CN1970518B - Separation process after synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide - Google Patents
Separation process after synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide Download PDFInfo
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- CN1970518B CN1970518B CN 200510110612 CN200510110612A CN1970518B CN 1970518 B CN1970518 B CN 1970518B CN 200510110612 CN200510110612 CN 200510110612 CN 200510110612 A CN200510110612 A CN 200510110612A CN 1970518 B CN1970518 B CN 1970518B
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Abstract
The invention discloses a separating technique of 3-hydroxy propionic ester from epoxyethane carbonyl, which is characterized by the following: reacting epoxyethane, carbon monoxide and low-carbon alcohol to do oxonation to generate 3-hydroxy propionic ester; making the compound into evaporator under reacting temperature and pressure; controlling the temperature less than 120 deg.c and evaporating pressure between 0 and 0.1Mpa; condensing evaporated material to obtain low-carbon alcohol and 3-hydroxy propionic ester; adopting mixture of catalyst, 3-hydroxy propionic ester, low-carbon alcohol and heavy component as evaporating tower flow; recycling partial or all tower flow into reactor.
Description
Technical field
The present invention relates to a kind of preparation and separating technology that produces simultaneously more than the oxygenatedchemicals of a class, relating to a kind of in particular is separating process behind the raw material synthesizing 3-hydroxy propionate by carbonyl with oxyethane.
Background technology
1, ammediol is the precursor of production Poly(Trimethylene Terephthalate) (PTT), serves many purposes in fields such as chemical fibre productions.Preparation 1 at present, the method for ammediol mainly contains three kinds: (1) acrolein hydration hydrogenation; (2) glucose biological fermentation; (3) oxirane carbonyl is synthetic.Wherein oxirane carbonyl is synthetic is big industrial production method commonly used, and oxirane carbonyl synthesizes 1, and ammediol has two kinds of technologies again: the one, and oxyethane is through 3-hydroxy propanal intermediate preparation 1, ammediol; The 2nd, oxyethane is through 3-hydroxy propionate intermediate preparation 1, ammediol.
Relevant oxyethane first part of patent of synthesizing 3-hydroxy propionate by carbonyl in low-carbon alcohol is U.S. Pat 4973741, rhodium and ruthenium catalyst and the mixture that contains various promotor compositions (for example triphenylphosphine) have been used, reaction product is a mixture, the transformation efficiency of oxyethane is 26.3%～31.2%, and the selectivity of 3-hydroxy propionate is 17.4%～43.5%.Chinese patent application number 00135647, it is raw material with oxyethane and synthetic gas that name is called " oxirane carbonyl synthesizes 3-hydroxy propanal and 1; the ammediol method ", in the catalyzer of forming by cobalt salt and organophosphorus ligand, step input reactant, straight line program heats up, under 110-150 ℃ and 11-13MPa, generate 3-hydroxy propanal and 1, ammediol has further been simplified operating process, has improved reaction efficiency.But above-mentioned two patents are not all mentioned the separation problem of oxonation product and catalyzer.U.S. Pat 6348632 has been discussed the carbonylation reaction of epoxy compounds and follow-up product separation method, this patent is with the promotor of imidazoles as the cobalt octacarbonyl catalyzer, the extracting process (if with ether or the alcohol more than the C4 as reaction solvent) that with the method for vacuum distilling (if with the alcohol of C3 or even lower level as reaction solvent) or with water is solvent obtains 3-hydroxy ester and derivative thereof, and cobalt catalyst and promotor are circulated to reactive system.U.S. Pat 6600065 proposes stability in use gas (for example nitrogen, hydrogen or carbon monoxide) again, comes separating catalyst by steam stripped method, isolated part or all of cobalt compound and promotor Returning reactor.Above-mentioned two patents relate to the separation problem of oxonation product and catalyzer, but the problem that all exists more serious reaction conversion ratio and selectivity to reduce along with the increase of catalyst recirculation number of times.And have now found that cobalt catalyst not only to the oxygen sensitivity, also responsive to temperature, as if contacting oxygen or being in for a long time under the comparatively high temps, activity of such catalysts can reduce.
Summary of the invention
Technical problem to be solved by this invention provides the separating technology behind a kind of new synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide, the present invention finishes separating of oxonation product and catalyzer in the short period of time, with this problem of avoiding reaction conversion ratio and selectivity to reduce along with the increase of catalyst recirculation number of times, improved the stability of catalyzer, process of the present invention on the other hand and equipment are simple, and more practical value is arranged.
The technical solution used in the present invention: the separating technology behind a kind of synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide, comprise the following steps: in the presence of conventional carbonylation catalyst and promotor, oxyethane, carbon monoxide and low-carbon alcohol oxonation generate the 3-hydroxy propionate, the throttling under temperature of reaction and pressure of mixture behind the oxonation enters flasher and carries out flash distillation, control flash vaporization point＜120 ℃, control flashing pressure 0～0.1MPa, the flash distillation overhead stream obtains containing the phlegma of low-carbon alcohol and 3-hydroxy propionate through condensation, the flashing tower bottoms stream is catalyzer and 3-hydroxy propionate, the mixture of low-carbon alcohol and heavy constituent, the flashing tower bottoms stream partly or entirely is circulated back to circulating reaction in the reactor.
Described low-carbon alcohol is selected from one or more the mixture in methyl alcohol, ethanol, propyl alcohol or the butanols.
Described in the presence of conventional carbonylation catalyst and promotor, it is one or more mixture in 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, the 3-hydroxy-propionic acid butyl ester that oxyethane, carbon monoxide and low-carbon alcohol oxonation generate the 3-hydroxy propionate.
Described flash distillation overhead stream is through condensation, in the phlegma amount of 3-hydroxy propionate be in the oxonation product 3-hydroxy propionate amount 5～100%.
Control flash vaporization point＜80 ℃ in oxonation product and the catalyst separating process, control flashing pressure＜50KPa.
The oxonation product carried out the gas-liquid separation pre-treatment before throttling enters flasher.
Described gas-liquid separation pre-treatment is that the throttling under temperature of reaction and pressure of oxonation product is entered gas-liquid separator, control gas-liquid separation pressure is 0.1～1.0Mpa, and the amount of the 3-hydroxy propionate in the control gaseous component is less than 2% of the amount of 3-hydroxy propionate in the oxonation product.
Beneficial effect of the present invention: the present invention separates target product 3-hydroxy propionate and excessive low-carbon alcohol fast with the method for flash distillation from reaction product, and the remaining mixture of catalysts that contains is partly or entirely got back to the reactor cycles use.Owing to finished separating of oxonation product and catalyzer in the short time, thus activity of such catalysts to reduce amplitude less, improved the stability of catalyzer.In addition, compared technological process of the present invention with former separation method and equipment fairly simple, better economy and practical value are arranged.
Description of drawings
Fig. 1 is the oxonation product comes separating catalyst by the decompression isothermal flash a process flow sheet;
Fig. 2 is oxonation product advanced promoting the circulation of qi liquid separation processes schema before the decompression isothermal flash.
Embodiment
1,2 couples of the present invention describe in further detail below by accompanying drawing: as shown in Figure 1, oxyethane is in the presence of catalyzer, with carbon monoxide and low-carbon alcohol reaction.The low-carbon alcohol here is not only as reactant but also as reaction solvent, and in order to obtain the 3-hydroxy propionate economically, then catalyzer must recycle.The preparation of synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide, separating technology comprise following two parts: (1) oxonation: in the presence of carbonylation catalyst and various promotor, oxyethane, carbon monoxide, low-carbon alcohol are under processing condition such as certain temperature, pressure (being generally 0.1-7.0Mpa), the residence time, and reaction generates the 3-hydroxy propionate; (2) catalyst separating: the oxonation product separates by flash distillation under suitable condition, produces two bursts of different logistics: the flash distillation overhead stream obtains containing the phlegma of low-carbon alcohol and 3-hydroxy propionate as intermediates through condensation; The flashing tower bottoms stream is catalyzer and part 3-hydroxy propionate, low-carbon alcohol, and the mixture of heavy constituent partly or entirely is circulated back to reactor.Its oxonation partly carries out with known method and condition, there is no particular limitation to reactant and product composition, catalyzer and promotor kind, reaction process condition etc., catalyzer and the promotor that can mention with reference to top each patent for example, processing condition such as reaction pressure, temperature of reaction, reaction times.But for the ease of the lock out operation of catalyzer, a kind of in methyl alcohol, ethanol, propyl alcohol and the butanols that said here low-carbon alcohol is carbonatoms≤4 or their mixture, preferential is a kind of in methyl alcohol and the ethanol or their mixture.The process description of its catalyst separating part is as follows:
1. the throttling under temperature of reaction and pressure of oxonation product enters flasher;
2. control flash vaporization point and pressure;
3. the flash distillation overhead stream is through condensation, and the phlegma that contains low-carbon alcohol and 3-hydroxy propionate is as intermediates;
4. the flashing tower bottoms stream is the mixture of catalyzer and part 3-hydroxy propionate, low-carbon alcohol and heavy constituent, partly or entirely is circulated back to reactor.
In the technological process of above-mentioned catalyst separating part, control of process condition mainly is flash vaporization point and pressure, and the difference of the 3-hydroxy propionate extraction yield that obtains according to temperature, pressure and the hope of oxonation product can be adjusted in the scope of broad.The general decompression isothermal flash that adopts, according to the extraction yield of 3-hydroxy propionate (because carbonylation catalyst and promotor are generally solid, carry out catalyst recirculation, need the solvent of certain 3-hydroxy propionate internal circulating load) as catalyzer, flash vaporization point generally is controlled at less than in 120 ℃ the scope, preferential being controlled at less than in 80 ℃ the scope, temperature is too high, and is unfavorable to activity of such catalysts; Under such temperature condition, pressure generally is controlled in the scope less than 0.1MPa, and in the preferential scope that is controlled at less than 50KPa, hypertonia can not obtain ideal 3-hydroxy propionate extraction yield.
According to method of the present invention, before the isothermal flash that reduces pressure, can do certain pre-treatment to the oxonation product, for example advanced promoting the circulation of qi liquid separates, and is dissolved in unreacted or excess air in the oxonation product with removal, is mainly oxyethane and carbon monoxide; The method of gas-liquid separation can be used known method, for example general gas-liquid separator, and gas-liquid separation (the flash evaporation here mainly is in order to carry out gas-liquid separation) is carried out in also available flash distillation, and as shown in Figure 2, its process comprises:
1. reaction product throttling under temperature of reaction and pressure enters gas-liquid separator;
2. control gas-liquid separation pressure;
3. the liquid stream throttling after gas-liquid separation enters flasher;
4. control flash vaporization point and pressure;
5. the flash distillation overhead stream is through condensation, and the phlegma that contains low-carbon alcohol and 3-hydroxy propionate is as intermediates;
6. the flashing tower bottoms stream is the mixture of catalyzer and part 3-hydroxy propionate, low-carbon alcohol and heavy constituent, partly or entirely gets back to reactor cycles and uses.
The control of temperature and pressure during gas-liquid separation makes the amount of the 3-hydroxy propionate in the gaseous component can not be too high, is controlled at less than 2% of 3-hydroxy propionate amount in the oxonation product and is advisable; In order to simplify the gas-liquid separation process, the oxonation product is not generally carried out heat exchange, the pressure-controlling during gas-liquid separation is generally in 0.1MPa～7.0Mpa scope, preferably in 0.1～1.0MPa scope.
Embodiment 1～6
(1) oxonation:
In 5 liters of chuck stainless steel autoclaves, under the condition of isolated environment oxygen, mol ratio by 100/600/1/6, add oxyethane, methyl alcohol, catalyzer cobalt octacarbonyl, promotor 3-pyridone, wherein cobalt octacarbonyl and 3-pyridone internal circulating load are 98%, and the fresh amounts of interpolation is 2%; Be pressurized to 7MPa with carbon monoxide, and be heated to 70 ℃, react after 4 hours, analyze with GLC, the transformation efficiency of oxyethane is 96%, and the selectivity that the 3-hydroxy methyl propionate is abbreviated as MHP is 97% (MHP yield 93.1%).
(2) catalyzer flash separation:
After reaction finished, above-mentioned reaction product was pressed the signal of Fig. 1 technology, the isothermal flash that under different conditions, reduces pressure, and advancing flasher reaction product flow is 160 Grams Per Hours, the result is compiled in table 1.
Table 1
Annotate: the MHP extraction yield: the amount of MHP accounts for the ratio of MHP amount in the oxonation product in the expression flash distillation overhead stream.
Embodiment 7～9
With oxonation process and the condition of embodiment 1～6, before different the is decompression isothermal flash, press Fig. 2 technology and illustrate, earlier reaction product is carried out gas-liquid separation, removal is dissolved in the unreacting gas in the reaction mixture, and with the condition decompression isothermal flash of embodiment 4, the result is compiled in table 2 then.
Table 2
Embodiment 10～12
With oxonation process and the condition of embodiment 1～6, different is changes catalyzer and promotor, does not circulate, and reaction product press Fig. 1 technology and illustrated, with the condition of embodiment 4 isothermal flash that reduces pressure, the result is compiled in table 3.
Table 3
Embodiment 13～15
Oxonation process and condition with embodiment 1～6, different is to replace methyl alcohol to carry out oxonation with ethanol or butanols, after reaction finishes, reaction product is pressed the signal of Fig. 1 technology, isothermal flash reduces pressure under different conditions, advancing flasher reaction product flow is 160 Grams Per Hours, and the result is compiled in table 4.
Table 4
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (7)
1. the separating technology behind the synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide, comprise the following steps: in the presence of conventional carbonylation catalyst and promotor, oxyethane, carbon monoxide and low-carbon alcohol oxonation generate the 3-hydroxy propionate, the throttling under temperature of reaction and pressure of mixture behind the oxonation enters flasher and carries out flash distillation, 50～120 ℃ of control flash vaporization points, control flashing pressure 0～0.1MPa, the flash distillation overhead stream obtains containing the phlegma of low-carbon alcohol and 3-hydroxy propionate through condensation, the flashing tower bottoms stream is catalyzer and 3-hydroxy propionate, the mixture of low-carbon alcohol and heavy constituent, the flashing tower bottoms stream partly or entirely is circulated back to circulating reaction in the reactor.
2. according to the separating technology behind the described a kind of synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide of claim 1, it is characterized in that: described low-carbon alcohol is selected from one or more the mixture in methyl alcohol, ethanol, propyl alcohol or the butanols.
3. according to the separating technology behind the described a kind of synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide of claim 1, it is characterized in that: described in the presence of conventional carbonylation catalyst and promotor, it is one or more mixture in 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, the 3-hydroxy-propionic acid butyl ester that oxyethane, carbon monoxide and low-carbon alcohol oxonation generate the 3-hydroxy propionate.
4. according to the separating technology behind the described a kind of synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide of claim 1, it is characterized in that: described flash distillation overhead stream is through condensation, in the phlegma amount of 3-hydroxy propionate be in the oxonation product 3-hydroxy propionate amount 5～100%.
5. according to the separating technology behind the described a kind of synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide of claim 1, it is characterized in that: described control flash vaporization point＜80 ℃, control flashing pressure＜50KPa.
6. according to the separating technology behind claim 1 or the 3 described a kind of synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide, it is characterized in that: the oxonation product carried out the gas-liquid separation pre-treatment before throttling enters flasher.
7. according to the separating technology behind the described a kind of synthesizing 3-hydroxy propionate by carbonyl of ethylene oxide of claim 4, it is characterized in that: described gas-liquid separation pre-treatment is that the throttling under temperature of reaction and pressure of oxonation product is entered gas-liquid separator, control gas-liquid separation pressure is 0.1～1.0Mpa, and the amount of the 3-hydroxy propionate in the control gaseous component is less than 2% of the amount of 3-hydroxy propionate in the oxonation product.
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| CN102050736A (en) * | 2010-12-10 | 2011-05-11 | 广东石油化工学院 | Method for synthesizing methyl 3-hydroxypropanoate |
| CN106431922B (en) * | 2015-08-12 | 2019-04-12 | 中国石油化工股份有限公司 | The method for preparing 3- hydroxy propionate |
| CN113845426B (en) * | 2020-06-28 | 2024-01-26 | 中国石油化工股份有限公司 | Method and device for preparing ester compound |
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Non-Patent Citations (3)
| Title |
|---|
| US 4,973,741 A,1990.11.27,全文. |
| US 6,348,632 B1,2002.02.19,6-7栏、权利要求1，2. |
| US 6,600,065 B2,2003.07.29,全文. |
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Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER NAME: SHANGHAI COKING CO., LTD. |
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Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee before: Shanghai Coking Co., Ltd. |