CN104387249A - Preparation method of acraldehyde - Google Patents
Preparation method of acraldehyde Download PDFInfo
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- CN104387249A CN104387249A CN201410601341.4A CN201410601341A CN104387249A CN 104387249 A CN104387249 A CN 104387249A CN 201410601341 A CN201410601341 A CN 201410601341A CN 104387249 A CN104387249 A CN 104387249A
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- glycerine
- propenal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
Abstract
The invention provides a method for preparing acraldehyde by carrying out catalytic dehydration on desalted crude glycerine. The method for preparing acraldehyde is characterized in that biodiesel byproduct crude glycerine is taken as a raw material, almost only desalination treatment is carried out, and a catalytic dehydration reaction is directly carried out for preparing acraldehyde without carrying out essential water evaporation concentration and removal of methanol, fatty acid, fatty acid ester and other impurity compounds. Experiments find that a catalytic effect is equivalent to that if refined glycerine is taken as a raw material when salt content of desalted crude glycerine is lower than 1wt%, and desalination operation cost is reduced; the biodiesel byproduct desalted crude glycerine is adopted as the raw material, and refining processes such as water evaporation concentration and removal of organic matter impurities with high energy consumption, complex steps and high cost are eliminated, thus the yield, the same as that if the refined glycerine is taken as the raw material, of the target product acraldehyde can be obtained; meanwhile, operation is simple, raw material cost is low, loss of glycerine in the refining process is reduced, the utilization rate of crude glycerine is high, the reaction rate is high, the yield of acraldehyde is high, catalyst life is long, and green chemistry industrial requirements are met.
Description
Technical field
The present invention relates in general to the method preparing propenal, particularly utilizes glycerine to prepare the method for propenal.
Background technology
Propenal is a kind of important organic synthesis intermediate, function served as bridge is played in raw glycerine trans-utilization---propenal can be oxidized further and generate broad-spectrum acrylicacidandesters, also can as the Material synthesis macromolecular material (as: sodium polyacrylate) carrying out polyreaction, reaction formula is such as formula shown in (1):
Propenal also can be used to synthetic methionine, reaction formula is such as formula shown in (2): methionine(Met) is the amino acid that a kind of organism can not be synthesized voluntarily, it can be used as to promote growth of animal, the methionine concentration that natural methionine(Met) source (plant, microorganism) provides and output all lower, cannot human's demand be met.Current global methionine(Met) production capacity reaches 500000 tons, and the mankind to the demand of methionine(Met) still with 3 ~ 7% speed increment.
In addition, propenal also can be used as the sterilant (suppress to inject the bacterial growth of water, prevent bacterium from causing the problems such as corrosion and blocking on stratum) of oilfield injection water; Its dimer can be used for twain-aldehyde compound compound processed, is widely used as papermaking, tanning and textile auxiliary agent; The raw material of propenal or glutaraldehyde, 1,2,6-hexanetriol and linking agent etc., also for the manufacture of colloid osmium, ruthenium, rhodium.Propenal and bromine effect can obtain 2,3-dibromopropanal.2.3-dibromopropanal is medicine intermediate, is used for producing antitumour drug MTX etc.
The industrial process of propenal mainly contains formaldehyde and acetaldehyde condensation, oxidation of propylene, propane oxidation and glycerin catalytic evaporation etc.As far back as 1938, Degussa company of the Germany impregnated silica gel of water glass adopts formaldehyde acetaldehyde to obtain propenal through vapour phase condensation, and in nineteen forty-one industrialization, formalin and acetaldehyde excessive are a little by the beds in tubular reactor, temperature of reaction 300 ~ 320 DEG C, yield counts 75% with acetaldehyde, along with the development of petroleum industry, provide a large amount of propylene feedstocks, oxidation of propylene becomes the route the most widely used in the world.Technical process is: propylene, air and water vapour mix in certain proportion, then at 290 ~ 380 DEG C, 200 ~ 300kPa, and oxidizing reaction is there is under the effect of catalyzer, generate propenal and other by product, release a large amount of heat simultaneously, this technique should control temperature of reaction and stablize, from reactor gas out through cooling and with a large amount of water quenchings, to remove acidic by-products.Containing propenal the aqueous solution through stripping, refining after obtain product propenal.In recent years, along with the exhaustion day by day of petroleum resources and going from bad to worse of ecotope, the method cost of the production propenal being raw material with propylene propane raises year by year.
Along with biofuel flourish with superior environmental-protecting performance, also increased year by year by the glycerol production of biodiesel byproduct, shown in (3), can find out, can raw raw glycerine byproduct simultaneously in the production process of biofuel.
According to statistics, often produce 10 tons of biofuel, will the raw glycerine of by-product 1 ton, along with the development of Biodiesel, the output of raw glycerine improves year by year, with it simultaneously, because purification of glycerin process comprises moisture evaporation concentration, desalination, methyl alcohol, lipid acid, fatty acid ester and other impurity compounds remove a series of process, the large cost of energy consumption is high.Therefore the output of refining glycerine and demand are not greatly improved, and therefore define the accumulation of raw glycerine more than needed gradually.The accumulation of raw glycerine result in plummeting of its price, and become the bottleneck of biofuel development, therefore finding rational downstream utilization ways for raw glycerine becomes urgent problem.Statistics display, nineteen ninety-five was by 2015 these 20 years, the price of raw glycerine is down to 150 dollars/t from 900 dollars/t, and raw glycerine main component is glycerine (40% ~ 50%), methyl alcohol (20% ~ 30%), alkaline salt catalyzer (3% ~ 5%) and soap (20% ~ 25%).Carry out being separated to biological diesel oil byproduct glycerin and refine, through decolouring, distillation process can obtain high-purity glycerol.Due to refining glycerine because sepn process cost is higher, refining glycerine price is at 900-1000 dollar/about t.Found by investigation, the price general trend of propenal steadily rises, and as from January, 2007 in December, 2013, propenal price rises to 1300 dollars/t from 1200 dollars/t.Therefore comprehensively analyze raw material and many-sided factor such as product and production cost, we can draw such conclusion: be have market outlook very much by raw glycerine preparing hydroxyacetone by selectively dewatering, are also necessary to its research.
Propenal prepared by glycerine homogeneous catalysis and heterogeneous catalysis two kinds of methods.Patent CN200810243155.2 describes under the condition of hot pressurized water, with the refining glycerine aqueous solution for raw material has investigated temperature of reaction, H
2sO
4concentration, glycerol concentration and pressure are on the impact of selective glycerol dehydration reactivity worth, and result shows, the glycerine of high density and H
2sO
4and higher temperature and pressure contributes to the generation of propenal, under 400 DEG C and 34.5MPa condition, glycerol conversion yield reaches 90%, and acrolein selectivity reaches 90%.Because homogeneous reaction is carried out under high temperature and high pressure criticality, the aqueous solution can etching apparatus, after acid adding or inorganic acid salt, and corrosion aggravation; Secondly, under the high temperature conditions, when raw glycerine acts on acid, coking is serious; Again, high top pressure operation is uneconomical, and reactive behavior is not high; Finally, owing to being homogeneous reaction, catalyzer and product need to be separated.Therefore, glycerine heterogeneous catalysis is prepared propenal and is had reaction conditions gentleness, and reactive behavior is high, low for equipment requirements, and catalyzer easily reclaims the remarkable advantages such as separation.Adopt multiphase solid acid catalytic systems to carry out gas-solid reaction Dehydration in sum, for propenal, there is obvious advantage.
Existing achievement in research many employings refining glycerine is raw material, higher in order to obtain purity, the glycerol stocks that foreign matter content is less, need raw glycerine through moisture evaporation concentration, the organism such as methyl alcohol remove, desalting treatment, decolouring, the series of preprocessing such as pH regulator, wherein moisture evaporation needs to carry out under vacuum, these purification operations energy consumptions are high, flow process is complicated, cause a large amount of glycerine to lose simultaneously, therefore in whole reaction process, the utilization ratio of raw glycerine is poor, do not meet the requirement of Green Chemistry, add the cost that biomass raw dehydrating glycerin prepares propenal, become the bottleneck of restriction glycerol production propenal.
It is that 20% smart aqueous glycerin solution of catalyzer prepares the method for propenal for raw material that patent FR 695931 proposes with solid acid, fixed-bed reactor are passed through under the high temperature conditions after allowing the 20wt% refining glycerine aqueous solution gasify, catalyzer adopts loading type triprotic acid, the highest yield of propenal can reach 80%, but carry out repetition according to patent DE 423493 pairs of the method, corresponding yield can not be obtained.
Patent US 5426249 and CN 1034803C discloses with aluminum oxide, and the phosphoric acid salt of HZSM-5, HY even load is catalyzer, take refining glycerine as the method that propenal prepared by raw material, but when the highest yield of propenal can reach 71%, glycerol conversion yield only has 19%
Chinese patent CN 201010213226.1 proposes with loaded by heteropoly acid at aluminum oxide, diatomite, gac, rutile titanium dioxide or kaolin are catalyzer is the method that propenal prepared by raw material with refining glycerine on micro fixed-bed reactor, glycerol conversion yield is 13.5 ~ 80.6%, and the highest yield of propenal reaches 49.0 ~ 90.5%, but catalyzer easy in inactivation, life-span is short, and later transformation rate selectivity all significantly reduces.
Patent CN200880105819.7 adopts the method for reactive evaporation directly to prepare propenal by raw glycerine, take raw glycerine as raw material, carry out evaporation in the reactor to purify simultaneously, moisture in deglycerizin and other partial impurities, then react on a catalyst, but due to evaporation purify and dehydration reaction wayward, glycerine purification operations is complete not, a large amount of salts substances is still had not to be removed before the reaction in raw glycerine, salt is caused to deposit on a catalyst in a large number, reaction later stage catalyst activity and selectivity is caused significantly to reduce, after reaction 26h, propenal yield is only 20-30%.
Summary of the invention
In view of the foregoing, the present invention has been made.
According to an aspect of the present invention, provide a kind of propenal preparation method preparing propenal, it is characterized in that taking raw glycerine as raw material, substantially only desalting treatment is carried out to this raw glycerine, utilize the raw glycerine after such desalting treatment and catalyzer in reactor, carry out dehydration reaction and prepare propenal.
Describedly substantially only desalting treatment is carried out to this raw glycerine and comprise any one process raw glycerine do not carried out in lower column processing: moisture evaporation concentration, methanol stripper, lipid acid remove, fatty acid ester removes, other impurity compounds remove.
It is described that to carry out desalting treatment to raw glycerine can be 1wt% or following by raw glycerine desalination to saltiness.
Raw glycerine desalting method can adopt electrodialysis, the one in reverse osmosis method and ion-exchange-resin process.
Raw glycerine desalting method can adopt ion-exchange-resin process.
In one example, in ion-exchange-resin process demineralising process, adopt large porous strong acid cation exchange resin desalination, raw glycerine operation flow is 2.0-3.0mL/min, and water/raw glycerine volume ratio is 0.5-2.In one example, raw glycerine operation flow is 2.5mL/min, and water/raw glycerine volume ratio is 1
In one example, about propenal preparation method, be 10%-60% in the concentration of the raw material desalination raw glycerine aqueous solution, reactor adopts fixed bed, and temperature of reaction is 250-350 DEG C, and reaction pressure is normal pressure.
In one example, propenal preparation method adopts supported heteropoly compound to be catalyzer.
In one example, the supported heteropoly compound adopted in propenal preparation method is phospho-wolframic acid, phospho-molybdic acid, the heteropolyacids such as silicotungstic acid or its Suanphosphotungstate, phosphomolybdate, the one in silicotungstate, carrier is each metalloid, the one in nonmetal oxide and molecular sieve.
The desalination raw glycerine of the embodiment of the present invention is utilized to produce the method for propenal by catalytic and dehydration reaction, direct employing biomass raw glycerine is raw material, substantially only desalting treatment is carried out to raw glycerine, desalination is to saltiness 1wt% or following, moisture evaporation concentration is not carried out to raw glycerine, methyl alcohol, lipid acid, fatty acid ester and other colored compounds remove, the object product yield same with refining glycerine and catalyst stability can be obtained, save raw glycerine evaporation concentration, organism removes, the purification step such as decolouring, reduce costs and energy consumption.
Such as, raw glycerine desalinating process can adopt electrodialysis, and reverse osmosis method and ion hand over exchange resin method, and preferred ion exchange resin method, desalination to saltiness is 1wt% or following.Desalination ion exchange resin adopts large porous strong acid cation exchange resin dealkalize metal ion; Raw glycerine operation flow in demineralising process is 2.0-3.0mL/min, preferred 2.5mL/min; Water/raw glycerine volume ratio 0.5-2, preferred volume ratio is 1.Ion-exchange-resin process desalination adopts following program to carry out: ion exchange column adopts the glass column of Φ 30 × 800mm, load macroreticular acidic Zeo-karb respectively, pump into the ion exchange column that resin is housed from capital with peristaltic pump, column bottom effluent liquid graduated cylinder is collected and measures efflux volume.
The preparation of raw glycerine dehydration catalyst can such as adopt following program to carry out:
1) Cs2CO3 is made into the aqueous solution that volumetric molar concentration is 0.1 ~ 0.25molL-1 concentration, is added in the described aqueous solution by SBA-15 carrier, at room temperature flood after stirring, make charge capacity be 5% ~ 70%, preferred negative carrying capacity is 50%, dry for standby;
2) Cs2CO3 in molar ratio: heteropolyacid=0.5:1 ~ 1.5:1, preferred molar ratio Cs2CO3: heteropolyacid=1.25:1.Take heteropolyacid and be made into the aqueous solution that volumetric molar concentration is 0.05 ~ 0.1molL-1 concentration, at room temperature flood after stirring, filter, wash and drying, at temperature is 400 ~ 700 DEG C, calcine 3 ~ 5h preferred calcination temperature is 500 DEG C, obtained active ingredient is the loaded catalyst of phospho-wolframic acid cesium salt, carry out compressing tablet to catalyzer, pulverizing is sieved for subsequent use again.
The exemplary technique preparing propenal can adopt following program to carry out: react and carry out in micro fixed-bed reactor, catalyzer is placed in isothermal section in the middle part of reactor, the concentration of aqueous glycerin solution is 10%-60%, preferred 10-30%, the desalination raw glycerine aqueous solution is pumped into reactor, also pass through on a catalyst subsequently in the gasification of reactor vaporization section, liquid air speed is 1.3h
-1, raw material contacts at 300 DEG C with catalyzer, and gas-phase dehydration reaction occurs, obtained propenal.Collect product with the condensation of ethanol cold gas liquid/gas separator, product is undertaken quantitatively and qualitative analysis by gas-chromatography.
Adopt catalyzer of the present invention to carry out the technique of raw glycerine Dehydration for propenal, its outstanding advantages is:
(1) raw glycerine that biopathways can be adopted to obtain is raw material, only through simple desalting treatment, without the need to carrying out moisture evaporation concentration and other unnecessary dedoping step, the target product propenal yield identical with taking refining glycerine as raw material can be obtained, belong to the green bio chemical process of environment-friendly type, avoid purifying the wastage of material caused to raw glycerine, simplify raw glycerine simultaneously and prepare propenal technical process, reduce production cost.
(2) desalting treatment is simple to operate, and glycerine purity requirement is low, and the salts contg in desalination raw glycerine is that 1wt% can meet the demands.
(3) adopt ion-exchange-resin process to carry out glycerine desalination, simple to operate, ratio of desalinization is high.
React under (4) 300 DEG C of normal pressures, mild condition, adopt solid catalyst gas-phase reaction low for equipment requirements.
(5) the catalyst inducement phase is short, reach optimal conversion and selectivity very soon, and selectivity is high, and by product (mainly pyruvic alcohol) is few, and the life-span is long.
(6) desalination raw glycerine transformation efficiency and acrolein selectivity high, optimal proportion 50HPW/Cs-SBA catalyzer can reach 100% and 88% respectively, and catalyst life is long, after reaction 120h, still keep initial reaction active.
(7) catalyzer Heat stability is good, can keep active by reaction of making charcoal at 500 DEG C.
(8) obtain the impurity removal process that the product propylene aldehyde solution containing partial impurities can directly utilize propane-propylene oxidation style to prepare propenal and carry out refining purification.
Embodiment
In order to make those skilled in the art understand the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Saying " raw glycerine " in this specification sheets and " smart glycerine " are the terms that those skilled in the art commonly use, and adopt the general implication in this area, the glycerol concentration in general raw glycerine is about 30-85%, and the glycerol concentration in smart glycerine is more than 95%.
Saying in this specification sheets " only carries out desalting treatment to raw glycerine " or " substantially " in " substantially only needing to carry out desalting treatment to raw glycerine " or " substantially merely through the raw glycerine of desalting treatment " substantially, refer to and desalting treatment is carried out to raw glycerine, and do not carry out the industrial process in order to make the essence needed for smart glycerine from raw glycerine, but do not get rid of and can carry out some basic simply and easy treat to raw glycerine, these basic simply and easy treat comprise such as filtration, desalination etc., but are not limited to these.
The present inventor expects, if be raw material from the raw glycerine of biomass by-product, determine to for the preparation of propenal the influential impurity of dehydration reaction and this impurity is removed specially, and without the need to passing through complicated rectification flow to raw glycerine, the flow process that raw glycerine prepares propenal can be simplified, reduce production cost.
Contriver finds through experiment, the dehydration reaction that salt pair in raw glycerine prepares propenal has considerable influence, by carrying out catalytic dehydration experiment to the raw glycerine containing different impurities component, find substantially only to need to carry out desalting treatment to raw glycerine, and do not need to carry out moisture evaporation concentration to raw glycerine, methyl alcohol, the organism such as fitter acids and its ester class remove, dehydration reaction can be carried out, obtain higher propenal yield, catalyst reaction effect be that raw material is suitable with refining glycerine, simultaneously the reaction effect of catalyzer and life-span can not be subject to moisture, methyl alcohol, the organic impacts such as fitter acids and its ester class.
Experiment finds, carry out dehydration reaction using the glycerine without desalting treatment as raw material, catalyst selectivity and transformation efficiency significantly decline after 40h, and therefore de-salting operation is necessary for dehydrating glycerin reaction.
Be determined by experiment the most supersalinity ensureing propenal yield and catalyst stability for this reason, reduce demineralising process cost, as long as being below the 1wt% propenal yield that can ensure to obtain through the glycerine saltiness of desalting treatment is that raw material is identical with refining glycerine, other impurity contained in desalination raw glycerine do not impact reaction result.
Based on experiment, by adding methyl alcohol in smart glycerine, the organism such as fitter acids and its ester class are that raw material carries out reaction evaluating, the moisture contained in known desalination raw glycerine, methyl alcohol, the organism such as fitter acids and its ester class can not impact catalyzed reaction, carry out moisture evaporation concentration to raw glycerine, methyl alcohol, the organism such as fitter acids and its ester class remove prepares acrolein reaction and non-essential process for glycerine.Compare moisture evaporation concentration, methyl alcohol, the organism such as fitter acids and its ester class remove, de-salting operation cost is low, simple to operate, only need to ensure that the saltiness of desalination raw glycerine can meet the requirement of catalyzed reaction Dehydration for propenal lower than 1wt% simultaneously, therefore the embodiment of the present invention substantially only desalting treatment is carried out to raw glycerine, namely utilize the raw glycerine after such desalting treatment and catalyzer in reactor, carry out dehydration reaction and prepare propenal, greatly can reduce the flow process and the reduction production cost that simplify raw glycerine and prepare propenal.
Raw glycerine desalting method can adopt electroosmose process, and reverse osmosis method or ion hand over exchange resin method, preferred ion exchange resin method.Ion exchange resin adopts large porous strong acid cation exchange resin to remove an alkali metal salt.Raw glycerine operation flow in demineralising process is 2.0-3.0mL/min, preferred 2.5mL/min; Water/raw glycerine volume ratio 0.5-2, preferably water/raw glycerine volume ratio 1
Catalytic reaction process can adopt fixed bed to carry out gas solid catalytic reaction, and temperature of reaction is 280-350 DEG C, preferably 300 DEG C, and reaction pressure is normal pressure, and the concentration of aqueous glycerin solution is 10%-60%, preferred 10-30%.Employing supported heteropoly compound is catalyzer, and heteropolyacid is phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid cesium salt or silicomolybdic acid.Preferred Suanphosphotungstate Cs
xh
3-xpW
12o
40middle Cs/H, x=2 ~ 3 and preferred x=2.5.Described carrier is each metalloid, nonmetal oxide or molecular sieve, preferred molecular sieve SBA-15.Activity component load quantity 5%-70%, and preferably 50%.
A kind of concrete mode of the present invention provides a kind of method that desalination raw glycerine catalytic dehydration prepares propenal, with the raw glycerine of biodiesel byproduct for raw material, only through desalting treatment, and do not carry out moisture evaporation concentration, removing of methyl alcohol, lipid acid, fatty acid ester and other impurity compounds, directly carries out the method that catalytic and dehydration reaction prepares propenal.Only to pass through simple desalting treatment, and do not carry out moisture evaporation concentration, methyl alcohol, lipid acid, fatty acid ester and other impurity compounds remove, and the desalination raw glycerine obtained is raw material, directly carry out catalytic and dehydration reaction.After reaction more than 100h, glycerol conversion yield reaches 100%, and acrolein selectivity reaches 87-90%.With with through moisture evaporation concentration, desalination, the refining glycerine obtained after methyl alcohol, lipid acid, fatty acid ester and other impurity compounds remove is raw material, and the propenal yield carrying out catalytic dehydration is suitable.Glycerine through containing different impurities composition is that raw material carries out reaction effect contrast, find that the salt in raw glycerine is the key factor affecting catalyst effect, moisture and other impurity compounds do not have a significant effect to catalyzed reaction, find in addition, when desalination raw glycerine saltiness is lower than ensureing catalytic effect and be that raw material is suitable with refining glycerine during 1wt%, to reduce de-salting operation cost.Therefore, the desalination raw glycerine adopting biodiesel byproduct is raw material, eliminate energy consumption is large, step is complicated, cost is high moisture evaporation concentration, the refining step such as organic impurities removes, the target product propenal yield identical with taking refining glycerine as raw material can be obtained.Simple to operate, raw materials cost is low, decreases the loss of glycerine in treating process, and raw glycerine utilization ratio is high, and speed of reaction is fast, and propenal yield is high, and catalyst life is long, meets the requirement of Green Chemistry industry.
Embodiment 1 (desalination raw glycerine and raw glycerine reaction effect contrast)
This embodiment is prepared propenal to carrying out dehydration reaction using the raw glycerine substantially merely through desalting treatment as raw material and is carry out the reaction effect that dehydration reaction prepares propenal under raw material condition to contrast with raw glycerine.
The making of catalyzer: the charge capacity by 20% takes the Cs of 0.25g
2cO
3, and be made into 0.2molL
-1the aqueous solution of concentration, adds 8g SBA-15 carrier in the above-mentioned aqueous solution, makes charge capacity be 50%, at room temperature floods a night, dry for standby at 80 DEG C after vigorous stirring 2 ~ 5h, take appropriate heteropolyacid H
3pW
12o
4012H
2o is also made into 0.08molL
-1the aqueous solution of concentration makes Cs
xh
3-xpW
12o
40middle x=2.5 also mixes with above-mentioned carrier, at room temperature floods a night, filters, washing after adopting incipient impregnation vigorous stirring 2 ~ 5h, dry.Dried catalyzer calcines 4h at 500 DEG C, and obtained carried heteropoly acid cesium salt 50HPW/Cs-SBA catalyzer, carries out compressing tablet to catalyzer, and pulverizing screening is again that 30-50 order is for subsequent use.
Substantially merely through the preparation of the raw glycerine (hereinafter referred for " desalination raw glycerine ") of desalting treatment: raw glycerine adopts the glass column of Φ 30 × 2 × 800mm to carry out ion-exchange desalination, filling macroreticular acidic Zeo-karb, Crude glycerin solution peristaltic pump pumps into the ion exchange column that resin is housed from capital, raw glycerine operation flow in demineralising process is 2.5mL/min, water/raw glycerine volume ratio 1, desalination is to saltiness lower than 1wt%, and column bottom effluent liquid graduated cylinder is collected.
Respectively using 20% the raw glycerine without any process and through the desalination raw glycerine aqueous solution of ion-exchange desalination as raw material, the reaction of raw glycerine selectively dewatering is carried out in micro fixed-bed reactor, be adopted as volume pump (Series 2, .001-5ml/min, SS, S.G.Seal Self Flush, Pulse Damper) continuously feeding, adopt stainless steel tube as reactor (Φ 10mm × 40mm).Wherein first paragraph (20mm) is preheating gasification section, and loading 0.5g catalyzer and diluting selectively dewatering temperature with quartz sand is 300 DEG C.After successive reaction 1,10,20,40h, carry out the activity sampling evaluate catalysts respectively, selectivity and stability, result compares in the following Table 1.
From table 1, directly adopt raw glycerine to be raw material, catalyzer active selectable after reaction 20h significantly declines, and adopt the raw glycerine after desalination to be that raw material reacts, catalyst stability is good, and after 40h, glycerol conversion yield is substantially constant, and acrolein selectivity is 88%.Known reactive behavior and object product propylene aldehyde yield raw glycerine desalting treatment being conducive to raising catalyzer, improves the stability of catalyzer, the extending catalyst life-span simultaneously.
Table 1
Embodiment 2 (desalination raw glycerine and smart glycerine are that raw material carries out reaction effect contrast)
This embodiment is carried out dehydration reaction to desalination raw glycerine as raw material and is prepared propenal and contrast with propenal to be prepared by smart glycerine reaction effect for carrying out dehydration reaction under raw material condition.
Adopt through moisture evaporation concentration respectively, desalination, smart glycerine after the organism such as methyl alcohol, fitter acids and its ester class remove, substantially merely through desalting treatment (such as desalting treatment to saltiness lower than 1wt%), and be raw material without the desalination raw glycerine of other purification operations, catalytic and dehydration reaction is carried out when other conditions are identical; The preparation of catalyzer and reaction conditions are with embodiment 1.Result compares in the following Table 2.
From table 2, utilize desalination raw glycerine to react, after 40h, glycerol conversion yield is substantially constant, and acrolein selectivity is 88%, identical with refining glycerine effect.Illustrate that raw glycerine only needs desalination to saltiness lower than 1wt%, and do not need to carry out moisture evaporation concentration to raw glycerine, methyl alcohol, the organism such as fitter acids and its ester class remove, can dehydration reaction be carried out, obtain higher propenal yield, catalyst reaction effect be that raw material is suitable with refining glycerine.
Table 2
Embodiment 3 (glycerine containing different impurities is that raw material carries out reaction effect contrast)
With through moisture evaporation concentration, desalination, the refining glycerine after the organism such as methyl alcohol, fitter acids and its ester class remove is raw material, and add 2wt% methyl alcohol respectively, 2wt% lipid acid, 2wt% fatty acid ester, 2wt% salt reacts.After successive reaction 40h, carry out the activity sampling evaluate catalysts, selectivity and stability, catalyst component and other reaction conditionss are with embodiment 1, and result compares in the following Table 3.
More known by the reaction yield in table 3, methyl alcohol in raw glycerine, lipid acid, the organic impurities such as fatty acid ester can not impact catalyst reaction effect, containing methyl alcohol, lipid acid, the refining glycerine of fatty acid ester still has the propenal yield of 88% after reaction 40h, and refining glycerine and desalination raw glycerin phase are worked as.But the refining glycerine catalyst activity containing salt impurity significantly reduces, and after 40h, transformation efficiency is 84%, and acrolein selectivity is reduced to 76%, the salt impurity in known raw glycerine is the principal element causing raw glycerine Dehydration to reduce for acrolein reaction yield.Further illustrate raw glycerine only to need carry out simple desalting treatment and do not need to carry out moisture evaporation concentration to raw glycerine, methyl alcohol, the organism such as fitter acids and its ester class remove, dehydration reaction can be carried out, obtain higher propenal yield, other impurity in desalination raw glycerine can not affect the reaction yield that desalination raw glycerine prepares propenal, catalyst reaction effect be that raw material is suitable with refining glycerine.
Table 3
Embodiment 4 (the desalination glycerine of different saltiness is that raw material carries out reaction effect contrast)
With saltiness 0.5wt ~ 1.5wt% for desalination raw glycerine for raw material carries out reacting the activity carrying out sampling evaluate catalysts after successive reaction 40h, selectivity and stability, catalyst component and other reaction conditionss are with embodiment 1, and result compares in the following Table 4.
More known by reaction yield in table 4, when saltiness is greater than 1wt%, can affect glycerin catalytic agent active, after 40h, transformation efficiency is significantly reduced to 86%, and acrolein selectivity is reduced to 79%.When desalination raw glycerine saltiness is 1wt%, still have the propenal yield of 88% after reaction 40h, and refining glycerine is suitable, continues to reduce saltiness and can not improve propenal yield.Saltiness in known desalination raw glycerine can ensure catalyst activity not by salt impurity effect lower than 1wt%.Further illustrate desalting treatment not need salt to remove completely, dehydration reaction can be carried out, obtain higher propenal yield, the remaining salt in desalination raw glycerine can not affect the reaction yield that desalination raw glycerine prepares propenal, catalyst reaction effect be that raw material is suitable with refining glycerine.
Table 4
Embodiment 5
Be 50%, Cs to preferred charge capacity
2cO
3: heteropolyacid=1.25:1, calcining temperature is 500 DEG C, calcination time be the loaded catalyst of 4 hours phospho-wolframic acid cesium salts with the desalination raw glycerine after desalination for raw material carries out life experiment.
Other reaction conditionss are with embodiment 1.
Carrying out sampling after reaction 120h, to obtain desalination raw glycerine transformation efficiency be 100%, and acrolein selectivity is 88%.Pass into air to carry out evaluation to the stability of catalyzer, make charcoal 3h at 500 DEG C, and carrying out regenerating rear glycerol conversion yield is 100%, and acrolein selectivity is 87%.Experimental result shows, raw glycerine only needs desalination, and do not need to carry out moisture evaporation concentration, methyl alcohol, the purification step such as the organism such as fitter acids and its ester class remove, can obtain higher propenal yield, other impurity in the raw glycerine of desalination simultaneously can not affect the thermostability of catalyzer, and catalyzer can carry out coke-burning regeneration reaction under 500 DEG C of high temperature.
Embodiment 6 (selection of glycerine desalination condition)
Raw glycerine adopts the glass column of Φ 30 × 800mm to carry out ion-exchange desalination, filling macroreticular acidic Zeo-karb, Crude glycerin solution peristaltic pump pumps into the ion exchange column that resin is housed from capital, raw glycerine operation flow in demineralising process is 1.5-3.5mL/min, water/raw glycerine volume ratio 1, column bottom effluent liquid graduated cylinder is collected, and adopts aas determination ratio of desalinization.
Result compares in the following Table 5.When raw glycerine operation flow is less than 2, reduce flow very little on the impact of ratio of desalinization, consider that flow reduction can reduce raw glycerine treatment capacity, therefore raw glycerine operations flows measures when being 2 optimum.
The increase being increased to water consumption after 1 when water/raw glycerine volume ratio is very little on the impact of ratio of desalinization, considers that water consumption increase can increase the concentrated energy consumption of glycerine, optimum when Gu Shui/raw glycerine volume ratio is taken as 1.
Illustrate that demineralising process cost is lower, simple to operate by experiment, can be met by ion-exchange de-salting operation the permission saltiness that desalination raw glycerine prepares propenal.
Table 5
Embodiment 7,7a and 7b (with existing COMPARATIVE CATALYST)
The desalination raw glycerine aqueous solution with 20% reacts for raw material, and other reaction conditionss are with embodiment 1
For embodiment 7b, incite somebody to action Cs in molar ratio
2cO
3: heteropolyacid=1.25:1 takes heteropolyacid and is made into volumetric molar concentration is 0.05molL
-1the aqueous solution of concentration, at room temperature filters after stirring, washs and drying, at 500 DEG C, calcine 4h, obtained Cs
2.5h
0.5pW
12o
40tricesium dodecatungstophosphate salt catalyst, carries out compressing tablet to catalyzer, and pulverizing screening is again that 30-50 order is for subsequent use.
Reaction conditions is with embodiment 1
Result compares in the following Table 6.Known for propenal three kinds of different catalysts reaction effects by comparing raw glycerine Dehydration, the best results of loaded catalyst, carries out sampling analysis during reaction 40h, can obtain 86% propenal yield.For existing SBA-15 molecular sieve catalyst, the acrolein selectivity of 16% only can be obtained.For the Tricesium dodecatungstophosphate salt catalyst without load, higher at reaction initial stage catalyst activity, the propenal yield of 94% can be obtained; And after reaction 40h, there is serious inactivation in catalyzer, catalyst stability is poor.Therefore consider the activity of catalyzer, selectivity and stability, loaded catalyst is optimum.
Table 6
Embodiment 8
Charge capacity by 5% takes the Cs of 0.7g
2cO
3, and be made into 0.2molL
-1the aqueous solution of concentration, adds 8g SBA-15 carrier in the above-mentioned aqueous solution, at room temperature floods after stirring, makes charge capacity be respectively 10%, 30%, 50%, 70%, dry for standby.Cs in molar ratio
2cO
3: phospho-wolframic acid=1.25:1 takes heteropolyacid and is made into volumetric molar concentration is 0.1molL
-1the aqueous solution of concentration, at room temperature flood after stirring, filter, wash and drying, at temperature is 500 DEG C, calcine 5h, obtained active ingredient is phospho-wolframic acid cesium salt Cs
2.5h
0.5pW
12o
40loaded catalyst.Carry out compressing tablet to catalyzer, pulverizing is sieved for subsequent use again.
Reaction conditions is with embodiment 1.
Result compares in the following Table 7.
Visible, preferred catalyst charge capacity is 50%, and now glycerol conversion yield is 100%, and acrolein selectivity is 88%.After 40h, glycerol conversion yield is substantially constant, and acrolein selectivity is 85%.
Table 7
Embodiment 9
By Cs
2cO
3being made into volumetric molar concentration is 0.1molL
-1the aqueous solution of concentration, adds SBA-15 carrier in the described aqueous solution, at room temperature floods after stirring, makes charge capacity be 50%, dry for standby.Cs in molar ratio
2cO
3: phospho-wolframic acid=0.5:1,1:1,1.25:1,1.5:1 takes heteropolyacid and be made into volumetric molar concentration is 0.1molL
-1the aqueous solution of concentration, at room temperature floods after stirring, filters, washs and drying, at temperature is 500 DEG C, calcines 3h.Obtained active ingredient is phospho-wolframic acid cesium salt Cs
2.5h
0.5pW
12o
40loaded catalyst, compressing tablet is carried out to catalyzer, pulverize sieve again for subsequent use.
Reaction conditions is with embodiment 1.
Result compares in the following Table 8.
Visible, preferred Cs
2cO
3: phospho-wolframic acid=1.25:1, now glycerol conversion yield is 100%, and acrolein selectivity is 88%.After 40h, glycerol conversion yield is substantially constant, and acrolein selectivity is 88%.
Table 8
Embodiment 10
By Cs
2cO
3being made into volumetric molar concentration is 0.1molL
-1the aqueous solution of concentration, adds SBA-15 carrier in the described aqueous solution, at room temperature floods after stirring, makes charge capacity be 50%, dry for standby.Cs in molar ratio
2cO
3: heteropolyacid=1.25:1, described acidic cs salts of heteropolyacid is phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid, silicomolybdic acid.Taking heteropolyacid and being made into volumetric molar concentration is 0.05molL
-1the aqueous solution of concentration, at room temperature flood after stirring, filter, wash and drying, at temperature is 500 DEG C, calcine 3h, obtained active ingredient is respectively the loaded catalyst of phospho-wolframic acid cesium salt, silicotungstic acid cesium salt, phospho-molybdic acid cesium salt, silicomolybdic acid cesium salt.Carry out compressing tablet to catalyzer, pulverizing is sieved for subsequent use again.
Reaction conditions is with embodiment 1.
Result compares in the following Table 9.
Visible, the loaded catalyst of preferred phospho-wolframic acid cesium salt, now glycerol conversion yield is 100%, and acrolein selectivity is 88%.After 40h, glycerol conversion yield is substantially constant, and acrolein selectivity is 88%.
Table 9
Below the specific embodiment of the present invention has been described in detail in conjunction with the embodiments, but has it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims.Those of ordinary skill in the art can carry out suitable change to these embodiments, substitute, combine and secondary combination in the scope not departing from technological thought of the present invention and purport, and all these include within protection scope of the present invention.
Claims (10)
1. prepare a propenal preparation method for propenal, it is characterized in that taking raw glycerine as raw material, substantially only desalting treatment is carried out to this raw glycerine, utilize the raw glycerine after such desalting treatment and catalyzer in reactor, carry out dehydration reaction and prepare propenal.
2. propenal preparation method as claimed in claim 1, describedly substantially only carries out desalting treatment to this raw glycerine and comprises any one process do not carried out raw glycerine in lower column processing: moisture evaporation concentration, methanol stripper, lipid acid remove, fatty acid ester removes, other impurity compounds remove.
3. propenal preparation method as claimed in claim 1, is characterized in that raw glycerine desalination to saltiness is 1wt% or following.
4. propenal preparation method as claimed in claim 1, is characterized in that raw glycerine desalting method adopts electrodialysis, the one in reverse osmosis method and ion-exchange-resin process.
5. propenal preparation method as claimed in claim 1, is characterized in that raw glycerine desalting method adopts ion-exchange-resin process.
6. propenal preparation method as claimed in claim 5, is characterized in that in ion-exchange-resin process demineralising process, adopts large porous strong acid cation exchange resin desalination, and raw glycerine operation flow is 2.0-3.0mL/min, and water/raw glycerine volume ratio is 0.5-2.
7. propenal preparation method as claimed in claim 6, it is characterized in that raw glycerine operation flow is 2.5mL/min, water/raw glycerine volume ratio is 1.
8. propenal preparation method as claimed in claim 1, is characterized in that the concentration of the raw material desalination raw glycerine aqueous solution is 10%-60%, and reactor adopts fixed bed, and temperature of reaction is 250-350 DEG C, and reaction pressure is normal pressure.
9. propenal preparation method as claimed in claim 1, is characterized in that adopting supported heteropoly compound to be catalyzer.
10. propenal preparation method as claimed in claim 1, described supported heteropoly compound is phospho-wolframic acid, phospho-molybdic acid, the heteropolyacids such as silicotungstic acid or its Suanphosphotungstate, phosphomolybdate, the one in silicotungstate, carrier is each metalloid, the one in nonmetal oxide and molecular sieve.
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