CN103274558A - Method for treating coked crude benzene hydrogenation refining process wastewater and waste gas - Google Patents
Method for treating coked crude benzene hydrogenation refining process wastewater and waste gas Download PDFInfo
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Abstract
The invention discloses a method for treating coked crude benzene hydrogenation refining process wastewater and waste gas. The method belongs to the field of wastewater and waste gas treatment in coal chemical industry. The method comprises the following steps of: by taking process wastewater, process waste gas, sulfuric acid with the concentration of 20 percent, nitrogen and activated carbon generated in the coked crude benzene hydrogenation refining production process as raw materials and taking a stripping tower, a sulfuric acid adsorption tank, a cryogenic unit, a desulfuration device and an adsorption tank as equipment, treating the process wastewater and process waste gas generated by the coked crude benzene hydrogenation refining. The method has the advantages that 1, the universal equipment serves as the common equipment in the field of chemical industry, and the manufacturing is simple; 2, the adsorbent activated carbon used for adsorbing benzene in waste water is wide in source and low in cost, the activated carbon adsorbs in a saturated mode, is easily regenerated and can be recycled, and secondary pollution is avoided; and 3, the method is simple in process, convenient to operate and high in continuity, so that the resources can be effectively recycled.
Description
Technical field
The invention belongs to coal chemical industrial waste water, off gas treatment field, relate in particular to and a kind ofly handle process for hydrofining coking crude benzene waster water process waste gas and reclaim the wherein method of organism and sulphur nitrogen hydrogen resource.
Background technology
Coking crude benzene is one of product in the raw gas that generates in the coal coking process, contain aromatic hydrocarbons such as benzene,toluene,xylene, trimethylbenzene, thiophene, indenes in the coke-oven gas behind deamination, contain unsaturated compound, sulfocompound, aliphatic hydrocarbon, naphthalene, phenols and pyridine compounds and their in addition, be referred to as crude benzol.Because the coking industry of China is numerous, produces a large amount of crude benzol per year, the direct purposes of crude benzol is less, is mainly used in products such as deep processing benzene,toluene,xylene processed, and benzene,toluene,xylene all is valuable basic Organic Chemicals, and is of many uses.The main flow complete processing of the coking crude benzene of domestic current has two kinds at present, a kind of is the pickling distillation method, the advantage of pickling distillation method is: technology is simple, facility investment is few, shortcoming be seriously polluted, yield is low, aftertreatment is difficult, this Technology to 2014 year will all be eliminated, and use few at present; Another kind is the hydrofining method, and this Technology is unusual proven technique in the industry, and domestic most of crude benzol device all adopts the hydrofining technology, its advantage is: the product purity height, shortcoming is that technology is complicated slightly, and facility investment is big, and the annual working ability of this technology reaches 4,000,000 tons.The hydrofining method is in the refining production process of crude benzole hydrogenation, can produce waste water and the waste gas that contains materials such as benzene, sulphur, nitrogen, as direct discharge, though benzene can biological degradation, but it is much lower than evaporation rate, contain the organic waste water of benzene and waste gas and will threaten fish and hydrobiological existence, also human beings'health in serious threat.These contain the waste water, waste gas of materials such as benzene, sulphur, nitrogen if can cause ambient atmosphere to pollute and the serious organic contamination of water body in the environment without dealing carefully with to be discharged into, it is generally acknowledged, concentration is low-concentration organic waste water below 500ppm, needs after the purifying treatment discharging or recycles.Benzene concentration is about 250ppm in the waste water that produces in the refining production of crude benzole hydrogenation, belong to low-concentration organic waste water, also contain compositions such as sulphur, nitrogen, toxicity is big, and is water insoluble at normal temperatures because of benzene, deals with the comparison difficulty, simultaneously owing to contain materials such as sulphur, nitrogen in the factory effluent, so have unpleasant foul odour, if do not handle, will have a strong impact on people and biological living environment.Therefore, seek that cost is low, non-secondary pollution, simple to operate, effectively handle the method for process for hydrofining coking crude benzene waster water process waste gas, process for hydrofining coking crude benzene waster water process treatment of waste gas is had very important significance.
At present, the common method of handling organic waste water has physics method, chemical method, biological treatment, high-level oxidation technology, and the defective of chemical method is the medicament expense height, and it is bad that chemical coagulation is removed some organism effect; The defective of biological process is that processing speed is slow, and the required cycle is long; The defective of oxidation technology is to need the development novel reactor to improve the efficient of wastewater treatment, the processing cost height; Therefore physisorphtion becomes and is commonly used to handle organic method in the waste water; with rectifying; the method that absorption combines with chemical method is handled process for hydrofining coking crude benzene waster water process waste gas; this method can not only be removed the benzene in the waste water and gas; sulphur; materials such as nitrogen; and can reclaim benzene in the waste water and gas; sulphur; materials such as nitrogen; order for the treatment of the device just of processing wastewater technology waste gas is disposable; these equipment all are common equipments at chemical field; make simple; the activated carbon of sorbent wide material sources that are used for absorption waste water benzene; cheap; and charcoal absorption saturated back regeneration easily; reusable; do not produce secondary pollution; therefore; the method that rectifying and absorption are combined with chemical method is to handle the most effective treatment technology of process for hydrofining coking crude benzene waster water process waste gas; than additive method; it is simple that this method has technology; easy to operate; cost is low; non-secondary pollution; continuity is strong; resource is effectively recycled, not only protected environment but also increase income for enterprise.With 100,000 tons of/year crude benzole hydrogenation refining plants, production time is that the waste water and gas that produced in 8000 hours calculates, annual recyclable hydrogen 1350000Nm3, ammonia 2400 Nm3, hydrogen sulfide 2400 Nm3,250 tons of benzene series things, calculate by present market value, annual for enterprise increases income 5,000,000 yuan, 1,000,000 yuan of the tooling costs of deduction waste water and gas, annual for enterprise increases by 4,000,000 yuan of pure profits, economic benefit is considerable.
Summary of the invention:
The problem that the present invention mainly solves provides a kind ofly to be handled process for hydrofining coking crude benzene waster water process waste gas and reclaims the wherein method of organism and sulphur nitrogen hydrogen resource, this method is raw material with the processing wastewater technology waste gas that hydrofining coking crude benzene produces, handle process for hydrofining coking crude benzene waster water process waste gas by operations such as stripping, charcoal absorptions, this method has that running cost is low, non-secondary pollution, operation is simple and feasible, and the advantage of recyclable resource.
The present invention can be achieved through the following technical solutions:
A kind of method of handling process for hydrofining coking crude benzene waster water process waste gas is characterized in that being made of following steps:
(1) processing wastewater that contains the about 250ppm of benzene series thing, the about 50ppm of total nitrogen, the about 100ppm of total sulfur that produces in the quantitative hydrofining coking crude benzene production process is preheated to 90 ℃ earlier after, send into stripping tower, opening for feed is located at the 15th block of column plate, operating parameters in the stripping tower is: tower is pressed 0.38-0.42Mpa, tower top temperature 108-112 ℃, 138-142 ℃ of tower reactor temperature, reflux ratio 0.3-0.5, in stripping tower, be dissolved in gases such as hydrogen sulfide in the processing wastewater, ammonia, benzene water azeotrope and a spot of low-boiling point material are discharged from cat head, and remaining liquid enters Shui Bao; The cat head expellant gas obtains portion gas and partially liq after withdrawing can reclaims cooling, the gas that obtains after knockout drum separates is that hydrogen sulfide, ammonia, methane and main component are the gas mixture of low-boiling-point organic compound steam such as butane, hexanaphthene, benzene, be designated hereinafter simply as stripping gas, remaining liquid is in the knockout drum.
After mixing, the technology waste gas that the main component that produces when (2) stripping gas being produced with the crude benzole hydrogenation device is about hydrogen 82%, methane 13.75%, benzene 4%, hydrogen sulfide, ammonia 0.25% sends into the sulfuric acid absorption groove, wherein having only ammonia and concentration is that 20% sulfuric acid reaction generates ammonium sulfate and crystallization, the chemical fertilizer ammonium sulfate that obtains after crystallization treatment; Low-boiling-point organic compound steam such as responseless hydrogen sulfide, hydrogen, methane, benzene, butane, hexanaphthene are sent into-5 ℃ cryogenic unit, and organic steam is cooled to liquid and reclaims in cryogenic unit.
(3) hydrogen sulfide, hydrogen, methane are gas still in cryogenic unit, are introduced into desulfurizer, and hydrogen sulfide is recovered as sulphur in desulfurizer; Gas after the desulfurization enters pressure-swing absorption apparatus and sends the device recycling after with hydrogen purification back to, and the tail gas main component of transformation absorption is hydrogen 60%, and methane 40% can be used as clean boiler oil gas and recycles.
(4) waste liquid in the water bag in the step (1), liquid in the knockout drum are all sent back to the stripping tower import again and enter stripping tower again behind stripping with processing wastewater, all waste water is flowed out from tower reactor, delivering to adsorption tanks after heat exchange is cooled to 70 ℃ adsorbs with gac, benzene remaining in the waste water is absorbed by gac, waste water benzene content after absorption can be used as middle water reuse less than 0.1 ppm.
(5) gac of absorption behind the benzene carries out intermittence purging with 78-82 ℃ nitrogen and regenerates, and the benzene vapour that purges out can be recycled after cooling off.
Further technical scheme of the present invention is:
Operating parameters in the described stripping tower of step (1) is: tower is pressed 0.4Mpa, 110 ℃ of tower top temperatures, 140 ℃ of tower reactor temperature, reflux ratio 0.4.
It is 80 ℃ that the described nitrogen of step (5) carries out the intermittent temperature that purges regenerated carbon.
The invention has the beneficial effects as follows: a kind of method of handling process for hydrofining coking crude benzene waster water process waste gas is provided, the advantage of this method is: use general-purpose equipment to be the chemical field common equipment, make simple, the activated carbon of sorbent wide material sources that are used for absorption waste water benzene, cheap, and charcoal absorption saturated back regeneration easily, and is reusable, do not produce secondary pollution; Technology is simple, easy to operate, continuity is strong, and resource is effectively recycled.
Embodiment
Embodiment 1
After the processing wastewater that contains the about 250ppm of benzene series thing, the about 50ppm of total nitrogen, the about 100ppm of total sulfur that produces in the quantitative hydrofining coking crude benzene production process is preheated to 90 ℃ earlier, send into stripping tower, opening for feed is located at the 15th block of column plate, operating parameters in the stripping tower is: tower is pressed 0.38Mpa, 112 ℃ of tower top temperatures, 138 ℃ of tower reactor temperature, reflux ratio 0.5, in stripping tower, be dissolved in gases such as hydrogen sulfide in the processing wastewater, ammonia, benzene water azeotrope and a spot of low-boiling point material are discharged from cat head, and remaining liquid enters Shui Bao; The cat head expellant gas obtains portion gas and partially liq after withdrawing can reclaims cooling, the gas that obtains after knockout drum separates is that hydrogen sulfide, ammonia, methane and main component are that the gas mixture of low-boiling-point organic compound steam such as butane, hexanaphthene, benzene is designated hereinafter simply as stripping gas, and remaining liquid is in the knockout drum.After mixing, the technology waste gas that the main component that produces when stripping gas is produced with the crude benzole hydrogenation device is about hydrogen 82%, methane 13.75%, benzene 4%, hydrogen sulfide, ammonia 0.25% sends into the sulfuric acid absorption groove, wherein having only ammonia and concentration is that 20% sulfuric acid reaction generates ammonium sulfate and crystallization, the chemical fertilizer ammonium sulfate that obtains after crystallization treatment; Low-boiling-point organic compound steam such as responseless hydrogen sulfide, hydrogen, methane, benzene, butane, hexanaphthene are sent into-5 ℃ cryogenic unit, and organic steam is cooled to liquid and reclaims in cryogenic unit.Hydrogen sulfide, hydrogen, methane are gas still in cryogenic unit, are introduced into desulfurizer, and hydrogen sulfide is recovered as sulphur in desulfurizer; Gas after the desulfurization enters pressure-swing absorption apparatus and sends the device recycling after with hydrogen purification back to, and the tail gas main component of transformation absorption is hydrogen 60%, and methane 40% can be used as clean boiler oil gas and recycles.Waste liquid in the water bag in the step (1), liquid in the knockout drum are all sent back to the stripping tower import again enter stripping tower again behind stripping with processing wastewater, all waste water is flowed out from tower reactor, delivering to adsorption tanks after heat exchange is cooled to 70 ℃ adsorbs with gac, benzene remaining in the waste water is absorbed by gac, waste water benzene content after absorption can be used as middle water reuse less than 0.1 ppm.Gac behind the absorption benzene carries out the regeneration of intermittence purging with 78 ℃ nitrogen, and the benzene vapour that purges out can be recycled after cooling off.
Embodiment 2
After the processing wastewater that contains the about 250ppm of benzene series thing, the about 50ppm of total nitrogen, the about 100ppm of total sulfur that produces in the quantitative hydrofining coking crude benzene production process is preheated to 90 ℃ earlier, send into stripping tower, opening for feed is located at the 15th block of column plate, operating parameters in the stripping tower is: tower is pressed 0.40Mpa, 110 ℃ of tower top temperatures, 140 ℃ of tower reactor temperature, reflux ratio 0.4, in stripping tower, be dissolved in gases such as hydrogen sulfide in the processing wastewater, ammonia, benzene water azeotrope and a spot of low-boiling point material are discharged from cat head, and remaining liquid enters Shui Bao; The cat head expellant gas obtains portion gas and partially liq after withdrawing can reclaims cooling, the gas that obtains after knockout drum separates is that hydrogen sulfide, ammonia, methane and main component are the gas mixture of low-boiling-point organic compound steam such as butane, hexanaphthene, benzene, be designated hereinafter simply as stripping gas, remaining liquid is in the knockout drum.After mixing, the technology waste gas that the main component that produces when stripping gas is produced with the crude benzole hydrogenation device is about hydrogen 82%, methane 13.75%, benzene 4%, hydrogen sulfide, ammonia 0.25% sends into the sulfuric acid absorption groove, wherein having only ammonia and concentration is that 20% sulfuric acid reaction generates ammonium sulfate and crystallization, the chemical fertilizer ammonium sulfate that obtains after crystallization treatment; Low-boiling-point organic compound steam such as responseless hydrogen sulfide, hydrogen, methane, benzene, butane, hexanaphthene are sent into-5 ℃ cryogenic unit, and organic steam is cooled to liquid and reclaims in cryogenic unit.Hydrogen sulfide, hydrogen, methane are gas still in cryogenic unit, are introduced into desulfurizer, and hydrogen sulfide is recovered as sulphur in desulfurizer; Gas after the desulfurization enters pressure-swing absorption apparatus and sends the device recycling after with hydrogen purification back to, and the tail gas main component of transformation absorption is hydrogen 60%, and methane 40% can be used as clean boiler oil gas and recycles.Waste liquid in the water bag in the step (1), liquid in the knockout drum are all sent back to the stripping tower import again enter stripping tower again behind stripping with processing wastewater, all waste water is flowed out from tower reactor, delivering to adsorption tanks after heat exchange is cooled to 70 ℃ adsorbs with gac, benzene remaining in the waste water is absorbed by gac, waste water benzene content after absorption can be used as middle water reuse less than 0.1 ppm.Gac behind the absorption benzene carries out the regeneration of intermittence purging with 80 ℃ nitrogen, and the benzene vapour that purges out can be recycled after cooling off.
Embodiment 3
After the processing wastewater that contains the about 250ppm of benzene series thing, the about 50ppm of total nitrogen, the about 100ppm of total sulfur that produces in the quantitative hydrofining coking crude benzene production process is preheated to 90 ℃ earlier, send into stripping tower, opening for feed is located at the 15th block of column plate, operating parameters in the stripping tower is: tower is pressed 0.42Mpa, 108 ℃ of tower top temperatures, 142 ℃ of tower reactor temperature, reflux ratio 0.3, in stripping tower, be dissolved in gases such as hydrogen sulfide in the processing wastewater, ammonia, benzene water azeotrope and a spot of low-boiling point material are discharged from cat head, and remaining liquid enters Shui Bao; The cat head expellant gas obtains portion gas and partially liq after withdrawing can reclaims cooling, the gas that obtains after knockout drum separates is that hydrogen sulfide, ammonia, methane and main component are the gas mixture of low-boiling-point organic compound steam such as butane, hexanaphthene, benzene, be designated hereinafter simply as stripping gas, remaining liquid is in the knockout drum.After mixing, the technology waste gas that the main component that produces when stripping gas is produced with the crude benzole hydrogenation device is about hydrogen 82%, methane 13.75%, benzene 4%, hydrogen sulfide, ammonia 0.25% sends into the sulfuric acid absorption groove, wherein having only ammonia and concentration is that 20% sulfuric acid reaction generates ammonium sulfate and crystallization, the chemical fertilizer ammonium sulfate that obtains after crystallization treatment; Low-boiling-point organic compound steam such as responseless hydrogen sulfide, hydrogen, methane, benzene, butane, hexanaphthene are sent into-5 ℃ cryogenic unit, and organic steam is cooled to liquid and reclaims in cryogenic unit.Hydrogen sulfide, hydrogen, methane are gas still in cryogenic unit, are introduced into desulfurizer, and hydrogen sulfide is recovered as sulphur in desulfurizer; Gas after the desulfurization enters pressure-swing absorption apparatus and sends the device recycling after with hydrogen purification back to, and the tail gas main component of transformation absorption is hydrogen 60%, and methane 40% can be used as clean boiler oil gas and recycles.Waste liquid in the water bag in the step (1), liquid in the knockout drum are all sent back to the stripping tower import again enter stripping tower again behind stripping with processing wastewater, all waste water is flowed out from tower reactor, delivering to adsorption tanks after heat exchange is cooled to 70 ℃ adsorbs with gac, benzene remaining in the waste water is absorbed by gac, waste water benzene content after absorption can be used as middle water reuse less than 0.1 ppm.Gac behind the absorption benzene carries out the regeneration of intermittence purging with 82 ℃ nitrogen, and the benzene vapour that purges out can be recycled after cooling off.
Claims (3)
1. method of handling process for hydrofining coking crude benzene waster water process waste gas, be that 20% sulfuric acid, nitrogen, gac are raw material to produce processing wastewater technology waste gas, concentration in the hydrofining coking crude benzene production process, be equipment with stripping tower, sulfuric acid absorption groove, cryogenic unit, desulfurizer, adsorption tanks, come process for hydrofining coking crude benzene waster water process waste gas is handled by following five steps, it is characterized in that:
Step (1) contains the about 250ppm of benzene series thing with what produce in the quantitative hydrofining coking crude benzene production process, the about 50ppm of total nitrogen, after the processing wastewater of the about 100ppm of total sulfur is preheated to 90 ℃ earlier, send into stripping tower, opening for feed is located at the 15th block of column plate, operating parameters in the stripping tower is: tower is pressed 0.38-0.42Mpa, tower top temperature 108-112 ℃, 138-142 ℃ of tower reactor temperature, reflux ratio 0.3-0.5, in stripping tower, be dissolved in the hydrogen sulfide in the processing wastewater, gases such as ammonia, benzene water azeotrope and a spot of low-boiling point material are discharged from cat head, and remaining liquid enters Shui Bao; The cat head expellant gas obtains portion gas and partially liq after withdrawing can reclaims cooling, the gas that obtains after knockout drum separates is that hydrogen sulfide, ammonia, methane and main component are the gas mixture of low-boiling-point organic compound steam such as butane, hexanaphthene, benzene, be designated hereinafter simply as stripping gas, remaining liquid is in the knockout drum;
After mixing, the technology waste gas that the main component that produces when step (2) is produced stripping gas with the crude benzole hydrogenation device is about hydrogen 82%, methane 13.75%, benzene 4%, hydrogen sulfide, ammonia 0.25% sends into the sulfuric acid absorption groove, wherein having only ammonia and concentration is that 20% sulfuric acid reaction generates ammonium sulfate and crystallization, the chemical fertilizer ammonium sulfate that obtains after crystallization treatment; Gases such as responseless hydrogen sulfide, hydrogen, methane, benzene, butane, hexanaphthene are sent into-5 ℃ cryogenic unit, and organic steam is cooled to liquid and reclaims in cryogenic unit;
Step (3) hydrogen sulfide, hydrogen, methane in cryogenic unit are gas still, are introduced into desulfurizer, and hydrogen sulfide is recovered as sulphur in desulfurizer; Gas after the desulfurization enters pressure-swing absorption apparatus and sends the device recycling after with hydrogen purification back to, and the tail gas main component of transformation absorption is that hydrogen is about 60%, and methane is about 40%, can be used as clean boiler oil gas and recycles;
Step (4) all sends back to the stripping tower import again with the waste liquid in the water bag in the step (1), liquid in the knockout drum and enters stripping tower again behind stripping with processing wastewater, all waste water is flowed out from tower reactor, delivering to adsorption tanks after heat exchange is cooled to 70 ℃ adsorbs with gac, benzene remaining in the waste water is absorbed by gac, waste water benzene content after absorption can be used as middle water reuse less than 0.1 ppm;
Gac behind step (5) the absorption benzene carries out the regeneration of intermittence purging with 78-82 ℃ nitrogen, and the benzene vapour that purges out can be recycled after cooling off.
2. a kind of method of handling process for hydrofining coking crude benzene waster water process waste gas according to claim 1, it is characterized in that: the operating parameters in the described stripping tower of step (1) is: tower is pressed 0.4Mpa, 110 ℃ of tower top temperatures, 140 ℃ of tower reactor temperature, reflux ratio 0.4.
3. a kind of method of handling process for hydrofining coking crude benzene waster water process waste gas according to claim 1 is characterized in that: it is 80 ℃ that the described nitrogen of step (5) carries out the intermittent temperature that purges regenerated carbon.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106348253A (en) * | 2016-09-29 | 2017-01-25 | 马鞍山钢铁股份有限公司 | Production process for preparing sulfur by using Claus furnace |
CN106430115A (en) * | 2016-09-29 | 2017-02-22 | 马鞍山钢铁股份有限公司 | Production process for preparing sulfuric acid with application of acid making combustion furnace |
CN106629624A (en) * | 2016-09-29 | 2017-05-10 | 马鞍山钢铁股份有限公司 | Manufacturing technique for preparing sulphur by adopting compound type Claus oven |
CN106672898A (en) * | 2017-01-17 | 2017-05-17 | 青海盐湖工业股份有限公司 | Method for synthesizing ammonia by taking byproduct tail gas in process of producing acetylene by pyrolyzing natural gas as raw material |
CN111252839A (en) * | 2020-01-18 | 2020-06-09 | 河北荣特化工股份有限公司 | Novel process for treating hydrogenation type waste water and waste gas |
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2013
- 2013-05-28 CN CN2013102010338A patent/CN103274558A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106348253A (en) * | 2016-09-29 | 2017-01-25 | 马鞍山钢铁股份有限公司 | Production process for preparing sulfur by using Claus furnace |
CN106430115A (en) * | 2016-09-29 | 2017-02-22 | 马鞍山钢铁股份有限公司 | Production process for preparing sulfuric acid with application of acid making combustion furnace |
CN106629624A (en) * | 2016-09-29 | 2017-05-10 | 马鞍山钢铁股份有限公司 | Manufacturing technique for preparing sulphur by adopting compound type Claus oven |
CN106672898A (en) * | 2017-01-17 | 2017-05-17 | 青海盐湖工业股份有限公司 | Method for synthesizing ammonia by taking byproduct tail gas in process of producing acetylene by pyrolyzing natural gas as raw material |
CN111252839A (en) * | 2020-01-18 | 2020-06-09 | 河北荣特化工股份有限公司 | Novel process for treating hydrogenation type waste water and waste gas |
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Application publication date: 20130904 |