2008102431552 A CNA2008102431552 A CN A2008102431552A CN 200810243155 A CN200810243155 A CN 200810243155A CN 101417928 A CN101417928 A CN 101417928A
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- molecular sieve
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Abstract
The invention discloses a preparation method of acrolein, taking biological glycerol as the raw material and the modified zeolite supported heteropolyacid as catalyst, the method prepares acrolein directly by dehydration reaction. 18 to 30 catalyst are put in the middle section of a normal pressure continuous fixed bed reactor, with the volume space velocity of 1 to 10 h<-1>; under the protection of N2, the catalyst bed raises the temperature to 180 to 540 DEG C, and the biological glycerol solvent which is added with inhibitor is put into the fixed bed reactor from a micro pump; after gasified, the glycerine solution reacts by the catalyst bed. After reaction, the product is absorbed by acetone, then is separated and purified, thus obtaining acetone. The invention adopts the alkali metal, phosphoric oxides, alkali metal compound improved catalyst as carrier to carry heteropoly acid catalyst which is green and environmental catalyst and has the advantages of high activity, regeneration property, no pollution, simple reaction, operation process, low production cost, high mole selectivity of acrolein and high conversion rate of biological glycerol.
Description
Technical field
The present invention relates to utilize a kind of novel method of biomass material preparing acrylic aldehyde by biological glycerol dehydration, specifically is that the by product biological glycerol with biofuel is a raw material, and continuously dehydrating prepares the method for propenal under the effect of catalyzer.
Background technology
Biological glycerol is the by product of biofuel, and 10 tons of biofuel of every production will produce 1 ton of biological glycerol.And biofuel is rich in the green of potentiality, " petroleum plant " of clean alternative fuel as 21st century, with its recyclability and good environmental friendliness characteristic, demonstrate powerful developing state in fossil fuel oil substitute field, be subjected to the extensive concern of countries in the world.Along with people have quickened the renewable resources development, biological glycerol receives much concern as its deep process technology of by product of biofuel, becomes the focus of research in addition.
Propenal is a kind of important fine-chemical intermediate, has purposes widely at aspects such as coating, papermaking, oil field, medicine, organic synthesis industry.In recent years, supply falls short of demand along with animal feedstuff additive methionine(Met), glutaraldehyde, agricultural chemicals and water conditioner etc. on the market, and biological glycerol is excessive, has driven the fast development of propenal industry, and the development to the propenal industry has simultaneously proposed more and higher requirement.
The researchdevelopment of propenal technology of preparing up to now, a lot of methods have appearred, all obtained application as formaldehyde acetaldehyde vapour phase condensation method, propylene ether pyrolysis method, propylene or oxidation of propane method, but these methods mainly depend on the development of oil industry industrial.As time goes on, oil will face exhaustion as a kind of Nonrenewable resources, thus utilize the by product biological glycerol of biofuel required for the feedstock production propenal becomes situation, and this novel method will be brought good economic and social benefit.
Utilize glycerine to prepare propenal, initial method is carried out in the laboratory, utilize mineral acid and inorganic acid salt to make dehydrating glycerin prepare propenal as catalyzer, but the mole selectivity of the propenal that this method prepares and yield are not high, and in reaction, there is coking phenomenon, serious to equipment corrosion, contaminate environment is not easy to realize industrialization.
People such as Wan Xinjun have reported the method for preparing propenal with sal enixum and vitriolate of tartar and glycerine reaction, although experiment increases than the mole selectivity of the simple propenal that makes as catalyzer with sulfuric acid, can reach 32.8%, but there is heavier coking phenomenon in the reaction, serious to equipment corrosion, be not suitable for suitability for industrialized production.
People such as Masaru Watanabe have reported under the condition of supercritical water, are solvent with the pure water, under the reaction conditions of sulfuric acid as catalyzer, can significantly improve the selectivity of propenal.The reaction conditions that the author also further prepares propenal to dehydrating glycerin under supercritical reaction conditions is studied, and thinks and improves the mole selectivity that reactant, catalyst consumption will help improving the reaction product propenal.But all exist in these homogeneous reactions by product many, to equipment requirements height, glycerol conversion yield and the low problem of propenal mole selectivity.
French Patent FR 695931 has proposed to be prepared by glycerine as catalyzer with solid acid the method for propenal, allow glycerin vapor under hot conditions, pass through fixed-bed reactor, catalyzer adopts triprotic acid or its salt to load on the float stone, according to patent report, the highest yield of propenal can reach 75%～80%, but repeat this method according to DE 4238493, find tried to obtain corresponding yield under the reaction conditions, draw this method and can not carry out the technology application.
Simultaneously, discloses among the patent DE 4238493 and used solid catalyst, but it has only realized relatively low transformation efficiency that selectivity reduces when transformation efficiency improves, so need to improve with the gas phase and the liquid phase reaction of transformation of glycerol as propenal.
It is the phosphoric acid of tripolite loading that patent US 2558520 discloses catalyzer, and glycerine carries out dehydration reaction in gas phase or liquid phase, and obtaining the mole selectivity that dehydrating glycerin is converted into propenal is 72.3%.
Disclose the phosphoric acid catalyst of oxidation with aluminium, HZSM-5, HY even load among patent US 5426249 and the CN 1034803C, but about 71% the time when the propenal selectivity, glycerol conversion yield has only 19%.
Chinese patent CN 101070276A has reported glycerine on acid zeolite, is 200～500 ℃ in temperature, and pressure is 0.001～3.0MPa and liquid air speed 0.1～100.0h
-1Condition under, directly dehydration generates propenal.But this result can not repeat, and in fact, the selectivity of propenal only is about 8～10%, even the mole selectivity of elevated temperature propenal does not have obvious variation yet, and the transformation efficiency of glycerine is not high in the whole reaction.
In the above-mentioned patent report,, reduced investment, all existed the transformation efficiency of the mole selectivity of propenal and glycerine not high, the problem that by product is more equipment though adopted the solid acid catalyst of " environmental protection ".
It is raw material that this patent adopts the biomass material biological glycerol, basic metal, phosphorous oxides, basic metal mixture modified zeolite molecular sieve carried heteropoly acid are as catalyzer, the catalysis biological glycerine preparation propenal that directly dewaters in the fixed-bed reactor of continuous flow has improved the mole selectivity of the transformation efficiency and the propenal of glycerine greatly.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with the renewable resources biological glycerol, and production cost is low, reaction conditions is gentle, operating process is simple, the mole selectivity of product propenal and the higher method of glycerol conversion yield.Mainly be the fixed-bed reactor that utilize normal pressure continuous flow, adopt the Al of modification
2O
3, SiO
2, the load of Ca type zeolite molecular sieve heteropolyacid as the Preparation of Catalyst propenal, the mole selectivity of propenal can reach about 83.7%, and catalyzer is the environmental type catalyzer, and is little to equipment corrosion, easily regeneration.
Purpose of the present invention can reach by following measure:
A kind of novel method for preparing propenal is to be raw material with the biological glycerol, and the zeolite molecular sieve carried heteropoly acid of modification is a catalyzer, directly prepares propenal by dehydration reaction, and concrete steps are:
With pack into the stage casing of fixed-bed reactor of normal pressure continuous flow of the catalyzer of the zeolite molecular sieve carried heteropoly acid of 18～30 order modifications, check sealing after, at mobile N
2Purging under slowly the raise temperature to 180 ℃ of beds～540 ℃, then the biological glycerol content 10%～50% that has added 1%～5% hydroquinone of polymerization retarder is squeezed into fixed-bed reactor for the aqueous solution by micro pump, glycerine solution is after gasification, the solid catalyst of flowing through, a series of dehydration reaction generation propenal takes place in biological glycerol under the effect of catalyzer, the product propenal is collected with acetone after by the low temperature thermostat bath condensation and is obtained, and propenal is a light yellow transparent liquid.Reaction conditions is a normal pressure, and volume space velocity is preferably 1h
-1～10h
-1, adopt the gas-chromatography of OV-17 chromatographic column that the product propenal is analyzed, gas-chromatography is a hydrogen flame detector.The mole selectivity that chromatogram detects propenal is 83.7%, and the transformation efficiency of glycerine is 100%.
Wherein the zeolite molecular sieve of modification is preferably the Al of alkali metals modified
2O
3, SiO
2, Ca type zeolite molecular sieve, phosphorous oxides modification Al
2O
3, SiO
2, Ca type zeolite molecular sieve, the composite modified Al of basic metal
2O
3, SiO
2, Ca type zeolite molecular sieve.
The Al of alkali metals modified
2O
3, SiO
2, Ca type zeolite molecular sieve method of modifying be: with K
+, Mn
2+, Ca
2+, Co
2+, Cu
2+, Ni
2+, La
3+Plasma, wherein K
+Can derive from saltpetre, vitriolate of tartar, Repone K, potassiumphosphate, potassium hydrogen phosphate etc., Mn
2+, Ca
2+, Co
2+, Cu
2+, Ni
2+, La
3+Plasma is mainly derived from its nitrate and villaumite, and the charge capacity in 0.5%～10% (with the quality of ionic oxide formation thing) stirs by dipping under 40 ℃～80 ℃ condition, then 300 ℃～800 ℃ following incinerating modes to Al
2O
3, SiO
2, Ca type zeolite molecular sieve carries out modification.
The Al of phosphorous oxides modification
2O
3, SiO
2, Ca type zeolite molecular sieve method of modifying be: with Al
2O
3, SiO
2, Ca type zeolite molecular sieve places 0.5%～5% phosphoric acid salt, dihydrogen phosphate, hydrophosphate, phosphoric acid solution to stir to soak, obtain the Al of phosphorous oxides modification 300 ℃～800 ℃ of following roastings then
2O
3, SiO
2, Ca type zeolite molecular sieve.
The Al that basic metal is composite modified
2O
3, SiO
2, Ca type zeolite molecular sieve method of modifying be: earlier with Co
2+Ion is carried on Al with 0.5%～10% charge capacity
2O
3, SiO
2, on the Ca type zeolite molecular sieve, the Cu of load 0.5%～10% again after dry, 300 ℃～800 ℃ roastings
2+Or earlier with Cu
2+Charge capacity with 0.5%～10% is carried on Al
2O
3, SiO
2, on the Ca type zeolite molecular sieve, the Co of load 0.5%～10% again after drying, the high-temperature roasting
2+, obtain having the Al of the alkali metals modified of higher catalytic activity after last drying and the high-temperature roasting
2O
3, SiO
2, Ca type zeolite molecular sieve.
The Al of modification
2O
3, SiO
2, Ca type zeolite molecular sieve is as carrier loaded heteropolyacid, heteropolyacid is generally selected for use: the mixture of silicotungstic acid, phospho-wolframic acid, molybdenum wolframic acid, phospho-molybdic acid, silicomolybdic acid and multiple heteropolyacid, the charge capacity of heteropolyacid are 0.1%～70%, preferred 20%～50%.
Al after the modification
2O
3, SiO
2, Ca type zeolite molecular sieve carried heteropoly acid catalyst preparation process be: will be through the Al after the modification
2O
3, SiO
2, Ca type zeolite molecular sieve is crushed to 18～30 orders, adopt equi-volume impregnating to prepare catalyzer: the consumption (quality with carrier is that 10g is a benchmark) that calculates good used heteropolyacid according to charge capacity 20%～50%, then according to the consumption that calculates good heteropolyacid, take by weighing 2g～5g heteropolyacid and be mixed with the aqueous solution, then with the Al of 18～30 order modifications that fragmentation is good
2O
3, SiO
2, Ca type zeolite molecular sieve carrier pours in the heteropolyacid aqueous solution that configures, behind the dipping 24h, 110 ℃ of oven dry down, roasting 4h in 350 ℃ retort furnace then prepares the Al after the modification in baking oven
2O
3, SiO
2, Ca type zeolite molecular sieve carried heteropoly acid catalyzer.
It is excessive with the viscosity that prevents glycerine that the raw material biological glycerol adds entry, alcohol, fatty acid ester or their mixed solution in the reaction, blocking pipe, and the concentration of biological glycerol is 10%～80%, preferred 10%～50%.
Add stopper in the reaction raw materials biological glycerol, preferred Resorcinol, concentration is 1%～5%, preferred 2%～3%.
Reaction conditions of the present invention: temperature of reaction is 180 ℃～540 ℃, and preferred 260 ℃～360 ℃, volume space velocity is 0.1～90h
-1, preferred 1～10h
-1, reaction kit is the fixed-bed reactor of normal pressure continuous flow.
The activity of the heteropolyacid catalyst of the modified zeolite molecular sieve load that the present invention is used is more than 200 hours.The Al that is adopted among the embodiment
2O
3For the Qilu Petrochemical catalyst plant is produced.
Concrete reaction mechanism of the present invention:
With the biological glycerol is raw material, the zeolite molecular sieve carried heteropoly acid of modification is as catalyzer, under the reaction conditions of gentleness, the biological glycerol of gasification contacts with the zeolite molecular sieve carried heteropoly acid catalyst of modification, at first sloughs a part water and generates 1,3-the dihydroxyl third rare and by product pyruvic alcohol, 1,3-dihydroxyl third rare isomerization generates the 3-hydroxy propanal, and then sloughs a part water under the effect of catalyzer again, generate the target product propenal, obtain through the condensation collection.Be attended by the side reaction that the 3-hydroxy propanal decomposes in the process of reaction.Simultaneously, in the process of dehydrating glycerin, may be attended by the generation of different sorts glyceryl ether.
The equation of concrete reaction is:
The advantage of production propenal of the present invention is mainly reflected in the following aspects:
1, reaction raw materials is a biological glycerol, wide material sources and low price, and the production cost of propenal is low.
2, the zeolite molecular sieve carried heteropoly acid of this reaction employing modification is as catalyzer, and catalyst life is long, the catalytic activity height, and the renewable use of catalyzer and little to the corrodibility of equipment has reduced the pollution to environment.
3, this reacts the mole selectivity height of the catalyzer of employing to propenal, and has avoided the generation of by product pyruvic alcohol.
What 4, this reaction was adopted is the fixed-bed reactor of normal pressure continuous flow, and the operation process is simple.
5, this reaction is normal pressure, the reaction conditions gentleness, and the speed of reaction is fast.
The present invention has the activity of such catalysts height, the mole selectivity of propenal and the transformation efficiency height of glycerine, and the segregative advantage of process " cleaning " is a kind of eco-friendly friendly process of preparation propenal.
Embodiment
To be specified with example below, but not thereby limiting the invention.
Embodiment 1
Take by weighing Mn (NO
3)
2The about 1.9g of solution is dissolved in the 35ml distilled water, and preparation obtains 2.5% Mn (NO
3)
2The aqueous solution.And then measure the Mn (NO of 10ml2.5%
3)
2The aqueous solution is with 10g Al
2O
3Molecular sieve mixes, in the beaker of 100ml 80 ℃ of heated and stirred 4 hours, in 120 ℃ baking oven dry 8 hours then, dry post-modification zeolite molecular sieve is put into retort furnace in 350 ℃ of following roastings 4 hours, at last it is crushed to 18～30 orders.
Preparation 18～30 purpose modified zeolite molecular sieve carried heteropoly acid catalysts, adopt equi-volume impregnating to prepare catalyzer, calculate good used silicotungstic heteropolyacid consumption according to charge capacity 20%, then according to the consumption that calculates good heteropolyacid, take by weighing the 2g heteropolyacid and be mixed with the aqueous solution, the Al of 18～30 then that fragmentation is good order modifications
2O
3The zeolite molecular sieve carrier is poured in the heteropolyacid solution for preparing, and behind the dipping 24h, 110 ℃ of oven dry down, roasting 4h in 350 ℃ retort furnace prepares Mn-Al then in baking oven
2O
3/ H
4SiW
12O
40Catalyzer.
With 5ml18～30 purpose Mn-Al
2O
3/ H
4SiW
12O
40Pack into the stage casing of fixed-bed reactor of normal pressure continuous flow of catalyzer, hypomere is filled with quartz sand, and epimere is filled with iron filings.After the systems inspection sealing, at mobile N
2Purging under slowly the raise temperature to 200 ℃ of beds, then 10% the biological glycerol aqueous solution that has added 1% hydroquinone of polymerization retarder is squeezed into fixed-bed reactor by micro pump, glycerine solution is after gasification, the solid catalyst of flowing through, a series of dehydration reaction generation propenal takes place in biological glycerol under the effect of catalyzer, the product propenal is collected with acetone after by the low temperature thermostat bath condensation and is obtained, and propenal is a light yellow transparent liquid.Reaction is carried out on-line analysis every sampling in 1 hour.The mole selectivity that obtains propenal is 82.1%, and the transformation efficiency of glycerine is 96.7%.
Embodiment 2
Take by weighing Ca (NO
3)
2About 2.4g is dissolved in the 57.6ml distilled water, and preparation obtains 4% Ca (NO
3)
2The aqueous solution.And then measure the Ca (NO of 10ml4%
3)
2The aqueous solution is with 10g Al
2O
3Molecular sieve mixes, in the beaker of 100ml,, in 120 ℃ baking oven dry 8 hours then, dry post-modification zeolite molecular sieve is put into retort furnace in 350 ℃ of following roastings 4 hours 80 ℃ of heated and stirred 4 hours, at last it is crushed to 18～30 orders, obtains Ca-Al
2O
3Carrier.
Preparation 18～30 purpose modified zeolite molecular sieve carried heteropoly acid catalysts, adopt equi-volume impregnating to prepare catalyzer, calculate good used phosphorus heteropoly tungstic acid consumption according to charge capacity 20%, then according to the consumption that calculates good heteropolyacid, take by weighing the 2g heteropolyacid and be mixed with the aqueous solution, the Al of 18～30 then that fragmentation is good order modifications
2O
3The zeolite molecular sieve carrier is poured in the heteropolyacid solution for preparing, and behind the dipping 24h, 110 ℃ of oven dry down, roasting 4h in 350 ℃ retort furnace prepares Ca-Al then in baking oven
2O
3/ H
3PW
12O
40Catalyzer.
With 5ml18～30 purpose Ca-Al
2O
3/ H
3PW
12O
40Pack into the stage casing of fixed-bed reactor of normal pressure continuous flow of catalyzer, hypomere is filled with quartz sand, and epimere is filled with iron filings.After the systems inspection sealing, at mobile N
2Purging under slowly the raise temperature to 290 ℃ of beds, then 20% the biological glycerol aqueous solution that has added 2% hydroquinone of polymerization retarder is squeezed into fixed-bed reactor by micro pump, glycerine solution is after gasification, the solid catalyst of flowing through, a series of dehydration reaction generation propenal takes place in biological glycerol under the effect of catalyzer, the product propenal is collected with acetone after by the low temperature thermostat bath condensation and is obtained, and propenal is a light yellow transparent liquid.Reaction is carried out on-line analysis every sampling in 1 hour.The mole selectivity that obtains propenal is 82.3%, and the transformation efficiency of glycerine is 97.5%.
Embodiment 3
Take by weighing 2.9gCo (NO
3)
2, being dissolved in about 55ml distilled water, preparation obtains 5% Co (NO
3)
2The aqueous solution, and then measure the Co (NO of 10ml5%
3)
2The aqueous solution is with 10g Al
2O
3Molecular sieve mixes, in the beaker of 100ml,, in 120 ℃ baking oven dry 8 hours then, dry post-modification zeolite molecular sieve is put into retort furnace in 350 ℃ of following roastings 4 hours 80 ℃ of heated and stirred 4 hours, at last it is crushed to 18～30 orders, obtains 5% Co-Al
2O
3Carrier; And then take by weighing about 2.4g Cu (NO
3)
2, being dissolved in about 45.6ml distilled water, preparation obtains 5% Cu (NO
3)
2The aqueous solution is measured the Cu (NO of 10ml5%
3)
2The aqueous solution is with 10g 5%Co-Al
2O
3Molecular sieve mixes, in the beaker of 100ml 80 ℃ of heated and stirred 4 hours, in 120 ℃ baking oven dry 8 hours then, dry post-modification zeolite molecular sieve is put into retort furnace in 350 ℃ of following roastings 4 hours, obtain Co-Cu-Al
2O
3Carrier.
Preparation 18～30 purpose modified zeolite molecular sieve carried heteropoly acid catalysts, adopt equi-volume impregnating to prepare catalyzer, calculate good used phosphorus heteropoly tungstic acid consumption according to charge capacity 25%, then according to the consumption that calculates good heteropolyacid, take by weighing the 2.5g heteropolyacid and be mixed with the aqueous solution, the Co-Cu-Al of 18～30 then that fragmentation is good order modifications
2O
3The zeolite molecular sieve carrier is poured in the heteropolyacid solution for preparing, and behind the dipping 24h, 110 ℃ of oven dry down, roasting 4h in 350 ℃ retort furnace prepares Co-Cu-Al then in baking oven
2O
3/ H
3PW
12O
40Catalyzer.
With 5ml18～30 purpose Co-Cu-Al
2O
3/ H
3PW
12O
40Pack into the stage casing of fixed-bed reactor of normal pressure continuous flow of catalyzer, hypomere is filled with quartz sand, and epimere is filled with iron filings.After the systems inspection sealing, at mobile N
2Purging under slowly the raise temperature to 320 ℃ of beds, then 30% the biological glycerol aqueous solution that has added 3% hydroquinone of polymerization retarder is squeezed into fixed-bed reactor by micro pump, glycerine solution is after gasification, the solid catalyst of flowing through, a series of dehydration reaction generation propenal takes place in biological glycerol under the effect of catalyzer, the product propenal is collected with acetone after by the low temperature thermostat bath condensation and is obtained, and propenal is a light yellow transparent liquid.Reaction is carried out on-line analysis every sampling in 1 hour.The mole selectivity that obtains propenal is 83.7%, and the transformation efficiency of glycerine is 100%.
Embodiment 4
Take by weighing 4.1gLa (NO
3)
3, being dissolved in about 47ml distilled water, preparation obtains 8% La (NO
3)
3The aqueous solution, and then measure the La (NO of 10ml8%
3)
3The aqueous solution and 10g Al
2O
3Molecular sieve mixes, in the beaker of 100ml,, in 120 ℃ baking oven dry 8 hours then, dry post-modification zeolite molecular sieve is put into retort furnace in 350 ℃ of following roastings 4 hours 80 ℃ of heated and stirred 4 hours, at last it is crushed to 18～30 orders, obtains La-Al
2O
3Carrier.
Preparation 18～30 purpose modified zeolite molecular sieve carried heteropoly acid catalysts, adopt equi-volume impregnating to prepare catalyzer, calculate good used phosphorus heteropoly tungstic acid consumption according to charge capacity 30%, then according to the consumption that calculates good heteropolyacid, take by weighing the 3g heteropolyacid and be mixed with the aqueous solution, the La-Al of 18～30 then that fragmentation is good order modifications
2O
3The zeolite molecular sieve carrier is poured in the heteropolyacid solution for preparing, and behind the dipping 24h, 110 ℃ of oven dry down, roasting 4h in 350 ℃ retort furnace prepares La-Al then in baking oven
2O
3/ H
3PW
12O
40Catalyzer.
With 5ml18～30 purpose La-Al
2O
3/ H
3PW
12O
40Pack into the stage casing of fixed-bed reactor of normal pressure continuous flow of catalyzer, hypomere is filled with quartz sand, and epimere is filled with iron filings.After the systems inspection sealing, at mobile N
2Purging under slowly the raise temperature to 330 ℃ of beds, then 40% the biological glycerol aqueous solution that has added 3% hydroquinone of polymerization retarder is squeezed into fixed-bed reactor by micro pump, glycerine solution is after gasification, the solid catalyst of flowing through, a series of dehydration reaction generation propenal takes place in biological glycerol under the effect of catalyzer, the product propenal is collected with acetone after by the low temperature thermostat bath condensation and is obtained, and propenal is a light yellow transparent liquid.Reaction is carried out on-line analysis every sampling in 1 hour.The mole selectivity that obtains propenal is 82.3%, and the transformation efficiency of glycerine is 98.2%.
Embodiment 5
Take by weighing 5.8gCo (NO
3)
2, being dissolved in about 52.2g distilled water, preparation obtains 10% Co (NO
3)
2The aqueous solution, and then measure the Co (NO of 10ml10%
3)
2The aqueous solution and 10g Al
2O
3Molecular sieve mixes, in the beaker of 100ml,, in 120 ℃ baking oven dry 8 hours then, dry post-modification zeolite molecular sieve is put into retort furnace in 350 ℃ of following roastings 4 hours 80 ℃ of heated and stirred 4 hours, at last it is crushed to 18～30 orders, obtains 10% Co-Al
2O
3Carrier; Take by weighing the 3.6g nickelous nitrate then, be dissolved in about 32.4g distilled water, preparation obtains 10% Ni (NO
3)
2The aqueous solution is measured the Ni (NO of 10ml10%
3)
2The aqueous solution and 10gCo-Al
2O
3Molecular sieve mixes, in the beaker of 100ml 80 ℃ of heated and stirred 4 hours, in 120 ℃ baking oven dry 8 hours then, dry post-modification zeolite molecular sieve is put into retort furnace in 350 ℃ of following roastings 4 hours, obtain Co-Ni-Al
2O
3Carrier.
Preparation 18～30 purpose modified zeolite molecular sieve carried heteropoly acid catalysts, adopt equi-volume impregnating to prepare catalyzer, calculate good used phosphorus heteropoly tungstic acid consumption according to charge capacity 40%, then according to the consumption that calculates good heteropolyacid, take by weighing the 4g heteropolyacid and be mixed with the aqueous solution, the Co-Ni-Al of 18～30 then that fragmentation is good order modifications
2O
3The zeolite molecular sieve carrier is poured in the heteropolyacid solution for preparing, behind the dipping 24h, in baking oven 110 ℃ of down oven dry, and then with 350 ℃ retort furnace in roasting 4h, prepare Co-Ni-Al
2O
3/ H
3PW
12O
40Catalyzer.
With 5ml18～30 purpose Co-Ni-Al
2O
3/ H
3PW
12O
40Pack into the stage casing of fixed-bed reactor of normal pressure continuous flow of catalyzer, hypomere is filled with quartz sand, and epimere is filled with iron filings.After the systems inspection sealing, at mobile N
2Purging under slowly the raise temperature to 360 ℃ of beds, then 50% the biological glycerol aqueous solution that has added 4% hydroquinone of polymerization retarder is squeezed into fixed-bed reactor by micro pump, glycerine solution is after gasification, the solid catalyst of flowing through, a series of dehydration reaction generation propenal takes place in biological glycerol under the effect of catalyzer, the product propenal is collected with acetone after by the low temperature thermostat bath condensation and is obtained, and propenal is a light yellow transparent liquid.Reaction is carried out on-line analysis every sampling in 1 hour.The mole selectivity that obtains propenal is 81.7%, and the transformation efficiency of glycerine is 98.3%.
Embodiment 6
Measure the phosphoric acid solution of 10ml2.5%, with 10g Al
2O
3Molecular sieve mixes, in the beaker of 100ml 50 ℃ of heated and stirred 4 hours, in 120 ℃ baking oven dry 8 hours then, dry post-modification zeolite molecular sieve is put into retort furnace in 350 ℃ of following roastings 4 hours, at last it is crushed to 18～30 orders.
Preparation 18～30 purpose modified zeolite molecular sieve carried heteropoly acid catalysts, adopt equi-volume impregnating to prepare catalyzer, calculate good used silicotungstic heteropolyacid consumption according to charge capacity 50%, then according to the consumption that calculates good heteropolyacid, take by weighing the 5g heteropolyacid and be mixed with the aqueous solution, the Al of 18～30 then that fragmentation is good order modifications
2O
3The zeolite molecular sieve carrier is poured in the heteropolyacid solution for preparing, and behind the dipping 24h, 110 ℃ of down oven dry, roasting 4h in 350 ℃ retort furnace then prepares the Al of phosphorous oxides modification in baking oven
2O
3/ H
4SiW
12O
40Catalyzer.
With pack into the stage casing of fixed-bed reactor of normal pressure continuous flow of the catalyzer of 5ml18～30 purpose phosphorous oxides modifications, hypomere is filled with quartz sand, and epimere is filled with iron filings.After the systems inspection sealing, at mobile N
2Purging under slowly the raise temperature to 450 ℃ of beds, then 30% the biological glycerol aqueous solution that has added 5% hydroquinone of polymerization retarder is squeezed into fixed-bed reactor by micro pump, glycerine solution is after gasification, the solid catalyst of flowing through, a series of dehydration reaction generation propenal takes place in biological glycerol under the effect of catalyzer, the product propenal is collected with acetone after by the low temperature thermostat bath condensation and is obtained, and propenal is a light yellow transparent liquid.Reaction is carried out on-line analysis every sampling in 1 hour.The mole selectivity that obtains propenal is 81.1%, and the transformation efficiency of glycerine is 95.4%.
Claims (7)
1. the method for preparing acrylic aldehyde by biological glycerol dehydration, it is characterized in that with the biological glycerol being raw material, the zeolite molecular sieve carried heteropoly acid of modification is a catalyzer, directly prepare propenal by dehydration reaction, concrete steps are: with pack into the stage casing of fixed-bed reactor of normal pressure continuous flow of the catalyzer of the zeolite molecular sieve carried heteropoly acid of 18～30 order modifications, after checking sealing, at mobile N
2Purging under slowly the raise temperature to 180 ℃ of beds～540 ℃, then the biological glycerol content 10%～50% that has added 1%～5% hydroquinone of polymerization retarder is squeezed into fixed-bed reactor for the aqueous solution by micro pump, glycerine solution is after gasification, the solid catalyst of flowing through, a series of dehydration reaction generation propenal takes place in biological glycerol under the effect of catalyzer, the product propenal is collected with acetone after by the low temperature thermostat bath condensation and is obtained, and propenal is a light yellow transparent liquid; Reaction conditions is a normal pressure, and volume space velocity is 1h
-1～10h
-1Wherein the zeolite molecular sieve of modification is the Al of alkali metals modified
2O
3, SiO
2, Ca type zeolite molecular sieve, phosphorous oxides modification Al
2O
3, SiO
2, Ca type zeolite molecular sieve, the composite modified Al of basic metal
2O
3, SiO
2, Ca type zeolite molecular sieve; The zeolite molecular sieve carried heteropoly acid of described modification, heteropolyacid are the mixture of silicotungstic acid, phospho-wolframic acid, molybdenum wolframic acid, phospho-molybdic acid, silicomolybdic acid and multiple heteropolyacid, and the charge capacity of heteropolyacid is 0.1%～70%; Described biological glycerol is 10%～80% aqueous solution, alcoholic solution, fatty acid ester solution or their mixed solution.
2. the method for preparing acrylic aldehyde by biological glycerol dehydration according to claim 1 is characterized in that the Al of described alkali metals modified
2O
3, SiO
2, Ca type zeolite molecular sieve is: with K
+, Mn
2+, Ca
2+, Co
2+, Cu
2+, Ni
2+, La
3+Deng with 0.5%～10% charge capacity to Al
2O
3, SiO
2, Ca type zeolite molecular sieve carries out modification.
3. the method for preparing acrylic aldehyde by biological glycerol dehydration according to claim 1 is characterized in that the Al of described phosphorous oxides modification
2O
3, SiO
2, Ca type zeolite molecular sieve is: will soak in 0.5%～5% phosphoric acid salt, dihydrogen phosphate, hydrophosphate, the phosphoric acid solution, ageing makes.
4. the method for preparing acrylic aldehyde by biological glycerol dehydration according to claim 1 is characterized in that the Al that described basic metal is composite modified
2O
3, SiO
2, Ca type zeolite molecular sieve is: earlier with Co
2+Ion with 0.5%～10% charge capacity to Al
2O
3, SiO
2, Ca type zeolite molecular sieve carries out modification, and then the Cu of load 0.5%～10%
2+Or earlier with Cu
2+Charge capacity with 0.5%～10% is to Al
2O
3, SiO
2, Ca type zeolite molecular sieve carries out modification, and then the Co of load 0.5%～10%
2+
5. the method for preparing acrylic aldehyde by biological glycerol dehydration according to claim 1 is characterized in that described catalyzer is the Al of modification
2O
3, SiO
2, Ca type zeolite molecular sieve is as carrier loaded heteropolyacid, its preparation process is: the zeolite molecular sieve of modification is crushed to 18～30 orders, adopt the method for incipient impregnation to prepare catalyzer, calculating the consumption of good used heteropolyacid according to charge capacity 20%～50%, is that 10g is a benchmark with the quality of carrier, and the heteropolyacid that takes by weighing mass range and be 2g～5g is mixed with the aqueous solution, then that fragmentation is good carrier is poured in the heteropolyacid solution for preparing, behind the dipping 24h, drying, roasting obtains catalyzer.
6. the method for preparing acrylic aldehyde by biological glycerol dehydration according to claim 1 is characterized in that described biological glycerol is 10%～50% the aqueous solution, alcoholic solution, fatty acid ester solution or their mixed solution.
7. the method for preparing acrylic aldehyde by biological glycerol dehydration according to claim 1 is characterized in that the reaction conditions of biological glycerol dehydration is: 260 ℃～360 ℃ of temperature, normal pressure, volume space velocity 1～10h
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