CN103242149A - Method for selectively preparing acraldehyde and hydroxy-acetone - Google Patents
Method for selectively preparing acraldehyde and hydroxy-acetone Download PDFInfo
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- CN103242149A CN103242149A CN2013101812825A CN201310181282A CN103242149A CN 103242149 A CN103242149 A CN 103242149A CN 2013101812825 A CN2013101812825 A CN 2013101812825A CN 201310181282 A CN201310181282 A CN 201310181282A CN 103242149 A CN103242149 A CN 103242149A
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Abstract
The invention discloses a catalyst for selectively preparing acraldehyde and hydroxy-acetone from biological glycerol in a controllable manner and a preparation method of the catalyst. The catalyst is prepared by adopting a novel impregnation in-situ reduction method; the Cu/HZSM-5 catalyst, which is prepared from pure glycerol by using the method, has a glycerol catalytic conversion rate of 92.1% in a reaction kettle under gentle condition and has controllable selectivity of 87.3wt% and 12.4wt% to acraldehyde and hydroxy-acetone, respectively; and 98.2wt% conversion rate for glycerol and 86.2wt% selectivity for hydroxy-acetone can be obtained by similar glycerol catalytic dehydration reaction in a reaction distillation device. The dispersed and stable catalyst, which is obtained by adopting a catalyst preparation method, is simple and easy to operate and favorable for large-scale production. Moreover, the catalytic glycerol is gentle in solvent-free dehydration reaction, high in catalytic activity, strong in controllable selectivity, and therefore, the method is a green process with advantages of environment friendliness and low cost.
Description
Technical field
The invention belongs to fine chemistry industry biomass catalyzing technical field, be specifically related to a kind ofly prepare the method for propenal and pyruvic alcohol and the new preparation process of the used loaded catalyst of this method from biomass glycerin catalytic dehydration selectivity.
Background technology
Along with the concern of the whole world to environment and Sustainable development, inexpensive biomass resource glycerine is a large amount of more than needed along with the fast development of biofuel, is the unit metering with 1,000,000 tons substantially, and annual with 50% speed increment nearly.Glycerine is a multi-functional molecule stripping and slicing, can be converted into a variety of important products or intermediate to substitute from non-renewable, day apparent exhausted petrochemical material.
Propenal and pyruvic alcohol are two kinds of important chemical material.Propenal is mainly for the production of various resins, agricultural chemical insecticide Provado, medical antitumour drug dibromopropanal, fodder additives methionine(Met), sterilant glutaraldehyde, vinylformic acid and methionine(Met) and pyridine and homologue thereof etc.Pyruvic alcohol is mainly used in synthesise vitamins H, 1,2-propylene glycol, 4-methylimidazole, 2-aminopropanol, 4-hydroxy methylimidazole, acetone ester and other fine chemicals, and as biochemical reagents and foodstuff additive etc.At present, two kinds of products are industrial mainly produces with petrochemical material for this, the former has aldol condensation method, oxidation of propylene and propylene ether pyrolysis method, the latter mainly adopts 1,2-propylene glycol oxidation style and one martonite/Mono Chloro acetone esterifying alcohol solution are produced, and two kinds of technology all is to be raw material with Nonrenewable resources, complex process, productive rate is low, the cost height.Therefore, produce these two kinds of raw materials from glycerine and not only can consume the superfluous and wasting of resources that brings of glycerine, and can substitute existing technology of producing these products with petrochemical material, the pyruvic alcohol cost that as glycerine is the Suppes explained hereafter of raw material only is 20% of petrochemical processing, reduce the derive cost of serial derived product of pyruvic alcohol greatly, yet the usefulness in this technology is the cupric chromate catalyzer, has the unfriendly composition of environment.
Mechanism about the glycerin catalytic dehydration studies show that at present, dehydrating glycerin is a complicated process, wherein the matrix material that constitutes of an acidic catalyst, metal and polycomponent all can dehydrating glycerin with catalyst, and intermediate wherein exists mutual conversion (ChemSusChem, 2009,2:719-730).The Cu/SiO that adopted immersion process for preparing among the patent CN101284234A
2Catalyzer transforms with 200 ℃～400 ℃ temperature of reaction catalyzing glycerols in the fixed bed flow-type reactor and obtains 99.8% transformation efficiency and to the mole selectivity of pyruvic alcohol 89.7%.Copper chromite and auxiliary agent thereof are the catalyzer of ZnO to have adopted immersion process for preparing among the patent CN101698151A, at 220 ℃ of dehydrating glycerin with catalyst, have obtained 92.3% transformation efficiency and to the selectivity of pyruvic alcohol 88.9% by the reaction distillation device.Also adopt pickling process that copper is loaded on the different carriers among the patent CN102070422A, in fixed-bed reactor catalyzing glycerol 220 ℃ of down reactions, obtain more than 60% transformation efficiency and to the selectivity of pyruvic alcohol 44%～75%.People such as Sato (Appl Catal A, 2008,347:186) reported the research that the copper of each form and load catalyzing glycerol thereof transform, the result can obtain the mole selectivity to pyruvic alcohol 30%-86%, and wherein by-product has propenal and other alcohols etc.And the copper catalyst catalyzing glycerol that all relates to different shape among patent US2005/0244312A1, US5616817 and the US5214219 is through the pyruvic alcohol intermediate, and its selectivity surpasses 80%.Mostly be an acidic catalyst greatly and be converted into the propenal catalyst system therefor at catalyzing glycerol.Adopt coprecipitation method to prepare La among the patent CN101318140A
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3In fixed bed continuous flow reaction unit, transform in 320 ℃ of catalyzing glycerols and obtain 40%～98% transformation efficiency and to the selectivity of propenal 36%～83%.Adopt pickling process to make supported acidic ion liquid among the CN102267882A, in fixed-bed reactor, transform in 240 ℃～360 ℃ catalyzing glycerols, obtain 100% transformation efficiency and to the selectivity of propenal more than 90%.Adopt pickling process to obtain the loaded by heteropoly acid catalyzer among the CN101879456A, transform in 220 ℃～300 ℃ catalyzing glycerols with the fixed-bed micro-reactor catalyzing glycerol, obtain 13%～81% transformation efficiency and to the selectivity of propenal 49%～91%, other also has the report of patent such as CN102655931 A, CN102659540A, WO2007/058221 etc. with similar heteropoly acid catalysis dehydrating glycerin.The molecular sieve catalytic dehydrating glycerin also has report, is catalyzer with H-ZSM type and H-Y type molecular sieve among the patent CN1087894 A, can obtain propenal preferably under 250 ℃～300 ℃ conditions.The glycerol conversion yield of dehydrating glycerin with catalyst acquisition 19% on HZSM-5 and the HY etc. and the selectivity of propenal 71% have been loaded at patent CN1034803C and US5426249 mini-bus phosphoric acid.Follow-on molecular sieve also has report, as people such as Li (Appl Catal A, 2012,429 – 430:9, annotate: various types of molecular sieve catalytic dehydrating glycerins all have argumentation in its foreword) adopt various types of HZSM molecular sieve catalyst dehydrating glycerins, obtain more than 80% transformation efficiency and to the selectivity of pyruvic alcohol 74.9%.Other has mentioned the niobium oxides dehydrating glycerin with catalyst as patent WO2012005348A, and the stability of this better selectivity and catalyzer is also arranged.
For the dehydrating glycerin reaction, because the recovery of considering catalyzer is convenient to separate the heterogeneous catalysts that adopt with product more, and for avoiding catalyst loss based on gas-phase dehydration, but the problem that exists is the instability of catalyzer under the high temperature, mainly show the easy coking of catalyzer and inactivation, simultaneously the glycerine gas-phase reaction is at high temperature carried out, and sees it is disadvantageous from the angle of energy consumption, and is to cause anxiety for heatproof not as its stability of catalyzer such as heteropolyacid.Dewater regardless of the glycerin catalytic that is the sort of form (liquid phase, gas phase and overcritical) from all kinds of catalyzer of present exploitation, or different reactor, though found active higher catalytic species, but more or less exist the deficiency of selectivity and stable aspect, be prone to coking after particularly reusing and inactivation is serious.Therefore, need to the dehydrating glycerin catalysts from the related rerum natura of structure require and the preparation method improve perfect, with raising selectivity of catalyst and stability.
Summary of the invention
The object of the present invention is to provide a kind of renewable resources biological glycerol is raw material, production cost is low, the reaction conditions gentleness, operating process is simple, the dehydrating glycerin with catalyst method of controlled selection propenal and pyruvic alcohol product and higher glycerol conversion yield, relate to a process that is different from preparation heterogeneous catalysts such as traditional pickling process and coprecipitation method in this method, namely flood local reduction way and prepare the metal load of high dispersive in the technology of carriers such as molecular sieve.Mainly be that copper salt solution impregnated in the molecular sieve, add the ortho phosphorous acid hydrogen salt then and under 90 ℃ of conditions, make the absorbing copper ion be reduced into metal simple-substance and load on the molecular sieve in the molecular sieve original position, thereby make the dehydrating glycerin catalyzer.Catalyzing glycerol carries out in reactor or tubular reactor in the laboratory, being used in the tank reactor regulation and control temperature of reaction with above-mentioned catalyzer can its selectivity to propenal and pyruvic alcohol of modulation, catalytic selectivity to propenal under the mild conditions can obtain more than 80%, and can realize in the tubular reactor the selectivity of pyruvic alcohol more than 80%.And catalyzer has very high activity, and the catalyzing glycerol transformation efficiency is more than 90%.This catalyzer does not have corrosion and nontoxic to equipment, should not run off and coking, and satisfactory stability is arranged, and belongs to the environmental type catalyzer.
The objective of the invention is to be achieved through the following technical solutions:
Selectivity of the present invention prepares the method for propenal and pyruvic alcohol, and the Cu/HZSM-5 for preparing by the dipping local reduction way reacts as catalyst glycerin liquid phase dehydration, preparation propenal and pyruvic alcohol.
Wherein said catalyzing glycerol liquid-phase dehydration reaction comprises the steps:
Step 2, adjust the temperature to 150 ℃～250 ℃ begin the reaction, reaction process is kept stirring;
Step 3, reaction were filtered and are obtained filtrate and solid after 2～12 hours, and solid is catalyzer, reclaims standby;
Step 4, rectifying filtrate obtain propenal and pyruvic alcohol.
Dipping local reduction way described in the present invention specifically comprises the steps:
Step a, get ZSM-5, add mantoquita and reductive agent more respectively, wherein the mass ratio of ZSM-5 and mantoquita is 1.6～6.4:1, and the mol ratio of mantoquita and reductive agent is 1:2, adds water to submergence, and room temperature left standstill more than 1 hour;
Step b, heating and stir and to finish until reaction in water bath with thermostatic control obtain filtrate;
Step c, filtrate obtain throw out after filtration, after throw out washing, drying, and roasting 3h, the cooling back obtains powder and is Cu/HZSM-5.
In step a, described mantoquita is copper sulfate or cupric chloride, and described reductive agent is ortho phosphorous acid or ortho phosphorous acid sodium dihydrogen.
The silica alumina ratio of described ZSM-5 is 50.
The temperature that heats in the water bath with thermostatic control among the step b is 90 ℃; 150 ℃～300 ℃ of maturing temperatures among the step c.
(illustrate: ZSM-5 represents mainly to be constituted, formed structural unit and form the molecular sieve with intersection pore canal system with 85 yuan rings by sial; Cu/HZSM-5 has been expressed as the acid ZSM-5 copper of having gone up load; Silica alumina ratio is the mol ratio that 50 ZSM-5 represents main component sial in this molecular sieve, and acid-basicity and the stability of this ratio and molecular sieve have relation)
The present invention has following innovative point:
1, reaction raw materials is the wide biological glycerol in cheap source, can reduce the cost of propenal and pyruvic alcohol in the industrial production.
2, this dehydrating glycerin with catalyst catalyzer adopts novel dipping local reduction way preparation, and Preparation of Catalyst is simple to operation; The good stability of catalyzer, catalytic activity is good, and the life-span is long; Catalyzer is easily regenerated and equipment is not corroded environmental sound, has friendly.
3, this catalyst reaction because the good stability of catalyzer can carry out in reactor, also can be carried out in other reactors such as serialization fixed bed, operation is simple, the reaction conditions gentleness, solvent-free reaction greatly reduces separating treatment cost behind the product.
4, this catalyzed reaction can strengthen the selectivity to one of propenal and pyruvic alcohol by charge capacity, temperature of reaction and the employing different reactor of regulation and control catalyzer.And temperature and catalyst loadings do not need production unit is changed when product is regulated and control, the product that can fully come motor-driven adjusting to produce according to market demand.
Than other technical scheme, this technology has following advantage:
Enable and be different from the dipping local reduction way that straight dipping, coprecipitation method prepare catalyzer, the catalyst stability that this method makes is good, and preparation process is simple to operation; Showing good activity in dehydrating glycerin with catalyst, controllably prepare propenal and pyruvic alcohol, realize solvent-free production, is a kind of environmental friendliness more, friendly process cheaply.
Description of drawings
The dipping local reduction way that Fig. 1 adopts for the present invention prepares the process synoptic diagram of catalyzer.Copper ion solution freely is diffused into various piece and forms finite concentration on the surface of carrier and settle out in carrier, then add reductive agent ortho phosphorous acid hydrogen sodium under the heat supply energy make cupric ion separately in-situ reducing become copper simple substance and precipitating load at carrier surface, thereby the process of chemical reduction simultaneously also forms the acidity that has strengthened carrier surface with proton, water repeatedly washs washes foreign ion off, and maturing temperature makes the catalyzer drying can regulate the acidity of carrier surface again.
Fig. 2 is the transmission electron microscope picture (TEM figure) with the catalyzer of this method preparation.Show among the figure that ZSM-5 is keeping original structural framing, and the cupric ion of load is scattered in carrier surface preferably, and from size, most copper particle are in nano level, but because the inhibition of carrier surface makes these copper particle be difficult for gathering, increased its stability.
Embodiment
(embodiment 1)
The ZSM-5 molecular sieve that takes by weighing 2.3g is put in the flask, adds the cupric sulfate pentahydrate of 0.72g and the ortho phosphorous acid sodium dihydrogen of 0.85g (excessive slightly) more respectively, adds the water of 20mL at last, and room temperature left standstill 1 hour.Heating and vigorous stirring are finished until reaction in 90 ℃ of waters bath with thermostatic control then.Throw out after filtration, washing, dry, the following 300 ℃ of roasting 3h of nitrogen protection.Make catalyst sample after the cooling.
Table 1
Take by weighing different loads amount Cu/HZSM-5 molecular sieve catalyst 0.2g in the 75ml reactor, add 5g glycerine, place the very hot formula constant temperature blender with magnetic force that has silicone oil, temperature adjustment degree to 200 ℃ keeps constant temperature to stir 2h.After reaction finishes, pour in the centrifuge tube product into after the centrifugation airtight depositing, with the gas-chromatography analysis of drawing a design.The result is as shown in table 1.
(embodiment 2)
Preparation of Catalyst is with the Preparation of Catalyst part among the embodiment 1.
Take by weighing the 8wt% charge capacity Cu/HZSM-5 molecular sieve catalyst 0.2g of different maturing temperatures in the 75ml reactor, add 5g glycerine, place the very hot formula constant temperature blender with magnetic force that has silicone oil, temperature adjustment degree to 200 ℃ keeps constant temperature to stir 2h.After reaction finishes, pour in the centrifuge tube product into after the centrifugation airtight depositing, with the gas-chromatography analysis of drawing a design.The result is as shown in table 2.
Table 2
(embodiment 3)
Preparation of Catalyst is with the Preparation of Catalyst part among the embodiment 1.
Take by weighing the 8wt% charge capacity Cu/HZSM-5 molecular sieve catalyst 0.2g of 300 ℃ of temperature roastings in the 75ml reactor, add 5g glycerine, place the very hot formula constant temperature blender with magnetic force that has silicone oil, transfer to desired temperature, keep constant temperature to stir 2h.After reaction finishes, pour in the centrifuge tube product into after the centrifugation airtight depositing, with the gas-chromatography analysis of drawing a design.The result is as shown in table 3.
Table 3
Nd-represents not detect this composition.
(embodiment 4)
Preparation of Catalyst is with the Preparation of Catalyst part among the embodiment 1.
Take by weighing the 8wt% charge capacity Cu/HZSM-5 molecular sieve catalyst 0.2g of 300 ℃ of temperature roastings in the 75ml reactor, add 5g glycerine, place the very hot formula constant temperature blender with magnetic force that has silicone oil, temperature adjustment degree to 200 ℃ keeps constant temperature to stir the desired time.After reaction finishes, pour in the centrifuge tube product into after the centrifugation airtight depositing, with the gas-chromatography analysis of drawing a design.The result is as shown in table 4.
Table 4
(embodiment 5)
Preparation of Catalyst is with the Preparation of Catalyst part among the embodiment 1.
Take by weighing the 8wt% charge capacity Cu/HZSM-5 molecular sieve catalyst of 300 ℃ of temperature roastings in the 75ml reactor, add 5g glycerine, place the very hot formula constant temperature blender with magnetic force that has silicone oil, temperature adjustment degree to 200 ℃ keeps constant temperature to stir 2h.After reaction finishes, pour in the centrifuge tube product into after the centrifugation airtight depositing, with the gas-chromatography analysis of drawing a design.The result is as shown in table 5.
Table 5
(embodiment 6)
Preparation of Catalyst is with the Preparation of Catalyst part among the embodiment 1.
The 8wt% charge capacity Cu/HZSM-5 molecular sieve catalyst 0.2g that takes by weighing 300 ℃ of temperature roastings is connected with in the reaction flask still of water distilling apparatus in 100ml, add 5g glycerine, place the very hot formula constant temperature blender with magnetic force that has silicone oil, temperature adjustment degree to 200 ℃ keeps constant temperature to stir 2h.After reaction finishes, pour in the centrifuge tube product into after the centrifugation airtight depositing, with the gas-chromatography analysis of drawing a design.Get the transformation efficiency 98.2wt% of glycerine, the selectivity of propenal is 13.4wt%, the selectivity 86.2wt% of pyruvic alcohol.
The selectivity that above-mentioned catalyst dehydrating glycerin prepares propenal and pyruvic alcohol can realize regulation and control by temperature control and selecting reactor type, and the qualitative and quantitative of product judged by retention time and the peak area of gas-chromatography respectively; The purification of propenal and pyruvic alcohol product adopts the product of collecting 58 ℃ and 145 ℃ boiling points on the rectification under vacuum device in laboratory respectively to get final product.
Claims (7)
1. a selectivity prepares the method for propenal and pyruvic alcohol, it is characterized in that: the Cu/HZSM-5 by the preparation of dipping local reduction way is as the reaction of catalyst glycerin liquid phase dehydration, preparation propenal and pyruvic alcohol.
2. selectivity according to claim 1 prepares the method for propenal and pyruvic alcohol, it is characterized in that described catalyzing glycerol liquid-phase dehydration reaction comprises the steps:
Step 1, be catalyzer with Cu/HZSM-5, getting glycerine is that 20～200:1 mixes with catalyzer according to mass ratio;
Step 2, adjust the temperature to 150 ℃～250 ℃ begin the reaction, reaction process is kept stirring;
Step 3, reaction were filtered and are obtained filtrate and solid after 2～12 hours, and solid is catalyzer, reclaims standby;
Step 4, rectifying filtrate obtain propenal and pyruvic alcohol.
3. selectivity according to claim 1 prepares the method for propenal and pyruvic alcohol, it is characterized in that described dipping local reduction way specifically comprises the steps:
Step a, get ZSM-5, add mantoquita and reductive agent more respectively, wherein the mass ratio of ZSM-5 and mantoquita is 1.6～6.4:1, and the mol ratio of mantoquita and reductive agent is 1:2, adds water to submergence, and room temperature left standstill more than 1 hour;
Step b, heating and stir and to finish until reaction in water bath with thermostatic control obtain filtrate;
Step c, filtrate obtain throw out after filtration, after throw out washing, drying, and roasting 3h, the cooling back obtains powder and is Cu/HZSM-5.
4. selectivity according to claim 3 prepares the method for propenal and pyruvic alcohol, it is characterized in that: described mantoquita is copper sulfate or cupric chloride.
5. selectivity according to claim 3 prepares the method for propenal and pyruvic alcohol, it is characterized in that: described reductive agent is ortho phosphorous acid or ortho phosphorous acid sodium dihydrogen.
6. selectivity according to claim 3 prepares the method for propenal and pyruvic alcohol, it is characterized in that: the silica alumina ratio of ZSM-5 is 50.
7. selectivity according to claim 3 prepares the method for propenal and pyruvic alcohol, it is characterized in that: the temperature that heats in the water bath with thermostatic control among the step b is 90 ℃; 150 ℃～300 ℃ of maturing temperatures among the step c.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2913106A4 (en) * | 2013-11-18 | 2017-03-01 | LG Chem, Ltd. | Catalyst for dehydration of glycerin, method for preparing same, and method for preparing acrolein |
| CN113617345A (en) * | 2021-08-13 | 2021-11-09 | 厦门欧米克生物科技有限公司 | Catalyst and preparation method and application thereof |
| CN113926463A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087894A (en) * | 1992-11-14 | 1994-06-15 | 底古萨股份公司 | Produce the method for propenal |
| WO2007058221A1 (en) * | 2005-11-15 | 2007-05-24 | Nippon Shokubai Co., Ltd. | Process for dehydration of polyhydric alcohols |
| CN101284245A (en) * | 2007-04-13 | 2008-10-15 | 湖南大学 | Reaction for preparing hydroxyacetone by selectively dewatering natural glycerol and catalyst |
| CN102259017A (en) * | 2010-05-31 | 2011-11-30 | 上海图和环保材料科技有限公司 | Novel composite nano visible light catalyst and preparation method thereof |
-
2013
- 2013-05-15 CN CN201310181282.5A patent/CN103242149B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087894A (en) * | 1992-11-14 | 1994-06-15 | 底古萨股份公司 | Produce the method for propenal |
| WO2007058221A1 (en) * | 2005-11-15 | 2007-05-24 | Nippon Shokubai Co., Ltd. | Process for dehydration of polyhydric alcohols |
| CN101284245A (en) * | 2007-04-13 | 2008-10-15 | 湖南大学 | Reaction for preparing hydroxyacetone by selectively dewatering natural glycerol and catalyst |
| CN102259017A (en) * | 2010-05-31 | 2011-11-30 | 上海图和环保材料科技有限公司 | Novel composite nano visible light catalyst and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2913106A4 (en) * | 2013-11-18 | 2017-03-01 | LG Chem, Ltd. | Catalyst for dehydration of glycerin, method for preparing same, and method for preparing acrolein |
| CN113926463A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method and application thereof |
| CN113926463B (en) * | 2020-06-29 | 2024-03-29 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method and application thereof |
| CN113617345A (en) * | 2021-08-13 | 2021-11-09 | 厦门欧米克生物科技有限公司 | Catalyst and preparation method and application thereof |
| CN113617345B (en) * | 2021-08-13 | 2023-07-28 | 厦门欧米克生物科技有限公司 | Catalyst and preparation method and application thereof |
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