CN114249704A - Preparation method of alkylene oxide - Google Patents
Preparation method of alkylene oxide Download PDFInfo
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- CN114249704A CN114249704A CN202011018033.0A CN202011018033A CN114249704A CN 114249704 A CN114249704 A CN 114249704A CN 202011018033 A CN202011018033 A CN 202011018033A CN 114249704 A CN114249704 A CN 114249704A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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Abstract
The invention discloses a preparation method of alkylene oxide. The preparation method comprises the following steps: contacting chlorohydrin aqueous solution containing high-concentration metal chloride with alkali to perform saponification reaction to obtain crude alkylene oxide and saponification waste liquid; the concentration of the metal chloride in the chlorohydrin aqueous solution is not less than 10 wt%. The preparation method of the epoxy alkane provided by the invention can reduce or even not generate waste water, and realizes green production of preparing the epoxy alkane by a chlorohydrination method.
Description
Technical Field
The invention belongs to the field of preparation of alkylene oxide, and particularly relates to a preparation method of alkylene oxide.
Background
The epoxy alkane is an important organic chemical product, is mainly used for preparing dihydric alcohol and polyether, and is widely applied to the industries of petroleum, chemical engineering, pesticides, textile, daily chemicals and the like. The production and preparation method of the alkylene oxide mainly comprises a chlorohydrination method, a co-oxidation method and a direct oxidation method, wherein the chlorohydrination method has the advantages of less investment, mild reaction, high production safety, mature process, short flow and the like. For example, chlorohydrination of propylene oxide involves: chlorine and propylene react to generate chloropropanol aqueous solution, the chloropropanol aqueous solution and calcium hydroxide are subjected to saponification reaction to obtain propylene oxide, and the main reaction and the side reaction are as follows:
chlorohydrination main reaction:
chlorohydrination side reaction:
saponification main reaction:
saponification side reaction:
however, the chlorohydrination method has the disadvantages of large amount of waste water, serious environmental pollution and the like. Particularly, the amount of the waste water containing salt is large, and the waste water containing salt is the biggest obstacle of the development of the chlorohydrination method, for example, in the existing chlorohydrination method propylene oxide production device, chlorohydrination reaction liquid containing 3-5 wt% of chloropropanol and 17 wt% of calcium hydroxide aqueous emulsion are sent into a saponification tower for saponification reaction, water vapor directly introduced into the saponification tower provides heat and steam to extract reaction product propylene oxide, crude propylene oxide obtained at the top of the saponification tower is further rectified and separated to prepare propylene oxide, saponification waste liquid containing 3 wt% of calcium chloride is obtained at the bottom of the saponification tower, and 45-50t of waste water containing 3 wt% of salt is obtained as a byproduct of each ton of products. In view of the defects of the method, methods for producing olefin oxide such as an oxidation method, a direct oxidation method and the like are industrially developed, the methods solve the problem of salt-containing wastewater, but because a strong oxidation reaction is introduced, the oxidation method and the direct oxidation method have the defects of more reaction byproducts, complex post-treatment and the like, and can not completely replace a chlorohydrination method, so that the chlorohydrination method still occupies more than half of the river mountains in the existing olefin oxide production device and process. With the increasing environmental protection pressure, how to develop the advantages of the chlorohydrination method and reduce or even eliminate the discharge amount of waste water generated by the process is an important subject of the alkylene oxide preparation industry.
Disclosure of Invention
The invention provides a preparation method of alkylene oxide, which comprises the following steps: contacting chlorohydrin aqueous solution containing metal chloride with alkali for saponification reaction to obtain crude alkylene oxide and saponification waste liquid;
the concentration of the metal chloride in the chlorohydrin aqueous solution is not less than 10 wt%.
According to an embodiment of the invention, the concentration of metal chloride in the aqueous chlorohydrin solution is 10 to 50 wt.%, more preferably 20 to 35 wt.%, exemplary 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 50 wt.%.
According to an embodiment of the invention, the metal in the metal chloride is at least one of a group I element, a group II element, preferably sodium and/or calcium. Preferably, the metal chloride is sodium chloride and/or calcium chloride.
According to an embodiment of the invention, the aqueous chlorohydrin solution containing a metal chloride is obtained by reacting chlorine gas and an olefin in a high concentration aqueous metal chloride solution. Specifically, the content of the metal chloride in the high-concentration metal chloride aqueous solution is greater than or equal to 10 wt%, preferably the concentration is 10 to 50 wt%, further preferably 20 to 35 wt%, and is exemplarily 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt% or any point in any two combinations of the above points.
Wherein the olefin is ethylene, propylene, chloropropene or butylene.
According to an embodiment of the invention, the chlorohydrin content of the aqueous chlorohydrin solution is 1 to 10 wt.%, preferably 2 to 5 wt.%, exemplarily 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 8 wt.%, 10 wt.%.
According to an embodiment of the invention, the molar ratio of the feed of chlorine to olefin is 1 (1.01-1.3), for example 1 (1.05-1.175), again as 1 (1.1-1.15).
According to an embodiment of the invention, the temperature of the reaction to prepare the aqueous chlorohydrin solution is 10 to 80 deg.C, such as 20 to 70 deg.C, illustratively 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C.
According to an embodiment of the invention, the pressure of the reaction to prepare the aqueous chlorohydrin solution is in the range of 0.1 to 0.5MPa, such as 0.2 to 0.4MPa, exemplary 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5 MPa.
According to an embodiment of the present invention, the preparation of the aqueous chlorohydrin solution may be carried out in a chlorohydrination reaction apparatus known in the art.
According to an embodiment of the invention, the saponification reaction temperature is 30-130 ℃, for example 50-100 ℃, exemplary 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃.
According to an embodiment of the invention, the pressure of the saponification reaction is 0.02-0.5MPa, such as 0.05-0.4MPa, exemplary 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5 MPa.
According to an embodiment of the invention, the molar ratio of chlorohydrin to base is 1 (1.01-3.0), such as a molar ratio of chlorohydrin to calcium hydroxide of 1 (1.1-1.4), as well as a molar ratio of chlorohydrin to calcium hydroxide of 1 (1.15-1.3), illustratively a molar ratio of chlorohydrin to calcium hydroxide of 1: 1.2.
According to an embodiment of the invention, the base is added in the form of an aqueous base solution or an aqueous base emulsion. For example, the concentration of the base in the aqueous solution or aqueous emulsion of the base is 10 to 40% by weight, preferably 15 to 35% by weight.
According to an embodiment of the present invention, the base means at least one of a hydroxide of a group I element, a hydroxide of a group II element, and a carbonate of a group I element, preferably at least one of calcium hydroxide, sodium hydroxide, and sodium carbonate.
According to an embodiment of the invention, the preparation method further comprises: after the saponification waste liquid is pretreated, one part of the saponification waste liquid is returned to the chlorohydrin reaction step (for example, the saponification waste liquid is returned to the chlorohydrin reaction and/or the saponification reaction is prepared by using an aqueous alkali solution or an aqueous alkali emulsion), and the other part of the saponification waste liquid is evaporated, concentrated, cooled, crystallized or dried to obtain the solid of the metal chloride.
According to an embodiment of the invention, the pre-treatment comprises at least one of filtration, neutralization and cooling.
According to an embodiment of the invention, the drying is spray drying.
According to an embodiment of the invention, the evaporation is a multiple effect evaporation.
According to an embodiment of the invention, the saponification reaction is carried out in a saponification column.
According to the embodiment of the invention, the saponified solution is subjected to evaporative concentration, and the water vapor obtained by the evaporative concentration is used as a heat source of a saponification column, and/or the water vapor obtained by the evaporative concentration is used as a heat source of a reboiler of a separation column for crude alkylene oxide.
According to an embodiment of the invention, said separation after temperature-decreasing crystallization is done by filtration or centrifugation.
According to the embodiment of the invention, the crude alkylene oxide is rectified and separated to obtain an alkylene oxide product.
According to an exemplary embodiment of the present invention, the method for preparing alkylene oxide comprises the steps of:
contacting an aqueous chlorohydrin solution containing a metal chloride with a concentration of not less than 10 wt% with an alkali to perform a saponification reaction to obtain crude alkylene oxide and a saponification waste solution; after the saponification waste liquid is pretreated, returning one part of the saponification waste liquid to the chlorohydrin reaction step, and evaporating and concentrating the other part of the saponification waste liquid, cooling and crystallizing or drying the other part of the saponification waste liquid to obtain a solid of the metal chloride;
the water vapor obtained by evaporating and concentrating the saponified solution is used as a heat source of a saponification tower, and/or the water vapor obtained by evaporating and concentrating is used as a heat source of a reboiler of a separation tower of crude alkylene oxide;
and rectifying and separating the crude alkylene oxide to obtain an alkylene oxide product.
The invention has the advantages of
The chlorohydrin aqueous solution containing more than 10 wt% of metal chloride is fed into a saponification tower to be contacted with alkali for saponification reaction, crude alkylene oxide is obtained at the top of the saponification tower, saponification waste liquid containing high-concentration metal chloride is obtained at the bottom of the saponification tower, the saponification waste liquid is concentrated to obtain a metal chloride concentrated solution and water vapor, the metal chloride obtained by further crystallizing and separating the metal chloride concentrated solution can be sold as a commodity, and the water vapor is used as a heat source of the saponification tower and/or a crude alkylene oxide separation tower. The preparation method of the epoxy alkane provided by the invention can reduce or even not generate waste water, and realizes green production of preparing the epoxy alkane by a chlorohydrination method.
Drawings
FIG. 1 is a process flow diagram of the olefin oxide production process of example 3.
Reference numerals: 1. the process water, 2, chlorine, 3, propylene, 4, chlorohydrination reaction liquid, 5, epoxypropane, 6, steam, 7, saponification waste liquid, 8, pretreated saponification waste liquid, 9, saponification waste liquid for preparing lime milk, 10, solid calcium hydroxide, 11, lime milk, 12, saponification waste liquid returned to a chlorohydrination reactor, 13, saponification waste liquid subjected to evaporation and concentration, 14, calcium chloride solid, 15, evaporation steam, 16, steam for saponification reaction, 17 and recovered steam used as a heat source of a crude epoxypropane rectification separation tower.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The analysis conditions for the products in the following examples are as follows:
an analytical instrument: agilent GC 7820; a chromatographic column: 30 m.times.530 μm.times.0.25 μm DB-FFAP; a detector: FID; sample inlet temperature: 225 ℃, detector temperature: and (3) temperature programming at 240 ℃: keeping at 40 deg.C for 5min, 30 deg.C/min to 230 deg.C for 5 min; h2：0.1Mpa，AIR：0.1Mpa；N2: 0.075 MPa; tail blowing: 0.1 MPa.
Example 1
Chlorohydrination reaction
The reaction device is a 1000ml four-neck round bottom glass flask, and is provided with mechanical stirring, the stirring speed is 100rpm, two bottom inserting tubes are arranged at two bottle mouths, one is used for introducing chlorine, and the other is used for introducing propylene. The reaction solution contains 20 wt% of calcium chloride solution, the volume of the total reaction solution is 800ml, the reaction temperature is controlled by a hot water bath at 50 ℃, and the reaction flask is wrapped by black plastic cloth and protected from light.
Chlorine gas was fed at a rate of 52ml/min (2.3mmol/min) and propylene was fed at a rate of 62ml/min (2.7 mmol/h).
The gas phase is removed from the gas phase space of the reaction bottle and is absorbed by alkali liquor and ethyl acetate.
And analyzing the contents of chloropropanol and impurities in the reaction material, and analyzing the contents of propylene and impurities in the gas phase removed from the reaction bottle.
And (3) comprehensively analyzing the results after the aeration reaction for 200 min: 3.02 wt% of chloropropanol (PCH), 0.14 wt% of Dichloropropane (DCP), 0.08 wt% of dichlorodiisopropyl ether (PCE), 0.010 wt% of chloropropone and 19.4 wt% of calcium chloride.
Saponification reaction
823g of chlorohydrination reaction liquid (containing 263mmol of PCH) and 137.5g of 17 wt% of calcium hydroxide aqueous emulsion (315.5mmol) are mixed and added into a reaction bottle, the reaction temperature is controlled to be 75 ℃, nitrogen for stripping is introduced below the liquid surface of the reaction bottle at the speed of 100L/min, the obtained gas phase reaction product, namely crude epoxy propane is firstly cooled by cold water at the temperature of 5 ℃, and tail gas is absorbed and trapped by 2000ml of methyl acetate at the temperature of 25 ℃. The reaction solution was analyzed and monitored, and when the chloropropanol content in the saponified solution was less than 0.01 wt%, the reaction was completed.
The waste saponification liquid in the reaction bottle is filtered, 2.50g of wet residue is filtered, and 925g of light yellow waste saponification liquid with the pH value of 12-13, wherein the pH value is 20.3 wt% of calcium chloride and 0.022 wt% of propylene glycol is obtained. The propylene oxide yield was 98.5%.
Example 2
Chlorohydrination reaction
The operation parameters and the charge amount were the same as those of example 1 except that the waste saponification solution of example 1 was used as the reaction solution.
And after the gas is ventilated for 205min, the mass fraction of chloropropanol in the reaction liquid reaches about 3.1 wt%, and the appearance of the reaction liquid is light yellow.
The analysis result shows that the reaction liquid contains 3.1 wt% of chloropropanol, 0.16 wt% of DCP, 0.083 wt% of PCE, 0.013 wt% of chloropropone and 19.6 wt% of calcium chloride.
Saponification reaction
823g of chlorohydrination reaction liquid (containing 270mmol of PCH) and 141g of 17 wt% calcium hydroxide aqueous emulsion (324mmol) are mixed and added into a reaction bottle, the reaction temperature is controlled at 75 ℃, nitrogen for stripping is introduced below the liquid surface of the reaction at the speed of 100L/min, the obtained reaction product gas phase-crude propylene oxide is firstly cooled by cold water at the temperature of 5 ℃, and tail gas is absorbed and trapped by 2000ml of methyl acetate at the temperature of 25 ℃. The reaction solution was analyzed and monitored, and when the chloropropanol content in the saponified solution was less than 0.01 wt%, the reaction was completed.
After the reaction, the saponified solution was filtered to remove 2.45g of wet residue, and 930g of pale yellow saponified waste solution having a pH of 12-13 and containing 20.4 wt% of calcium chloride and 0.020 wt% of propylene glycol was obtained. The propylene oxide yield was 98.5%.
Example 3
As shown in a preparation process flow chart of propylene oxide shown in figure 1, process water 1 and/or saponified waste liquid 12 returning to a chlorohydrination reactor are/is added into the chlorohydrination reactor, chlorine 2 and propylene 3 are introduced to obtain chlorohydrination reaction liquid 4 with chloropropanol concentration of 2-5 wt%, the chlorohydrination reaction liquid 4 enters the saponification reactor to be saponified with lime milk 11, and the lime milk 11 is prepared by a mixture of solid calcium hydroxide 10 and saponified waste liquid 9 for preparing lime milk and/or process water. The heat of the saponification reaction is provided by steam 6 and/or recovered steam 16 generated by evaporation concentration, the propylene oxide 5 and the saponified waste liquid 7 are generated by saponification, the saponified waste liquid 7 is pretreated to obtain pretreated saponified waste liquid, and the pretreated saponified waste liquid is divided into recycled saponified waste liquid 8 and saponified waste liquid 13 subjected to evaporation concentration. And evaporating and concentrating the saponified waste liquid 13 subjected to evaporation and concentration to obtain a calcium chloride concentrated solution and evaporated steam 15, performing post-treatment such as cooling and crystallization on the calcium chloride concentrated solution to obtain solid calcium chloride 14, wherein the evaporated steam 15 can be used as steam 16 for saponification reaction and/or recovered steam 17 used as a heat source of a crude propylene oxide rectification separation tower.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of alkylene oxide is characterized by comprising the following steps: contacting chlorohydrin aqueous solution containing metal chloride with alkali, and performing saponification reaction to obtain crude alkylene oxide and saponification waste liquid;
the concentration of the metal chloride in the chlorohydrin aqueous solution is not less than 10 wt%.
2. The process according to claim 1, wherein the concentration of the metal chloride in the aqueous chlorohydrin solution is 10 to 50 wt.%, preferably 20 to 35 wt.%.
3. The method according to claim 1 or 2, wherein the metal in the metal chloride is at least one of group I element and group II element, preferably sodium and/or calcium; preferably, the metal chloride is sodium chloride and/or calcium chloride.
4. The production method according to any one of claims 1 to 3, wherein the aqueous chlorohydrin solution containing a metal chloride is obtained by reacting chlorine gas and an olefin in an aqueous metal chloride solution.
5. The process according to claim 4, wherein the olefin is ethylene, propylene, chloropropene or butene.
Preferably, the chlorohydrin content of the chlorohydrin aqueous solution is 1 to 10 wt%, preferably 2 to 5 wt%.
Preferably, the molar ratio of the feed of chlorine to olefin is 1 (1.01-1.3), for example 1 (1.05-1.175).
Preferably, the temperature of the reaction to prepare the aqueous chlorohydrin solution is from 10 to 80 deg.C, for example from 20 to 70 deg.C.
Preferably, the pressure of the reaction to prepare the aqueous chlorohydrin solution is in the range of from 0.1 to 0.5MPa, for example from 0.2 to 0.4 MPa.
6. A method according to any of claims 1-5, characterized in that the saponification reaction is carried out at a temperature of 30-130 ℃, such as 50-100 ℃.
Preferably, the pressure of the saponification reaction is 0.02-0.5MPa, for example 0.05-0.4 MPa.
Preferably, the molar ratio of chlorohydrin to base is 1 (1.01-3.0), for example the molar ratio of chlorohydrin to calcium hydroxide is 1 (1.1-1.4).
7. The method according to any one of claims 1 to 6, wherein the base is added in the form of an aqueous solution of the base or an aqueous emulsion of the base.
8. The method according to claim 7, wherein the concentration of the alkali in the aqueous solution or aqueous emulsion of an alkali is 10 to 40% by weight.
Preferably, the base means at least one of a hydroxide of a group I element, a hydroxide of a group II element, and a carbonate of a group I element, preferably at least one of calcium hydroxide, sodium hydroxide, and sodium carbonate.
9. The production method according to any one of claims 1 to 8, characterized by further comprising: after the saponification waste liquid is pretreated, one part of the saponification waste liquid returns to the chlorohydrin reaction step, and the other part of the saponification waste liquid is evaporated, concentrated, cooled, crystallized and/or dried to obtain the solid of the metal chloride.
Preferably, the pre-treatment comprises at least one of filtration, neutralization and cooling.
Preferably, the drying is spray drying.
Preferably, the evaporation is multiple effect evaporation.
Preferably, the saponification reaction is carried out in a saponification column.
10. The preparation method according to any one of claims 1 to 9, wherein the crude alkylene oxide is subjected to rectification separation to obtain an alkylene oxide product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115253341A (en) * | 2022-08-15 | 2022-11-01 | 惠州市红墙化学有限公司 | Method and device for removing and converting alkylene oxide |
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| CN101062924A (en) * | 2007-04-23 | 2007-10-31 | 锦化化工集团氯碱股份有限公司 | Device and method for producing trimethylene oxide by using electrolytic solution as saponification agent |
| CN102241647A (en) * | 2011-05-24 | 2011-11-16 | 淄博永大化工有限公司 | Preparation technology of propylene oxide |
| CN106831659A (en) * | 2017-01-19 | 2017-06-13 | 于加全 | A kind of chlorohydrination production technology of saponification waste-water zero-emission |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062924A (en) * | 2007-04-23 | 2007-10-31 | 锦化化工集团氯碱股份有限公司 | Device and method for producing trimethylene oxide by using electrolytic solution as saponification agent |
| CN102241647A (en) * | 2011-05-24 | 2011-11-16 | 淄博永大化工有限公司 | Preparation technology of propylene oxide |
| CN106831659A (en) * | 2017-01-19 | 2017-06-13 | 于加全 | A kind of chlorohydrination production technology of saponification waste-water zero-emission |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115253341A (en) * | 2022-08-15 | 2022-11-01 | 惠州市红墙化学有限公司 | Method and device for removing and converting alkylene oxide |
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