CN106518610A - Treatment method of tail gas containing hydrogen chloride - Google Patents
Treatment method of tail gas containing hydrogen chloride Download PDFInfo
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- CN106518610A CN106518610A CN201610981896.5A CN201610981896A CN106518610A CN 106518610 A CN106518610 A CN 106518610A CN 201610981896 A CN201610981896 A CN 201610981896A CN 106518610 A CN106518610 A CN 106518610A
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- hydrogen chloride
- tail gas
- gas containing
- containing hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fertilizers (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a treatment method of tail gas containing hydrogen chloride and solves the technical problems that existing treatment methods of tail gas containing hydrogen chloride are high in treatment cost and not ideal in treatment effect. The treatment method comprises steps as follows: a catalyst is added to a reaction kettle, glycerin is added, and the catalyst and glycerin are fully mixed under the slight stirring condition; byproduct gas containing hydrogen during hydrogen and potassium conversion of sulfonyl compound fertilizer sequentially passes through a foam remover, a first-stage or multi-stage condenser and a demister, foam , insoluble matter and vapor in the tail gas are trapped, separated and removed, and then the tail gas enters a buffer tank and is slowly sent into a reaction kettle after flow metering to react with glycerin; the reaction is performed under the homogenous stirring condition; after the reaction ends, dichlorohydrin is evaporated out through reduced pressure distillation and obtained. The treatment method can be applied to the treatment field of the byproduct gas containing hydrogen chloride during hydrogen and potassium conversion of the sulfonyl compound fertilizer.
Description
Technical field
The present invention relates to the process field of tail gas, specifically a kind of processing method of tail gas containing hydrogen chloride.
Background technology
S-based compound fertilizer hydrogen potassium conversion procedure, concentrated sulphuric acid produce the gas containing hydrogen chloride, the portion with the reaction of potassium chloride
Divide gas that by-product hydrochloric acid is carried out substantially all by the way of falling film absorption.The depression in hydrochloric acid market, zero profit of most of enterprise is very
Sell to outside losing money instead of making money, increase the production cost of major product compound fertilizer.As country is increasingly strict to environmental requirement, enterprise also needs to throw
Enter substantial amounts of energy to ensure tail gas qualified discharge.
On the other hand, glycerol production quantity constantly rises price drops, and demand of the downstream epoxy resin to expoxy propane
Amount is continuously increased, the supply of cheap glycerol, has promoted with glycerol as raw material production expoxy propane industrial expansion, industrially
Using glycerol production epoxychloropropane, become an important developing direction.
Therefore, exist in the vent gas treatment containing hydrogen chloride gas for producing in existing S-based compound fertilizer hydrogen potassium conversion procedure
Processing cost is high, the technical problem that treatment effect is undesirable.
The content of the invention
The present invention is exactly to solve to there is processing cost in existing method vent gas treatment of the process containing hydrogen chloride gas
A kind of undesirable technical problem of high, treatment effect, there is provided tail gas containing hydrogen chloride for reducing processing cost, improving treatment effect
Processing method.
For this purpose, the present invention provides a kind of processing method of tail gas containing hydrogen chloride, which comprises the steps：(1) by catalyst
It is added in reactor, while adding glycerol, the adding proportion of the catalyst is controlled in the glycerol mass percent
4%～6%, under conditions of micro- stirring, be sufficiently mixed both；(2) S-based compound fertilizer hydrogen potassium is converted into the chloride of by-product
Change hydrogen, sequentially pass through demister, one or more levels condenser, demister, foam, insoluble matter in tail gas, and water are steamed
Gas trapping, separation are removed, subsequently into surge tank, slow Jing after flow measurement to send into reactor so as to carry out instead with glycerol
Should；(3) in the case that homogenizing is stirred, reaction is carried out, and makes the content of glycerol be less than 5%；(4), after reaction reaches terminal, take
Dichlorohydrin is steamed by vacuum distillation, obtains dichlorohydrin.
Preferably, the catalyst in step (1) be glacial acetic acid, octanoic acid, one or more in ethanedioic acid.
Preferably, in step (2), tail gas containing hydrogen chloride mass percent is 5%～20%.
Preferably, in step (3), course of reaction is carried out in two steps：First step chlorination reaction, by adjusting adding for hydrogen chloride
Enter amount, reaction temperature is controlled at 90～115 DEG C；Second step chlorination reaction, controlling reaction temperature is at 85～100 DEG C.
Preferably, in step (4), after chlorination reaction by-product moisture is separated, return S-based compound fertilizer device and do washings
Recycle, it is not outer to arrange.
The present invention according to above reaction mechanism, and chlorination hydrogen feedstock source and characteristic synthetic consider, it is multiple using sulfenyl
The gas containing hydrogen chloride of Hefei by-product, and relatively inexpensive glycerol be raw material, produce dichloropropanol product, be epoxychloropropane
Production qualified intermediate is provided.The present invention can carry out synthesis to the gas containing hydrogen chloride that S-based compound fertilizer hydrogen potassium converts by-product
Administer, reduce the environmental protection pressure of manufacturing enterprise, while reduce or prevent low value-added hydrochloric acid product, produce added value it is high two
Chloropropyl alcohol product, the hydrogen chloride gas utilization for S-based compound fertilizer enterprise provide a kind of new approach.Method therefor in the present invention
It is that the hydrochloric acid product cost that can change existing fertilizer production enterprise loses money instead of making money the outer quagmire sold, on the one hand reduces by 30-80 yuan/ton of salt
Cost is lost money instead of making money in acid, by taking 100,000 tons/year of sour method composite heat transfers as an example, produces about 30,000 tons of hydrochloric acid per year, can save about 90-240 ten thousand/
Year；On the other hand the output of by-product harmful influence hydrochloric acid is eliminated, emptying tail gas hydrogen chloride content is less than 80mg/m3。
Description of the drawings
Fig. 1 is present invention process schematic flow sheet.
In Fig. 1,1, demister；2nd, condenser；3rd, demister；4th, surge tank；5th, effusion meter.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
Apply the content described by example and be merely to illustrate the present invention, and should not also without limitation on this described in claims
It is bright.
Embodiment 1
By glacial acetic acid by the adding proportion for calculating, chlorination primary response kettle (A, B, C, D ...) is added to, while adding correspondence number
The glycerol (glycerol) of amount, wherein：4% (mass fraction) scope of the adding proportion control of organic acid catalyst in glycerin weight
It is interior, under conditions of micro- stirring both is sufficiently mixed.
The gas containing hydrogen chloride produced in S-based compound fertilizer hydrogen potassium conversion process, sequentially pass through 1 demister, 2 condensers, 3
Demister, foam, insoluble matter in tail gas, and vapor trapping, separation is removed, subsequently into 4 surge tanks, 5 effusion meters of Jing
After amount, the slow chlorinating container A that sends into makes which be reacted with glycerol.
During the course of the reaction, change the addition of adjustment hydrogen chloride gas according to temperature of reaction kettle, by reaction temperature control
At 105 DEG C or so；When question response temperature starts continuous decrease, by heater controlling reaction temperature at 90 DEG C or so, until anti-
The layering ratio of mix products is answered to reach requirement.
After reaction reaches terminal, dichloropropanol mixture is put into into chlorinating container B, vacuum distillation is taken by dichloro third
Alcohol is steamed, the dichlorohydrin steaming thing storage for obtaining, as the raw material for further producing expoxy propane or other products.
It is pair that the liquid discharge outlet arranged by chlorinating container removes hydrogen chloride in time with the chlorination reaction liquid of glycerol
Product water, it is ensured that the forward direction of reaction is carried out.The emptying up to standard Jing after the washing of end recirculated water of chlorination reaction tail gas, chlorination reaction are discharged
Liquid water return S-based compound fertilizer device do fertilizer washing tail gas water circulation use.
Specific implementation step is as follows：
(1) catalyst glacial acetic acid is added in chlorinating container A according to the adding proportion for calculating, while adding correspondence
The glycerol (glycerol) of quantity, wherein：(mass fraction, radix are the third three 4% for the adding proportion control of organic acid catalyst
Alcohol) in the range of under conditions of micro- stirring both is sufficiently mixed；
(2) S-based compound fertilizer hydrogen potassium converts the gas containing hydrogen chloride of by-product, sequentially passes through demister, one or more levels condensation
Device, demister, foam, insoluble matter in tail gas, and vapor trapping, separation are removed, subsequently into surge tank, Jing effusion meters
After amount, the slow chlorinating container A that sends into makes which be reacted with glycerol；
(3), in the case that homogenizing is stirred, reaction carries out at least to make the content of glycerol less than 5% in 1h, course of reaction
It is carried out in two steps.First step chlorination reaction, the reaction is exothermic reaction, and product is dissolved in the glycerine monochlorohydrin of water, process
Middle temperature can rise to more than 120 DEG C, can pass through to adjust the addition of hydrogen chloride, reaction temperature is controlled at 105 DEG C or so；Second
One-step chlorination reacts, and reaction starting temperature suitably can decline, and product is insoluble in the dichlorohydrin of water, now can be by heating
Device controlling reaction temperature is at 90 DEG C or so, until the layering ratio of mixed reaction product reaches requirement, you can be considered as reaction end；
(4), after reaction reaches terminal, dichloropropanol mixture is put into into chlorinating container B, vacuum distillation is taken by two
Chloropropyl alcohol is steamed, the dichlorohydrin steaming thing storage for obtaining, as the raw material for further producing expoxy propane or other products；
(5) detection of layering ratio is as follows：10ml reaction mixtures, 10ml soda baths (1N) are taken respectively adds 20ml amounts
Cylinder, mix homogeneously stand 20min, and observation oil phase, the volume of water phase, 3～5cm of oil phase volume are up to standard；
(6) hydrogen chloride and the chlorination reaction water byproduct of glycerol, need to be removed in time, be carried out with sharp reaction forward.Chlorination is anti-
Answer the position at various height of kettle that liquid flooding mouth is set, overflowing liquid enters ultimate chlorinating container.Reaction end gas Jing ends
Prime reactor is returned in emptying up to standard after recirculated water washing, qualified mixture, is returned S-based compound fertilizer device and is done fertilizer washing tail gas
Water circulation is used.
(7) after the course of reaction is that semicontinuous reaction, the reaction of A chlorinating containers terminate, B, C, D ... chlorinating container according to
Secondary to carry out (arrange reactor quantity according to production scale), the tail gas of containing hydrogen chloride is continuously added to, mass content 5%～20%；
In the glycerol raw material for being used, 90～99%, the preferred high-load of both contents is produced glycerol mass content with profit
Cost is reduced.
1 example of table, 1 vent gas treatment effect data table
Embodiment 2
In step (1), catalyst is octanoic acid, and the adding proportion of catalyst is controlled in the glycerol mass percent
6%；In step (3), course of reaction is carried out in two steps：First step chlorination reaction, by the addition for adjusting hydrogen chloride, will reaction
Temperature control is at 90 DEG C；Second step chlorination reaction, controlling reaction temperature is at 85 DEG C.
The other the same as in Example 1.
2 example of table, 2 vent gas treatment effect data table
Embodiment 3
In step (1), catalyst is ethanedioic acid, and the adding proportion control of catalyst is in the glycerol mass percent
5%；In step (3), course of reaction is carried out in two steps：First step chlorination reaction, by the addition for adjusting hydrogen chloride, will reaction
Temperature control is at 115 DEG C；Second step chlorination reaction, controlling reaction temperature is at 100 DEG C.
The other the same as in Example 1.
3 example of table, 3 vent gas treatment effect data table
Claims (5)
1. a kind of processing method of tail gas containing hydrogen chloride, is characterized in that comprising the steps：
(1) catalyst is added in reactor, while adding glycerol, the adding proportion of the catalyst is controlled described third
The 4%～6% of triol mass percent, under conditions of micro- stirring, is sufficiently mixed both；
(2) S-based compound fertilizer hydrogen potassium is converted the gas containing hydrogen chloride of by-product, demister, one or more levels condensation is sequentially passed through
Device, demister, foam, insoluble matter in tail gas, and vapor trapping, separation are removed, subsequently into surge tank, Jing effusion meters
It is slow after amount to send into reactor so as to be reacted with glycerol；
(3) in the case that homogenizing is stirred, reaction is carried out, and makes the content of glycerol be less than 5%；
(4), after reaction reaches terminal, take vacuum distillation to steam dichlorohydrin, obtain dichlorohydrin.
2. the processing method of tail gas containing hydrogen chloride according to claim 1, it is characterised in that urging in the step (1)
Agent is glacial acetic acid, octanoic acid, one or more in ethanedioic acid.
3. the processing method of tail gas containing hydrogen chloride according to claim 1, it is characterised in that in the step (2), tail gas
Containing hydrogen chloride mass percent is 5%～20%.
4. the processing method of tail gas containing hydrogen chloride according to claim 1, it is characterised in that in the step (3), reaction
Process is carried out in two steps：First step chlorination reaction, by the addition for adjusting hydrogen chloride, reaction temperature is controlled 90～115
℃；Second step chlorination reaction, controlling reaction temperature is at 85～100 DEG C.
5. the processing method of tail gas containing hydrogen chloride according to claim 1, it is characterised in that in step (3), chlorination reaction
After by-product moisture is separated, return S-based compound fertilizer device and do washings recycling, it is not outer to arrange.
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| CN201610981896.5A CN106518610A (en) | 2016-11-08 | 2016-11-08 | Treatment method of tail gas containing hydrogen chloride |
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| CN201610981896.5A CN106518610A (en) | 2016-11-08 | 2016-11-08 | Treatment method of tail gas containing hydrogen chloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293596A (en) * | 2018-09-30 | 2019-02-01 | 江苏润泽鑫生物科技有限公司 | The preparation method of 2- chloro-5-chloromethyl thiazole |
| WO2021129377A1 (en) * | 2019-12-27 | 2021-07-01 | 李宏峰 | Method for treating byproduct hydrogen chloride in fluorine-containing olefin production process |
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| CN101704722A (en) * | 2009-12-02 | 2010-05-12 | 兖州市天成化工有限公司 | Method for synthesizing dichloropropanol by catalyzing glycerol for chlorination under existence of dicarboxylic acid-rare earth chloride |
| CN102234224A (en) * | 2010-04-24 | 2011-11-09 | 广东理文化工研发有限公司 | Method for catalytic synthesis of dichloropropanol by hydrogen chloride-containing industrial waste gas and glycerol |
| EP2669247A1 (en) * | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing dichloropropanol |
| CN203816452U (en) * | 2014-05-16 | 2014-09-10 | 重庆海洲化学品有限公司 | System for treating by-product exhaust generated in chloromethane production |
| CN105272385A (en) * | 2015-11-27 | 2016-01-27 | 宜昌鄂中化工有限公司 | Method for producing magnesium calcium chloride by utilizing phosphate tailing |
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2016
- 2016-11-08 CN CN201610981896.5A patent/CN106518610A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704722A (en) * | 2009-12-02 | 2010-05-12 | 兖州市天成化工有限公司 | Method for synthesizing dichloropropanol by catalyzing glycerol for chlorination under existence of dicarboxylic acid-rare earth chloride |
| CN102234224A (en) * | 2010-04-24 | 2011-11-09 | 广东理文化工研发有限公司 | Method for catalytic synthesis of dichloropropanol by hydrogen chloride-containing industrial waste gas and glycerol |
| EP2669247A1 (en) * | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing dichloropropanol |
| CN203816452U (en) * | 2014-05-16 | 2014-09-10 | 重庆海洲化学品有限公司 | System for treating by-product exhaust generated in chloromethane production |
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| 无: "《盘锦恒兴化工有限责任公司4000t/a硫酸钾及联产6000t/a环氧氯丙烷项目环境影响报告书》", 16 July 2013 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293596A (en) * | 2018-09-30 | 2019-02-01 | 江苏润泽鑫生物科技有限公司 | The preparation method of 2- chloro-5-chloromethyl thiazole |
| WO2021129377A1 (en) * | 2019-12-27 | 2021-07-01 | 李宏峰 | Method for treating byproduct hydrogen chloride in fluorine-containing olefin production process |
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Application publication date: 20170322 |
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