CN1294087C - Method for treating waste acid from refining benzene for coking plant - Google Patents
Method for treating waste acid from refining benzene for coking plant Download PDFInfo
- Publication number
- CN1294087C CN1294087C CNB2003101096060A CN200310109606A CN1294087C CN 1294087 C CN1294087 C CN 1294087C CN B2003101096060 A CNB2003101096060 A CN B2003101096060A CN 200310109606 A CN200310109606 A CN 200310109606A CN 1294087 C CN1294087 C CN 1294087C
- Authority
- CN
- China
- Prior art keywords
- spent acid
- carbolic oil
- coke
- ammonium sulfate
- waste acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for treating waste acid from benzene refining in a coking plant. Ammonia gas is introduced into the waste acid to react sulfuric acid for generating ammonium sulfate; then, carbolic oil is used for extracting organic substances in the neutralization liquor of the waste acid; through separation, the mother liquor of the ammonium sulfate, which can be used for producing the ammonium sulfate, is obtained; through circular use to reach saturation, the carbolic oil can be directly used as products for sales. The waste acid treatment method of the present invention has the advantages of simple technology, thorough purification, no secondary pollutant generation, low treatment cost, and easy popularization and implementation; the problem of environmental pollution is thoroughly solved; in addition, all products can be regenerated and utilized after purification.
Description
Technical field
The present invention relates to a kind of recycling of sulfuric acid waste, specifically relate to a kind of coke-oven plant commercial benzene workshop section and produce the recovering waste acid utilization.
Background technology
Mainly adopt sulfuric acid scrubbing and two kinds of processing methodes of hydrogenation with the industrial benzene of coking-light benzene processing.Need invest more than 200,000,000 yuan owing to build the benzene hydrogenation process unit of 50,000 tons in a cover, investment cost is huge, and the coke-oven plant of China and other developing country also generally adopts the working method of sulfuric acid scrubbing as coking-light benzene at present.
In the sulfuric acid scrubbing process of coking-light benzene, can produce a large amount of spent acid solutions, its outward appearance is chocolate, and general sulfur acid about 30～60% also contains organism such as some oligomeric acid tar, phenolic compound in addition.Because spent acid solution contains organism, belongs to strong acid again, directly discharging can cause serious environmental to pollute, and need carry out purifying treatment.
Treatment process the earliest is to be directly used in spent acid solution in the production of sulphur ammonium as raw material, but use undressed spent acid as raw material, bring certain difficulty can for the production and the operation of sulphur ammonium, influence the quality of ammonium sulfate products, make that sulphur crystalline ammonium particle diminishes, darkens, organic impurity content is higher, sulphur ammonium saturated solution is non-crystallizable when more serious.Therefore, spent acid solution can not directly be used for producing the sulphur ammonium more now.
Treatment process commonly used at present both at home and abroad is that employing extraction process or absorption method are removed the organism in the spent acid, uses thereby be treated to regenerating acid.But reasons such as owing to be difficult to select a kind of efficient, nontoxic, inexpensive, extraction agent that the source is wide, and sorbent material costs an arm and a leg, and the regeneration activating difficulty is big make these two kinds of methods lack industrial economic benefit, are difficult to promotion and implementation.Extract simultaneously or adsorb the organism that and still exist and cause environmental pollution and insurmountable problem.
Chinese patent CN1113214A has introduced a kind of treatment process of reclaimed acid from coking plant, is to come organism in the oxidation regeneration acid by the strong oxidizing property of hydrogen peroxide, thereby reduces the colourity of regenerating acid, reaches the purpose of purification.Yet through overtesting, find that the decontamination effect improving of this method is still undesirable, also have the organism of more amount in the regenerating acid, recovery utilization rate is not high.
Chinese patent CN1114292A provides a kind of method of utilizing reclaimed acid from coking plant to produce the high purity ferrous sulfate, is to remove most of organism by the mode that feeds water vapor in the regenerating acid waste liquid, adds iron filings again and aquatic product crystalline sulfuric acid is ferrous.Though the organism of this method filtering can be used for coal-blending coking, but in the ferrous sulfate production process, produced new residual impurity again, there is environmental pollution problems equally, consumption that the more important thing is iron filings in this processing method is 2.5 times of theoretical consumption, and the iron filings price is more high again than ferrous sulfate price, make that adopting this processing method to produce ferrous sulfate does not only have economic benefit, also will produce loss, without any practical value and dissemination.
Summary of the invention
The treatment process that the purpose of this invention is to provide a kind of coke-oven plant commercial benzene spent acid uses this method to handle spent acid completely, and the product after the purification all can utilize once more, does not have the secondary pollutant discharging, has thoroughly solved problem of environmental pollution.And this treatment process is simple for process, and the cheap economy of expense is easy to promotion and implementation.
The concrete treatment process of spent acid of the present invention is: the spent acid solution that benzin system process is produced joins in the reactor quantitatively, under continuous condition of stirring, feeds ammonia in reactor, in and the sulfuric acid in the spent acid solution to generate the sulphur ammonium.PH value to solution is 1～3 o'clock stopped reaction, leaves standstill and is cooled to room temperature, obtains the spent acid neutralizer.
The spent acid neutralizer is driven in the extraction tank with pump, according to spent acid: the mass ratio of carbolic oil=1: 3, in extraction tank, add carbolic oil, stirred 10 minutes, standing demix obtains ammonium sulfate liquor and carbolic oil respectively after the separation.
Employed carbolic oil is a coal tar at 200～280 ℃ cut in the treating processes, 200～210 ℃ of products of distillation intercepting after the washing dephenolize.Its quality index is: quantity of distillate 〉=45% before naphthalene≤30%, water≤2%, 200 ℃.
The COD value of the ammonium sulfate liquor that obtains after the carbolic oil extraction is by 100,000 mg/L of original spent acid neutralizer, 20,000 mg/L have been reduced to, be lower than the index request of the desired ammonium sulfate liquor COD of Chemical Manufacture value 2.5 ten thousand mg/L, can directly feed sulphur ammonium saturex system and be used to produce the sulphur ammonium.With the ammonium sulfate products that ammonium sulfate liquor of the present invention is produced, crystallisation process is smooth, and crystal grain is bigger, and granularity and whiteness all meet the requirements, the above index of salable product during quality product is up to state standards after tested.
The carbolic oil that obtains after the extraction can also recycle extraction spent acid neutralizer once more, and general 1 ton of carbolic oil can be handled 3～5 tons of spent acid neutralizers, reaches capacity up to extraction, no longer till the layering.Carbolic oil after saturated is as direct distribution.
After spent acid treatment process purifying treatment of the present invention, sulfuric acid in the spent acid is used to produce the sulphur ammonium, organism such as oligomeric acid tar, phenolic compound have been transferred in the carbolic oil, various compositions in the spent acid have all obtained recycling once more, not only without any the discharge contaminate environment, thoroughly solved environmental issue, and the utilization once more of various compositions has also increased benefit for enterprise.Therefore, it is simple to operation that spent acid treatment process of the present invention has technology, can greatly reduce the spent acid processing costs, and less investment, and the advantage of remarkable in economical benefits are easy to utilize, no matter in environmental protection, still all has certain application value economically.
Embodiment
Embodiment one:
Get 3 tons of washing back, refining benzene workshop, coke-oven plant spent acid stostes, its sulfuric acid concentration is 40% (m/m) after tested, in this spent acid solution injecting reactor, under agitation feeds 546Nm
3Ammonia reacts, and after reaction finished, the pH value of measuring the spent acid neutralizer was 2.0, and the COD value is 9.8 ten thousand mg/L.The spent acid neutralizer is driven in the extraction tank with acid proof pump, add after 9 tons of carbolic oil fully mix 10 minutes, leave standstill and make its layering, the ammonium sulfate liquor COD value of lower floor's water is reduced to 1.8 ten thousand mg/L, directly feeding sulphur ammonium is produced in the saturex system and is used to produce the sulphur ammonium, and the carbolic oil on upper strata is collected standby.
Embodiment two:
Get 3 tons of spent acid stostes, its sulfuric acid concentration is 42% (m/m) after tested, is injected in the reactor, stirs to feed 570Nm down
3Ammonia fully reacts, and the pH value that finishes to measure the spent acid neutralizer in the back is 2.5, and the COD value is 10.0 ten thousand mg/L.The spent acid neutralizer is driven in the extraction tank, continues to extract and standing demix with carbolic oil among the embodiment one, the COD value of lower floor's ammonium sulfate liquor is reduced to 2.0 ten thousand mg/L, is used to produce the sulphur ammonium, and the carbolic oil on upper strata continues to collect standby.
Embodiment three:
Get 3 tons of spent acid stostes, record sulfur acid 39% (m/m), be injected in the reactor, stir and feed 534Nm down
3It is 1.8 that ammonia, reaction finish back mensuration system pH, and the COD value is 9.6 ten thousand mg/L.The spent acid neutralizer is squeezed in the extraction tank, continue to extract with carbolic oil among the embodiment two, behind the standing demix, the COD value of lower floor's ammonium sulfate liquor is reduced to 1.9 ten thousand mg/L after tested, feed in the sulphur ammonium saturex and produce the sulphur ammonium, carbolic oil continues on for extracting the spent acid neutralizer, till layering no longer, as production marketing.
Claims (5)
1, coke-oven plant's commercial benzene spent acid treatment process is characterized in that feeding ammonia in spent acid, reaction obtains the spent acid neutralizer; According to the spent acid neutralizer: the mass ratio of carbolic oil=1: 3 adds carbolic oil and stirs extraction in the spent acid neutralizer, separate obtaining ammonium sulfate liquor and carbolic oil behind the standing demix;
Use therein carbolic oil is a coal tar at cut 200～210 ℃ of products of distillation intercepting after the washing dephenolize of 200～280 ℃.
2, coke-oven plant according to claim 1 commercial benzene spent acid treatment process is characterized in that the spent acid neutralizer pH value that obtains is 1～3.
3, coke-oven plant according to claim 1 commercial benzene spent acid treatment process, it is characterized in that separating the carbolic oil that obtains can recycle, and carbolic oil per ton can be handled 3～5 tons of spent acid neutralizers.
4, coke-oven plant according to claim 1 commercial benzene spent acid treatment process is characterized in that separating the ammonium sulfate liquor that obtains and feeds the sulphur ammonium and produce the saturex system and be used to produce the sulphur ammonium.
5,, it is characterized in that handling carbolic oil behind the spent acid neutralizer as direct distribution according to claim 1,3 described coke-oven plant commercial benzene spent acid treatment processs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101096060A CN1294087C (en) | 2003-10-08 | 2003-10-08 | Method for treating waste acid from refining benzene for coking plant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101096060A CN1294087C (en) | 2003-10-08 | 2003-10-08 | Method for treating waste acid from refining benzene for coking plant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1528678A CN1528678A (en) | 2004-09-15 |
| CN1294087C true CN1294087C (en) | 2007-01-10 |
Family
ID=34304645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101096060A Expired - Fee Related CN1294087C (en) | 2003-10-08 | 2003-10-08 | Method for treating waste acid from refining benzene for coking plant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1294087C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979629B (en) * | 2014-05-29 | 2015-10-21 | 济钢集团有限公司 | A kind of retrieving arrangement doctor solution being carried to gained clear liquid after salt |
| CN109516626A (en) * | 2018-12-18 | 2019-03-26 | 山东世纪阳光科技有限公司 | A kind of processing method of CLT acid waste acid water |
| CN111888831A (en) * | 2020-06-24 | 2020-11-06 | 刘发业 | Waste sulfuric acid recovery processing device and application thereof |
| CN116101983B (en) * | 2023-03-13 | 2024-04-23 | 江苏庆峰工程集团有限公司 | Process and device for recycling industrial waste sulfuric acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1009547B (en) * | 1987-05-06 | 1990-09-12 | 黄卓林 | Recovery technique of iron oxide red and ammonia sulphate from waste liquid of pickle |
| CN1114292A (en) * | 1994-06-30 | 1996-01-03 | 本溪钢铁公司 | Process for producing high-pure ferrous sulfate using reclaimed acid from coking plant |
| CN1036129C (en) * | 1994-06-06 | 1997-10-15 | 李静怡 | Method for purifying and treating regenerated acid of coking plant |
-
2003
- 2003-10-08 CN CNB2003101096060A patent/CN1294087C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1009547B (en) * | 1987-05-06 | 1990-09-12 | 黄卓林 | Recovery technique of iron oxide red and ammonia sulphate from waste liquid of pickle |
| CN1036129C (en) * | 1994-06-06 | 1997-10-15 | 李静怡 | Method for purifying and treating regenerated acid of coking plant |
| CN1114292A (en) * | 1994-06-30 | 1996-01-03 | 本溪钢铁公司 | Process for producing high-pure ferrous sulfate using reclaimed acid from coking plant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1528678A (en) | 2004-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1318387C (en) | Cleaning production process of extracting L-isoleucine from fermented liquor using ion-exchange | |
| CN108128826B (en) | Nitric acid-containing wastewater treatment device and treatment method | |
| CN1940098A (en) | Gray manganese ore leaching out process | |
| CN101648864B (en) | Purification method of citric acid fermentation broth | |
| CN102267769A (en) | Vacuum potassium carbonate method for utilizing coke oven coal gas desulphurization and decyanation waste liquid as resource | |
| CN1986390A (en) | Process of purifying and recovering waste sulfuric acid containing organic impurity | |
| CN105502551A (en) | Technology for recycling lithium from industrial wastewater | |
| CN1884144A (en) | Method for treating waste water in production of para-hydroxyphenyl hydantoin | |
| CN1294087C (en) | Method for treating waste acid from refining benzene for coking plant | |
| CN100494081C (en) | Recovering handling method for amino C acid wastewater | |
| CN113461284A (en) | Municipal sludge treatment method for nitrate-enhanced pyrohydrolysis | |
| CN103014338A (en) | Method for processing poor organic phase after solvent extraction indium extracting | |
| CN113354024A (en) | Method for preparing nickel nitrate by using electroplating wastewater | |
| CN102351270A (en) | Oil dephenolizing extractant in brown coal tar, and preparation method and application thereof | |
| CN100532261C (en) | Process for preparing solid potassium ferrate | |
| CN1654317A (en) | Purified wet-process technique for producing phosphoric acid and equipment thereof | |
| CN102602890A (en) | Method and device for recycling useful substances from waste hydrochloric acid liquor | |
| CN115069313A (en) | Ion exchange column desorption regeneration process | |
| CN1861525A (en) | Treatment process of active hargil waste acid | |
| CN214830137U (en) | Low-quality transformer oil recycling system | |
| CN1752032B (en) | Treatment and recovery technology for mixed acid from industrial waste water 3,3-dichlorobenzidine hydrochloride | |
| CN102701513B (en) | New process for wastewater recycling comprehensive treatment in alga processing | |
| CN111410212A (en) | Method for recycling sulfuric acid production wastewater | |
| CN100346858C (en) | Separation method of bergmeal and rolling oil | |
| CN1113214A (en) | Method for purifying and treating regenerated acid of coking plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |