CN104524941A - Method of absorbing tail gas containing ethylene oxide - Google Patents
Method of absorbing tail gas containing ethylene oxide Download PDFInfo
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- CN104524941A CN104524941A CN201410753158.6A CN201410753158A CN104524941A CN 104524941 A CN104524941 A CN 104524941A CN 201410753158 A CN201410753158 A CN 201410753158A CN 104524941 A CN104524941 A CN 104524941A
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- absorption tower
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Abstract
The invention provides a method of absorbing tail gas containing ethylene oxide. The method comprises the following steps: S1, introducing an absorbent and the tail gas containing the ethylene oxide into an absorption tower (1), and carrying out absorption to form an absorption liquid; S2, sending the absorption liquid into a reaction kettle (2), and carrying out hydrolysis to form a reaction liquid; and S3, sending the reaction solution back to the absorption tower (1), carrying out cyclic reaction until the content of the residual ethylene oxide in the absorption tower (1) is lower than a preset value, and emptying the absorption tower (1). The invention aims at providing a method with capability of effectively absorbing the tail gas containing the ethylene oxide.
Description
Technical field
The present invention relates to the vent gas treatment field in petrochemical industry, more specifically, relate to a kind of method of the tail gas absorption containing oxirane.
Background technology
Ethylene glycol (being called for short EG) is a kind of very important aliphatic dihydroxy alcohol, not only be widely used for producd fibers, film, engineering plastics etc., directly can also be used as cooling agent and antifreezing agent, ethylene glycol is also one of basic material producing the products such as alkyd resins, plasticizer, paint, adhesive, surfactant, explosive and capacitor electrolyte simultaneously.
It is legal that the process route of current industrial production ethylene glycol is mainly epoxyethane water, namely under the effect of catalyst, and oxirane and water generation water and react generating glycol, therefore, in the tail gas of glycol unit, containing a large amount of oxirane.Oxirane is a kind of flammable explosive gas, can form explosive mixture with air, and its explosion limit is 3 ~ 10%, and heat source or naked light have the danger of combustion explosion.Especially, when temperature is higher than 500 DEG C, easily there is violent decomposition in oxirane, causes vessel breaks or explosion accident.In addition, oxirane or a kind of toxic gas, suck the headache that anesthesia too much can be caused poisoning, violent, dizzy, expiratory dyspnea, cardiomotility obstacle etc.Therefore, according to the relevant criterion of country, could discharged to air after the tail gas of glycol unit has to pass through process.
Current industrial process adopts pure water as absorbent containing the method major part of oxirane waste gas, and assimilation effect is bad, causes the content overproof of residual ethylene in the tail gas after process.In addition, because the impurity of waste gas ethylene oxide is more, concentration is unstable, is back to the reaction unit refine and reclaim ethylene glycol of ethylene glycol and uneconomical, and the best way is the cooling agent that it can be used as in public work.
Summary of the invention
For Problems existing in correlation technique, the object of the present invention is to provide a kind of method can carrying out effectively absorption to the industrial tail gas containing oxirane.
For achieving the above object, the invention provides a kind of method for the tail gas absorption containing oxirane, comprise the steps:
S1: absorbent is passed into absorption tower with the tail gas comprising oxirane and carries out absorbing to form absorbing liquid;
S2: absorbing liquid is sent into reactor and be hydrolyzed reaction with forming reactions liquid; And
S3: reactant liquor is sent back to absorption tower to carry out circular response, until residual epoxide ethane content carries out emptying lower than during preset value to absorption tower in absorption tower.
According to the present invention, also comprised the steps: before step S3
S201: reactant liquor is sent into circulating tank, and in circulating tank, the density of reactant liquor is detected, wherein, when the density of reactant liquor is greater than setting density, reactant liquor is discharged from circulating tank; Otherwise perform step S3.
According to the present invention, after the above-mentioned step that reactant liquor is discharged from circulating tank, also comprise the steps:
S202: during the reactant liquor of discharge is delivered to and still, and in and in utilizing nertralizer to carry out reactant liquor in still and, until after reactant liquor is neutralized to neutrality, from and still discharge.
According to the present invention, nertralizer is the sodium hydroxide solution of mass concentration 5%.
According to the present invention, also comprise the steps: in step s 2
S203: acidity detection is carried out to the absorbing liquid in reactor, and carry out sulfuric acid auto feed according to acidity testing result in reactor.
According to the present invention, further comprising the steps of in step s 2:
S204: pass into nitrogen to the ullage of absorbing liquid in reactor, to send the ethylene oxide gas deviate from from absorbing liquid back to absorption tower.
According to the present invention, preset value is 1ppm, and absorbent is the dilute sulfuric acid of mass concentration in 1 ~ 5% scope.
According to the present invention, absorption tower in operating temperature is within the scope of 20 ~ 50 DEG C, operating pressure is absorb under condition within the scope of 1.0 ~ 1.5Mpa.
According to the present invention, in step s 2, agitating device is utilized to stir the absorbing liquid sending into reactor.
According to the present invention, in step S1 and S2, the thermal insulation layer being arranged on absorption tower and reactor outside is respectively utilized to be incubated.
Advantageous Effects of the present invention is:
In tail gas absorption method of the present invention, to the device such as relating to oxirane, first the tail gas produced as ethylene glycol preparation technology carry out absorption reaction in absorption tower, then be hydrolyzed reaction in a kettle., secondary response to be again sent back in absorption tower through the reactant liquor of hydrolysis, thus to form circular response loop; When residual epoxide ethane content in absorption tower just carries out emptying to absorption tower, meeting the toxic emission of discharge standard in air lower than during preset value.Therefore, the tail gas that the present invention can produce the chemical plant installations relating to oxirane reclaims effectively, and can reclaim the oxirane waste gas produced in removal process, reaches the object of energy-saving and emission-reduction.
Accompanying drawing explanation
Fig. 1 is the general flow chart of tail gas absorption method of the present invention;
Fig. 2 is the structure diagram of the system applying tail gas absorption method of the present invention.
Detailed description of the invention
Existing composition graphs 1 and Fig. 2 are described the method for carrying out tail gas absorption to ethylene glycol preparation technology of the present invention.Particularly, this tail gas absorption method comprises the steps:
S1: absorbent is passed into absorption tower 1 with the tail gas comprising oxirane and carries out absorbing to form absorbing liquid;
S2: absorbing liquid is sent into reactor 2 and be hydrolyzed reaction with forming reactions liquid; And
S3: reactant liquor is sent back to absorption tower 1 to carry out circular response, until residual epoxide ethane content carries out emptying lower than during preset value to absorption tower 1 in absorption tower 1.In a preferred embodiment, preset value can be 1ppm, but should be appreciated that and also can adopt other preset values; In addition, absorbent can be the dilute sulfuric acid of mass concentration in 1 ~ 5% scope, and this all can determine according to concrete service condition, and the present invention is not limited to this.
Therefore, in tail gas absorption method of the present invention, first in absorption tower 1, absorption reaction is carried out to the tail gas that the chemical plant installations relating to oxirane produces, then be hydrolyzed reaction in reactor 2, secondary response to be again sent back in absorption tower 1 through the reactant liquor of hydrolysis, thus to form circular response loop; When residual epoxide ethane content in absorption tower 1 just carries out emptying to absorption tower, meeting the toxic emission of discharge standard in air lower than during preset value.Therefore, the tail gas that the present invention can produce the chemical plant installations relating to oxirane reclaims effectively, and can reclaim the oxirane waste gas produced in removal process, reaches the object of energy-saving and emission-reduction.
Further, can also comprise the steps: before step S3
S201: reactant liquor is sent into circulating tank 3, and in circulating tank 3, the density of reactant liquor is detected, and, when being greater than setting density when the density of reactant liquor, reactant liquor is discharged from circulating tank 3; Otherwise perform above-mentioned steps S3.This setting density can set according to the actual conditions in concrete operations, and the present invention is not limited to this.
Further, after the above-mentioned step of being discharged from circulating tank 3 by reactant liquor, perform following steps:
S202: during the reactant liquor of discharge is delivered to and still 4, and in and in utilizing nertralizer to carry out reactant liquor in still 4 and, until reactant liquor be neutralized to neutrality after from and still 4 discharge.Particularly, in a preferred embodiment, this nertralizer can be the sodium hydroxide solution of mass concentration 5%.Certainly should be appreciated that choosing of nertralizer can be determined according to concrete service condition, the present invention is not limited to this.
In addition, in a preferred embodiment, also comprise the steps: in above-mentioned steps S2
S203: acidity detection is carried out to the absorbing liquid in reactor 2, and carry out sulfuric acid auto feed according to acidity testing result in reactor 2.Specifically, operator can carry out arranging default acidity value according to required acidity value, when detecting that the acidity in reactor 2 does not reach default acidity value, carries out sulfuric acid auto feed by automatic control system, thus improves acidity in reactor 2.The sulfuric acid be added in reactor 2 can be the dilute sulfuric acid of mass concentration in 1 ~ 5% scope.
Continue with reference to Fig. 2, further comprising the steps of in step s 2:
S204: nitrogen is passed into, to send the ethylene oxide gas deviate from from absorbing liquid back to absorption tower 1 to the ullage of absorbing liquid in reactor 2.
In an alternate embodiment of the invention, absorption tower 1 can be within the scope of 20 ~ 50 DEG C in operating temperature, operating pressure is absorb under condition within the scope of 1.0 ~ 1.5Mpa.Further, in step s 2, agitating device can be utilized to stir the absorbing liquid sending into reactor 2.In addition, in step S1 and step S2, the thermal insulation layer being arranged on absorption tower 1 and reactor 2 outside respectively can be utilized to be incubated absorption tower 1 and reactor 2, to reduce thermal loss.
Existing composition graphs 1 and Fig. 2, be described method of the present invention with the form of instantiation.The tail gas that the chemical plant installations that tail gas absorption method of the present invention can be used for relating to oxirane produces absorbs, particularly, as mentioned above, method of the present invention forms primarily of absorption (being realized by absorption tower 1) and hydrolysis (carrying out in reactor 2) two steps, and the liquid after hydrolysis can circulate and be back in absorption tower 1, therefore form circulation and stress mode of the present invention, thus effectively reduce the discharge rate of waste liquid.
Specifically, added by the tower top of absorbent from absorption tower 1, pending tail gas enters by the bottom of the tower on absorption tower 1.In a preferred embodiment, absorption tower can adopt the form of packed tower, thus can ensure that the most of oxirane in pending tail gas is absorbed, in this external absorption process, absorption tower 1 keeps lower temperature, such as, the operating temperature on absorption tower 1 can be 20 ~ 50 DEG C, and operating pressure can be 1.0 ~ 1.5Mpa.After absorption tower 1, the most of oxirane in tail gas is absorbed liquid phase by the dilute sulfuric acid as absorbent, and absorbing liquid enters bottom reactor 2 with the reaction that is hydrolyzed at the bottom of the tower of absorption tower 1.
In reactor 2, oxirane, through the raw aquation generating glycol of dilute sulfuric acid catalytic reaction, meanwhile, is monitored the acidity of wherein absorbing liquid and suitably supplements dilute sulfuric acid thus ensure that in reactor 2, absorbing liquid is at suitable hydrolyzed under acidic conditions.Due to the acid condition in reactor 2 and higher temperature, thus the hydrolysis of oxirane can be promoted, reach maximum hydrolysis efficiency.In addition it is noted that the circulation fluid in reactor 2 should remain certain acidity and temperature.In addition, in an alternate embodiment of the invention, agitating device can also be set in reactor 2 to accelerate hydrolysis reaction.
For reactor 2, its inside can also pass into nitrogen.Particularly, the nitrogen of certain flow can be passed at the ullage of reactor 2 inside, and be communicated with the waste gas inlet on absorption tower 1, check valve is set in this communicating pipe simultaneously.In this way, the ethylene oxide gas deviate from solution is taken back in absorption tower 1 with circular response.
Further, the glycol water that in reactor 2, hydrolysis is formed loops back absorption tower 1 tower top by circulating pump and enters absorption tower 1, until tail gas ethylene oxide content carries out emptying after being less than such as 1ppm.Circulating tank 3 is provided with in the middle of the above-mentioned circulatory system, packing density meter while of on circulating tank 3, because glycol water density can increase with the increase of its concentration, when circulation fluid density exceedes the density of setting, the blow-off valve of circulating tank 3 will be opened automatically, with still 4 during circulation fluid enters.
In and still 4 in utilize certain density sodium hydroxide solution (such as, mass concentration is the sodium hydroxide solution of 5%) to neutralize ethylene glycol solution, the ethylene glycol solution after neutralization from and still 4 in be delivered in public work as cooling agent.
In the present invention's method as above, preferably, absorption tower 1 can be packed tower, and its bed stuffing height, filler pattern and the parameter such as size, tower diameter can carry out concrete calculating to set according to technological requirement.In addition, the heat insulation layer being arranged on absorption tower 1 and reactor 2 outside can be rock wool heat-preservation layer.
In sum, tail gas absorption method of the present invention is applied in the chemical plant installations such as ethylene glycol preparation technology relating to oxirane, tail gas absorption method can be made simple to operate, be easy to realize industrialization and serialization.In addition, method of the present invention can make up the deficiency of traditional ethylene glycol exhaust gas treating method, more thoroughly reduces ethylene oxide content remaining in tail gas, adds security, decrease environmental pollution.In addition, the present invention has recycled the oxirane in tail gas, is translated into the cooling fluid of public work, reduces production cost, reaches the object of energy-saving and emission-reduction, has significant economic benefit.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1., for the method to the tail gas absorption containing oxirane, it is characterized in that, comprise the steps:
S1: absorbent is passed into absorption tower (1) with the tail gas comprising oxirane and carries out absorbing to form absorbing liquid;
S2: described absorbing liquid is sent into reactor (2) and be hydrolyzed reaction with forming reactions liquid; And
S3: described reactant liquor is sent back to described absorption tower (1) to carry out circular response, until residual epoxide ethane content carries out emptying lower than during preset value to described absorption tower (1) in described absorption tower (1).
2. method according to claim 1, is characterized in that, also comprises the steps: before described step S3
S201: described reactant liquor is sent into circulating tank (3), and in described circulating tank (3), the density of described reactant liquor is detected,
Wherein, when the density of described reactant liquor is greater than setting density, described reactant liquor is discharged from described circulating tank (3); Otherwise perform described step S3.
3. method according to claim 2, is characterized in that, after the described step of being discharged from circulating tank (3) by reactant liquor, also comprises the steps:
S202: during the reactant liquor of discharge is delivered to and still (4), and in described and utilize nertralizer to neutralize reactant liquor in still (4), until after reactant liquor is neutralized to neutrality, from described and still (4) discharge.
4. method according to claim 3, is characterized in that, described nertralizer is the sodium hydroxide solution of mass concentration 5%.
5. method according to claim 1, is characterized in that, also comprises the steps: in described step S2
S203: acidity detection is carried out to the absorbing liquid in described reactor (2), and carry out sulfuric acid auto feed according to acidity testing result in described reactor (2).
6. method according to claim 1, is characterized in that, further comprising the steps of in described step S2:
S204: nitrogen is passed into, to send the ethylene oxide gas deviate from from absorbing liquid back to described absorption tower (1) to the ullage of absorbing liquid in described reactor (2).
7. the method according to any one of claim 1-6, is characterized in that,
Described preset value is 1ppm, and described absorbent is the dilute sulfuric acid of mass concentration in 1 ~ 5% scope.
8. the method according to any one of claim 1-6, is characterized in that,
Described absorption tower (1) in operating temperature is within the scope of 20 ~ 50 DEG C, operating pressure is absorb under condition within the scope of 1.0 ~ 1.5Mpa.
9. the method according to any one of claim 1-6, is characterized in that, in described step S2, utilizes agitating device to stir the absorbing liquid sending into described reactor (2).
10. the method according to any one of claim 1-6, is characterized in that, in described step S1 and S2, utilizes the thermal insulation layer being arranged on described absorption tower (1) and described reactor (2) outside to be respectively incubated.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104815535A (en) * | 2015-04-07 | 2015-08-05 | 山西大同大学 | Recycling method of ethylene oxide-containing organic waste gas |
CN106110832A (en) * | 2016-06-29 | 2016-11-16 | 句容宁武新材料股份有限公司 | A kind of polyether polyol produces the processing method of waste gas |
CN106139199A (en) * | 2015-04-24 | 2016-11-23 | 南通华尔康医疗科技股份有限公司 | A kind of method and device quickly carrying out oxirane parsing |
CN106268186A (en) * | 2016-09-30 | 2017-01-04 | 中石化上海工程有限公司 | Containing oxirane, the waste gas processing method of expoxy propane |
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WO1997032660A2 (en) * | 1996-03-09 | 1997-09-12 | Bernd Drzevitzky | Process and device for scrubbing waste gases containing ethylene oxide |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104815535A (en) * | 2015-04-07 | 2015-08-05 | 山西大同大学 | Recycling method of ethylene oxide-containing organic waste gas |
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CN106268186A (en) * | 2016-09-30 | 2017-01-04 | 中石化上海工程有限公司 | Containing oxirane, the waste gas processing method of expoxy propane |
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Application publication date: 20150422 |