CN105399624A - Method for preparing acetic ester by adopting acid-resistant molecular sieve membrane reactor - Google Patents
Method for preparing acetic ester by adopting acid-resistant molecular sieve membrane reactor Download PDFInfo
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Abstract
The invention relates to a method for preparing acetic ester by adopting an acid-resistant molecular sieve membrane reactor. According to the method, an esterification reaction stock solution with excess acetic acid is utilized, concentrated sulfuric acid is utilized as a catalyst, an acid-resistant MOR-type molecular sieve membrane reactor prepared from a reaction stock solution which is not added with an organic template agent is in full contact with the reaction stock solution at a certain working pressure and temperature, so that the relatively reaction energy loss and dosage of catalysts of the esterification reaction are achieved, the conversion rates of ethanol and butanol are increased, and the continuous production of acetic ester can be realized. The method has the advantages of high efficiency, environmental friendliness, high selectivity, low equipment requirement, simple operation, and the like; the beneficial basis is provided for the industrial continuous production of acetic ester, furthermore, the method can be broadened to be applied to other organic reaction systems such as esterification of inorganic oxyacid and alcohol, intramolecular dehydration of alcohol, intermolecular dehydration of alcohol, aldol condensation, and dehydration condensation of amino acid.
Description
Technical field
The present invention relates to the method adopting acid resistance molecular film reactor to produce acetic ester, belong to inorganic material film Synthesis and applications field.
Background technology
Acetates product is widely used in the fields such as solvent, softening agent, tensio-active agent and polymer monomer in recent years.Domestic coating industry just progressively stops using the solvent of high VOC according to environmental requirement, as methylethylketone, methyl iso-butyl ketone (MIBK) etc., and acetic ester belongs to environment-friendly type solvent, just progressively substitutes some low-grade solvents, visible acetic ester market is just developed towards green channel, prospect Worth Expecting.The production capacity of China's vinyl acetic monomer will rise to about 3,400,000 tons of 2015,2013, N-BUTYL ACETATE effective capacity about 102.5 ten thousand tons from 2012 about 2,500,000 tons.Direct esterification is that domestic industry produces the dominating process route of acetic ester, and with acetic acid and ethanol or butanols for raw material, sulfuric acid is that catalyst for making direct esterification obtains vinyl acetic monomer, then through dehydration, fractionation is refining to obtain finished product.Esterification can generate water, in reaction system the existence of water reaction can be made to be unfavorable for the direction of ester is carried out.For this reason, people adopt the method constantly water being shifted out system in reaction process, form azeotrope or utilize main resultant and water byproduct to form azeotrope water is shifted out reaction system as adopted water entrainer and water in the reaction unit of gap.The technology of current exploitation has rectification method, molecular sieve drying method etc. to remove esterification generation water thus the method for direct Synthesis of Butyl Acetate, there is the shortcomings such as the high energy consumption caused of dehydration temperaturre is large, material loss is large, expense is high in these methods, during as Synthesis of n-Butyl Acetate, adopt through the saturated anhydrous cupric sulfate post water suction of butanols, copper sulfate after water suction needs to reclaim butanols through centrifugation, copper sulfate at high temperature dewater make anhydrous cupric sulfate after just can reuse.Thus be necessary the ester class synthesis technique of development of new completely, make it both have higher ester productive rate, low reaction temperatures, less energy-consumption and low cost production can be realized again.
Membrane sepn, as novel chemical engineering unit operation, has efficient and energy-conservation advantage, is widely applied in petrochemical complex, grocery trade and pharmaceutical industry.Film is membrane technique " chip ", not only plays a significant role in sepn process, can also it be core component structure membrane reactor (membranereactors).Membrane reactor is coupled at process independent to reaction and membrane sepn two, realization response and the combination be separated, while realizing highly effective reaction and reduction feed separation energy consumption, can also accelerated reaction process, improve reaction preference or yield, make integrated reaction and separation, simplification of flowsheet and enhancing productivity is the important developing direction of chemical industry, field of petrochemical industry.The pervaporation membrane material being applied to dehydration esterification reaction system at present mainly concentrates on polymer and the complex polyelectrolyte particle of hydrophilic group.It is external that as far back as the sixties in last century, just someone did the work of this respect, pervaporation is applied to dehydration esterification reaction by the BASF AG as Germany, in recent years, U.S., day, English have scholar with patent or paper report, domestic also have membrane technique worker to be engaged in this research, but be still in the experimental exploring stage at present.Organic film material is mainly used in the bioprocesses of biofilm reactor and enzyme mebrane reactor moderate condition gentleness, but is difficult to life-time service under chemical industry and petrochemical complex severe rugged environment.
Zeolite membrane material is a kind of novel inorganic mould material that development in recent years is got up, and have regular pore passage structure, excellent chemical stability and thermostability, the mass-producing of membrane reactor in chemical industry and petrochemical complex main flow is applied becomes possibility.In recent years Pervaporation Technology is attached in the production technique of esterification, with the productive rate of the equilibrium conversion and ester that improve esterification, becomes a research topic of many investigators in recent years.Type T molecular sieve film is applied to the preparation of ethyl acetate and ethyl lactate by infiltration evaporation and water vapour penetration technology by Tanaka etc., ([J] Chem.Eng.Sci., 2002 (57) 1577-1584) and [J] .Chem.Eng.J., 2010 (162) 355-363); Type T molecular sieve film is applied to the esterification system of acetic acid and propyl carbinol by Zhou Han etc. ([J] catalysis journal, 2008 (29) 592-594); Jafar etc. are by the esterification (J.Membr.Sci., 2002 (199) 117-123) of the water vapour penetration reactor application lactic acid of NaA type molecular screen membrane and ethanol; Zhourong flies, and high-throughout MOR type molecular screen membrane is used for Zr (SO by (petroleum journal (refining of petroleum), 2013,29261-268)
4)
2/ H-β catalysis acetic acid and ethyl esterification react, and under the esterification condition optimized, in 12h, acetic acid conversion almost reaches 100%, and molecular screen membrane shows satisfactory stability in investigated repeatedly using, and acetic acid conversion is without obvious decline.Above-mentioned molecular film reactor has broken the balance of esterification in traditional reactor with being coupled of esterification, improve the purity of ester yield and sepn process in reaction process, reduce the energy consumption required for esterification and the requirement to equipment, make process to the future development being of value to environment.But about membrane reactor is inserted with the vitriol oil be catalyzer esterification liquid in, particularly in the esterification that organic acid is excessive, the report realizing the operation of real-time online original position Separation of Water not yet has precedent.
For acid resistance and the poor stability of existing membrane reactor, cost and equipment requirements high, the problem such as the low and acetic ester demand of esterification yield is large, the esterification stoste that the present invention adopts acetic acid excessive, take the vitriol oil as catalyzer, fully contact never using the MOR type molecular film reactor prepared in the reaction stoste of organic formwork agent with reaction stoste, under the condition of lower service temperature and catalyst levels, realize real-time online by Pervaporation Technology and be separated the water that produces of esterification, the esterification balance broken traditions, improve the transformation efficiency of ethanol and butanols, the consecutive production of acetic ester can be realized.The present invention has efficiently, environmental protection, equipment requirements are low and simple operation and other advantages, for the consecutive production of realization of industrialization acetic ester provides the foundation.
Summary of the invention
The problems such as the productive rate that the object of the invention is the ester occurred in the process of producing for existing acetates is low, equipment requirements is high, separating energy consumption is high and demand is large, are adopted the acid resistance molecular screen membrane of preparation to be coupled with esterification by Pervaporation Technology and prepare acetic ester.First adopt diauxic growth Hydrothermal Synthesis technology never to use in the colloidal sol of organic formwork agent and prepare acid resistance molecular screen membrane, be coupled with the esterification taking the vitriol oil as catalyzer by the acid resistance molecular film reactor of seepage slope technology by preparation, acid resistance molecular film reactor is online to dehydration esterification reaction, break the balance of esterification in traditional reactor, reduce the energy consumption required for esterification and the requirement to conversion unit, improve the yield of ester and the purity of sepn process in reaction process, make process to the future development being of value to environment.
The present invention is a kind of molecular screen membrane that adopts is the method that membrane reactor prepares acetates, and its concrete steps are as follows:
1. be raw material by silicon sol, Tai-Ace S 150, sodium hydroxide, Sodium Fluoride and water, be mixed with and do not add organic formwork agent and consist of 1SiO
2: (0-0.1) Al
2(SO
4)
3: (0.2-0.8) NaOH:(0-2) NaF:(15-80) H
2the film synthesis colloidal sol of O, the aging 0-12 hour of colloidal sol;
2. adopt cladding process that micron-sized MOR type molecular sieve crystal is coated in porous ceramic support, process rear supports is 80
odrying 0 ~ 6 hour in the baking oven of C;
3. the supporter processed by step (2) is put into synthesis colloidal sol prepared by step (1), 150 ~ 200
ohydrothermal Synthesis 12-72 hour under C, after having reacted, washes away surperficial alkali lye, 80 with distilled water
odrying 12 hours under C;
4. take a certain amount of acetic acid and ethanol or acetic acid by a certain percentage and carry out esterification by a certain percentage, adding a certain amount of take the vitriol oil as catalyzer, and the mol ratio of acetic acid and alcohols material is 0.6 ~ 2.5, and the consumption of catalyzer is 0 ~ 0.35wt%;
5. the acid resistance molecular screen membrane after step (3) process is directly placed in the reaction solution of esterification as membrane reactor simultaneously, infiltration evaporation device is coupled with esterification device, temperature of reaction and time are respectively 70 ~ 100oC and 4 ~ 16 hour, and membrane area and reaction solution volume ratio are 0 ~ 0.5cm
2/ cm
3;
6. every a hr collections reaction solution and membrane permeation liquid, and with its component concentration of gas Chromatographic Determination, according to the selection separation performance of the transformation efficiency of Analysis result calculation reactant and the productive rate of product and film;
7., after reacting completely, take out the cleaning of molecular screen membrane distilled water to pH ≈ 7,80
oits stuctures and properties can be characterized after dry 12 hours under C or reuse.
The present invention adopts highly-acidproof molecular screen membrane to be coupled with esterification by Pervaporation Technology to prepare the method for acetic ester, and the method is simple to operate, and reaction-ure conversion-age is high, and energy consumption is low and low for equipment requirements, is conducive to successional production acetic ester.In addition prepare acid resistance molecular screen membrane in esterification reaction process, show excellent dehydration property and acid resistance.Except realizing except the consecutive production of acetic ester, highly-acidproof molecular film reactor prepared by the present invention can also be applied in other organic reaction system, as inorganic oxacid and alcohol esterification, alcohol intramolecular dehydration, the intermolecular dehydration of alcohol, aldol condensation and amino acid dehydrating condensation etc.
Accompanying drawing explanation
Fig. 1 is that infiltration evaporation is coupled with esterification and prepares the setting drawing of acetic ester;
Fig. 2 is ethanol conversion change curve in time in embodiment 1;
Fig. 3 is ethanol conversion change curve in time in embodiment 2;
Fig. 4 is ethanol conversion change curve in time in embodiment 3;
Fig. 5 is ethanol conversion change curve in time in embodiment 4;
Fig. 6 is ethanol conversion change curve in time in embodiment 5;
Fig. 7 is propyl carbinol transformation efficiency change curve in time in embodiment 6;
Fig. 8 is the XRD figure spectrum of the MOR type molecular screen membrane that take part in repeatedly before and after esterification
(a) molecular screen membrane synthesized; B () is after repeatedly esterification;
Fig. 9 is the SEM surface picture of the MOR type molecular screen membrane that take part in repeatedly before and after esterification
(a) molecular screen membrane synthesized; B () is after repeatedly esterification.
In order to further describe the present invention, provide several concrete case study on implementation below, but patent right is not limited to these examples.
Specific embodiment
embodiment 1
Be raw material by silicon sol, Tai-Ace S 150, sodium hydroxide, Sodium Fluoride and water, be mixed with the film synthesis colloidal sol not adding organic formwork agent, the composition 1SiO of colloidal sol
2: 0.1Al
2(SO
4)
3: 0.45NaOH:0.5NaF:45H
2o, aging 12 hours of colloidal sol; Then adopt cladding process that micron-sized MOR molecular sieve crystal is coated in porous ceramic support, process rear supports is 80
odrying 6 hours in the baking oven of C; Moreover the supporter by step process put into synthesis colloidal sol prepared by step, 180
ohydrothermal Synthesis 12 hours under C, after having reacted, washes away surperficial alkali lye, 80 with distilled water
odrying 12 hours under C;
Take a certain amount of acetic acid and ethanol or acetic acid by a certain percentage and carry out esterification by a certain percentage, adding a certain amount of take the vitriol oil as catalyzer, and the mol ratio of acetic acid and second alcohols material is 1.5, and the consumption of catalyzer is 0.1wt%; Directly be placed in the reaction solution of esterification as membrane reactor by the acid resistance molecular screen membrane of preparation, temperature of reaction and time are respectively 80oC and 12 hour simultaneously, and membrane area and reaction solution volume ratio are 0.4cm
2/ cm
3.Every a hr collections reaction solution and membrane permeation liquid, and with its component concentration of gas Chromatographic Determination, according to the selection separation performance of the transformation efficiency of Analysis result calculation reactant and the productive rate of product and film; After reacting completely, take out the cleaning of molecular screen membrane distilled water to pH ≈ 7,80
oits stuctures and properties can be characterized after dry 12 hours under C or reuse.
Infiltration evaporation is coupled with esterification prepare acetic ester setting drawing as shown in Figure 1, the reaction solution of esterification is heated to predetermined temperature by azeotropic water-bath and well heater, adopts circulation tap water to be concentration and the homogeneous temperature that water coolant and magnetic stirrer make reaction solution.Molecular screen membrane is directly inserted in the middle of esterification liquid, and molecular screen membrane pipe one end is airtight, and the T-valve of vacuum line is connected by emulsion tube by the other end, and it is below 100Pa that vacuum pump maintains system vacuum.The water that reaction produces enters cold-trap in the mode of vapor permeable through molecular screen membrane under negative pressure promotes, and is switched every one hour by T-valve, and is collected by the rapid condensation of liquid nitrogen.Electronic pressure transmitter is connected with vacuum line with detection system vacuum tightness.
The degree transformation efficiency of ethanol that carries out of this esterification represents,
In esterification, the transformation efficiency time history plot of ethanol as shown in Figure 2
The infiltration evaporation performance of molecular screen membrane is by permeation flux J and gas selectivity α two parametric representations.Permeation flux J penetrates through the material total mass of the film of unit surface in the representation unit time.
The J=unit time interior quality through thing/(unit time × membrane area), unit is kgm
-2h
-1, gas selectivity α
w/o=(Y
w/ Y
o)/(X
w/ X
o), wherein Y
wwith Y
obe illustrated respectively in the mass percent concentration of water and organism two kinds of components in penetrant, X
wwith X
obe illustrated respectively in the mass percent concentration of water and organism two kinds of components in stock liquid.Table 1 shows the transformation efficiency of alcohol in esterification under different condition.
embodiment 2:
The synthesis condition of esterification is identical with step embodiment 1.Unlike the device not taking membrane reactor and esterification to be coupled.In esterification, the transformation efficiency time history plot of ethanol as shown in Figure 3.
embodiment 3:
The synthesis condition of esterification is identical with the preparation process embodiment 1 of molecular screen membrane.Be 70oC unlike no esterification temperature of reaction.In esterification, the transformation efficiency time history plot of ethanol as shown in Figure 4.
embodiment 4:
The synthesis condition of esterification is identical with the preparation process embodiment 1 of molecular screen membrane.Concentration unlike the catalyzer vitriol oil is 0.2wt%.In esterification, the transformation efficiency time history plot of ethanol as shown in Figure 5.
embodiment 5:
The synthesis condition of esterification is identical with the preparation process embodiment 1 of molecular screen membrane.Mol ratio unlike ethanol in esterification and acetic acid is 1.5:1.In esterification, the transformation efficiency time history plot of ethanol as shown in Figure 6.
embodiment 6
The synthesis condition of esterification is identical with the preparation process embodiment 1 of molecular screen membrane.Be butanols unlike the alcohol adopted in this embodiment, the ester of preparation is N-BUTYL ACETATE.In esterification, the transformation efficiency time history plot of ethanol as shown in Figure 7.
X-ray diffraction (XRD) and electronic scanning Electronic Speculum (SEM) instrument is adopted to characterize the molecular screen membrane of synthesis and the molecular screen membrane after take part in repeatedly esterification.Fig. 8 is the XRD figure spectrum of MOR type molecular screen membrane prepared by tubulose mullite supporter and the molecular screen membrane that take part in repeatedly after esterification, as shown in the figure, the film of preparation is typical MOR type molecular screen membrane, after participating in repeatedly esterification as membrane reactor, molecular screen membrane still shows the characteristic peak of typical MOR type molecular screen membrane, and feature peak height is consistent with the MOR type molecular screen membrane of synthesis.Fig. 9 shows the surface microstructure of MOR type molecular screen membrane and the molecular screen membrane that take part in repeatedly after esterification prepared by tubulose mullite supporter, supporting body surface is covered by the MOR type molecular sieve crystal of the fine and close square of one deck, after participating in repeatedly esterification, molecular sieve crystal layer still keeps original pattern and symbiosis.
Alcohol conversion in table 1 embodiment
table 1
| Embodiment | The transformation efficiency [%] of alcohol |
| Embodiment 1 | 98.13 |
| Embodiment 2 | 75.68 |
| Embodiment 3 | 92.63 |
| Embodiment 4 | 91.81 |
| Embodiment 5 | 75.93 |
| Embodiment 6 | 98.73 |
Claims (5)
1. the method adopting acid resistance molecular film reactor to prepare acetates, it is characterized in that adopting strong acid resistance and hydrophilic MOR type molecular screen membrane to be that membrane reactor is coupled with esterification and prepares the method for acetic ester, its concrete steps are: silicon sol, Tai-Ace S 150, sodium hydroxide, Sodium Fluoride and water are raw material by (1), are mixed with mol ratio and consist of 1SiO
2: (0-0.15) Al
2(SO
4)
3: (0.2-0.8) NaOH:(0-2) NaF:(15-80) H
2the film synthesis colloidal sol of O, the aging 0-12 hour of colloidal sol; (2) adopt cladding process that micron-sized MOR molecular sieve crystal is coated in porous ceramic support, process rear supports in the baking oven of 80 DEG C dry 0 ~ 6 hour; (3) supporter processed by step (2) is put into synthesis colloidal sol prepared by step (1), Hydrothermal Synthesis 3-24 hour at 150 ~ 200 DEG C, after having reacted, wash away surperficial alkali lye with distilled water, drying 12 hours at 80 DEG C; (4) take a certain amount of acetic acid and ethanol or butanols by a certain percentage and carry out esterification by a certain percentage, the vitriol oil adding a certain amount of 98wt% is catalyzer, and the mol ratio of acetic acid and alcohols material is 0.5 ~ 3, and the consumption of catalyzer is 0 ~ 1wt%; (5) the acid resistance molecular screen membrane after step (3) process is directly placed in the reaction solution of esterification as membrane reactor simultaneously, infiltration evaporation device is coupled with esterification device, temperature of reaction and time are respectively 60 ~ 100 DEG C and 2 ~ 20 hours, and membrane area and reaction solution volume ratio are 0 ~ 0.5cm
2/ cm
3; (6) every a hr collections reaction solution and membrane permeation liquid, and with its component concentration of gas Chromatographic Determination, according to the selection separation performance of the transformation efficiency of Analysis result calculation reactant and the productive rate of product and film; (7), after reacting completely, take out the cleaning of molecular screen membrane distilled water to pH ≈ 7, at 80 DEG C, its stuctures and properties can be characterized after dry 12 hours or reuse.
2. a kind of method adopting acid resistance molecular film reactor to prepare acetates according to claim 1, it is characterized in that: step (4) takes a certain amount of acetic acid and ethanol or butanols by a certain percentage and carries out esterification by a certain percentage, the mol ratio of acetic acid and alcohols material is 0.6 ~ 2.5, and the consumption of concentrated sulfuric acid catalyst is 0.01 ~ 0.4wt%.
3. a kind of method adopting acid resistance molecular film reactor to prepare acetates according to claim 1, it is characterized in that: infiltration evaporation device is coupled with esterification device by step (5), temperature of reaction and time are respectively 70 ~ 95 DEG C and 4 ~ 16 hours, and membrane area and reaction solution volume ratio are 0.10 ~ 0.45cm
2/ cm
3.
4. a kind of method adopting acid resistance molecular film reactor to prepare acetates according to claim 1, is characterized in that: step (1) is not added the synthesis colloidal sol of organic formwork agent, and its mole consists of 1SiO
2: (0.03-0.1) Al
2(SO
4)
3: (0.2-0.5) NaOH:(0.5-1.5) NaF:(20-60) H
2the film synthesis colloidal sol of O, the aging 2-8 hour of colloidal sol.
5. a kind of method adopting acid resistance molecular film reactor to prepare acetates according to claim 1, is characterized in that: the generated time of the molecular screen membrane in step (3) 4 ~ 16 hours, synthesis temperature 160 ~ 190 DEG C.
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| CN110361381A (en) * | 2019-08-23 | 2019-10-22 | 江西师范大学 | A kind of color sensation acid base detemination device and method based on molecular screen membrane |
| CN111440182A (en) * | 2020-04-23 | 2020-07-24 | 陈华明 | Preparation method of isosorbide |
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| CN109651141A (en) * | 2018-12-12 | 2019-04-19 | 温州瑞思生物科技有限公司 | A kind of synthesis technology of preservative dodecyl nipagin ester |
| CN110361381A (en) * | 2019-08-23 | 2019-10-22 | 江西师范大学 | A kind of color sensation acid base detemination device and method based on molecular screen membrane |
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