CN104876190A - Oxygen-enriched combustion-supporting waste acid cracking process - Google Patents
Oxygen-enriched combustion-supporting waste acid cracking process Download PDFInfo
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- CN104876190A CN104876190A CN201510185566.0A CN201510185566A CN104876190A CN 104876190 A CN104876190 A CN 104876190A CN 201510185566 A CN201510185566 A CN 201510185566A CN 104876190 A CN104876190 A CN 104876190A
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- oxygen
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- spent acid
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Abstract
The invention provides an oxygen-enriched combustion-supporting waste acid cracking process and belongs to the technical field of environmental protection. Oxygen-enriched air having the oxygen concentration of more than 25% (volume) is produced by an oxygen enrichment apparatus and directly supplied to a combustor; the combustor is arranged in a cracking furnace for combustion, and high-temperature smoke generated by combustion is used for waste acid cracking; meanwhile, a weak oxygen atmosphere is mainly kept in the cracking furnace, and the cracked smoke is discharged out of the furnace and cooled before going into an acid production system for producing thickened sulfuric acid. The oxygen-enriched combustion-supporting waste acid cracking process is characterized in that the combustion condition is partially improved by use of oxygen-enriched air so that the combustion efficiency of a fuel can be guaranteed, and meanwhile, the weak oxygen atmosphere needed by cracking is not broken; as a result, the system safety is improved.
Description
Technical field
The invention belongs to environmental protection technical field, be applicable to the recycle of alkylation spent acid, be specifically related to a kind of spent acid cracking technology of oxygen-enriched combustion-supporting.
Background technology
At present, in domestic alkylation oil refining production process, a large amount of waste sulfate is produced.This not only causes a large amount of wastes in resource, also the huge destruction to environment structure.
Substantially have two kinds of technology to the process of this kind of alkylation spent acid both at home and abroad, one is dry method relieving haperacidity, and another kind is wet method relieving haperacidity.Domesticly be partial to dry method relieving haperacidity, the method is simple and reliable.External then be partial to wet method relieving haperacidity, the method thermal utilization is abundant.
Technology related to the present invention has:
1. domestic technique
The method of 1.1 200910212787 preparing high concentration sulfuric acid by cracking low concentration sulfuric acids.The invention belongs to waste ' s reclamation chemical technology field, relate to the method to produce high-concentration sulfuric acid containing low-concentration sulfuric acid mixture cracking process.Be greater than the sulfuric acid mixture of 80% for raw material with sulfur acid concentration expressed in percentage by weight, produced the method for high-concentration sulfuric acid by cracking process, namely utilize thermal source, as Sweet natural gas, coal gas or coal mine gas and air combustion carry out the vitriolated mixture of heating pyrolyze, through cracking, obtain mainly containing SO
2, SO
3, CO
2with the high-temperature furnace gas of water vapour, this gas is through waste heat recovery, closed acid-scrubbing cleaning cool-down dehumidification, furnace-heated, employing double conversion and double absorption explained hereafter technical grade sulfuric acid.
1.2 CN 1751984 A treatment technology of producing sulfuric acid from alkylated spent sulfuric acid through high temperature decomposition.The present invention relates to Waste Sulfuric Acid Pintsch process, adiabatic humidification acid-scrubbing cleaning, double conversion and double absorption technique, i.e. treatment technology of producing sulfuric acid from alkylated spent sulfuric acid through high temperature decomposition, divide spent acid cracking purification section, conversion section, dry absorption section three part, by spent acid treatment process, make Waste Sulfuric Acid cracking under 1000 ~ 1100 DEG C of high temperature, through acid-scrubbing cleaning, twice contact process transforms and twice absorption, produce qualified sulfuric acid product, reuse for alkyl plant, reach the object of protection of the environment simultaneously, the raw material that this technological process uses is the waste sulfuric acid from alkylation of single 85 ~ 90%, the Waste Sulfuric Acid rate of recovery can reach 90%.
2. foreign technology
English Patent GB596386 only introduces and acid mistization is sprayed into process furnace acid mist again, then carries out thermolysis process to Waste Sulfuric Acid, does not introduce next step technique in detail.US Patent No. 1995-544046 introduces Waste Sulfuric Acid regeneration first can resolve into each component in stove, then reclaims sulfurous gas, is become by oxidizing sulfur dioxide sulphur trioxide, sulphur trioxide aquation to form sulfuric acid.Decomposition step: the biosolids (water containing < 85%) of dehydration is reached desired state to strengthen biosolids decomposition at high temperature and burning, the biosolids of Waste Sulfuric Acid, oxygen-rich air, the state that meets the requirements and fuel are imported in stove, temperature maintains Horeg2000 °F, control the amount of sulfuric acid, biosolids, fuel and air, realize the burning completely of decomposition and the biosolids completely of Waste Sulfuric Acid.Above-mentioned process introduction be make biosolids material obtain in spent acid pyrolyzer burn technological process.US Patent No. 1994-228238 introduces and reclaims containing SO from sulfur waste treatment unit
2gas, by this gas and containing H
2s gas is sent in the thermal reactor of Cross unit together, at least partly containing SO
2gas and oxygen-enriched gas mixtures react, and what finally reclaim from device is sulphur product.Russia's " Zhurnal Prikladnoi Khimii " magazine, useless H in quartz sand fluidized-bed when number of the edition ISSN0044-4618 introduces temperature 700-800 °
2sO
4in thermal decomposition process, the not solidifying resolvent of the formation of gas is verified is SO
2, CO
2and CO.The useless H that Japanese Patent introduction is produced by alkylation
2sO
4by with oxygen-containing gas and oxidizer (such as liquid S and/or H
2s) thermolysis is carried out in burning together, produces containing H
2sO
3gas, a part for this gas recycles together with oxygen-containing gas.The high-concentration oxygen concentration obtained by adsorbing a separation is 50-100% (volume).Japanese Patent JP61251502 describes at 1140 DEG C, and gauge pressure is 0.5kg/cm
2under condition, by air, (volumn concentration is H
2s 91.8, CH
43.8 and H
2o 4.4) flame waste sulfuric acid from alkylation (H
2sO
488%, oil 7.3%, water 4.5% and SO
20.2%), containing CO
25.4% (body), SO
221.5% (body), SO
3150ppm, O
2nothing, balance N
2(with butt) and dust 1mg/m
3generation gas by Cross unit, reclaim S.US Patent No. 3773917 describes containing water and polymeric hydrocarbon in spent acid, it and from H
2sO
4(it is containing the H of lower concentration for recovery process spent acid
2sO
4with the hydrocarbon of high density) mix.This mixture burns in acid sludge conversion system, does not add more fuel, generates SO
2, then its accelerated oxidation is become SO
3.
After internal method only discusses sulfuric acid at high temperature cracking, for producing high-concentration sulfuric acid.To how can all not describe by Thorough combustion.
Foreign technology refer to oxygen enrichment technology, but its air is all oxygen enrichment, and this can destroy the weak oxygen atmosphere required for cracking.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of spent acid cracking technology of oxygen-enriched combustion-supporting, not only environmental protection but also there is economic worth.
The present invention mainly utilizes the oxygen level increasing flame kernel, minor betterment combustion conditions, ensures the efficiency of combustion of fuel, does not destroy again the weak oxygen atmosphere required for cracking simultaneously.
Technical problem to be solved by this invention realizes by the following technical solutions:
A kind of spent acid cracking technology of oxygen-enriched combustion-supporting, it is characterized in that: low-purity oxygen plant obtains the oxygen-rich air of more than oxygen concentration 25% (volume), direct supplied burner, burner burns in pyrolyzer, and the high-temperature flue gas that burning produces is used for spent acid cracking; Simultaneously keep weak oxygen atmosphere in pyrolyzer, the flue gas after cracking is come out of the stove and after cooling, is entered acid making system produce the vitriol oil.
Pass into fuel gas, normal air and oxygen-rich air in described burner, oxygen-rich air amount is enter air total amount 1% ~ 5% simultaneously.
Described oxygen-rich air supplements the flame kernel entering burner, and combustion-supporting scope is at flame kernel.
Described weak oxygen atmosphere keeps oxygen concentration content in kiln gas to be no more than 6% (volume).
Flue gas after described cracking enters the concentration > 92% (quality) that acid making system produces the vitriol oil.
A spent acid cracking apparatus for oxygen-enriched combustion-supporting, is characterized in that: comprise pyrolyzer, and the side of described pyrolyzer is provided with burner and spent acid spray gun, and the opposite side of described pyrolyzer is exhanst gas outlet, and exhanst gas outlet connects heat sink and acid making system successively; Described burner is provided with fuel gas entrance, normal air entrance and oxygen-enriched inlet simultaneously, described fuel gas and normal air pass into from outer tube, described oxygen-rich air passes into from interior pipe, and described interior pipe inserts in outer tube, and the center of flame is directly led in the outlet of interior pipe.
In pyrolyzer, Control for Oxygen Content is below 6%, and Control for Kiln Temperature is more than 1000 DEG C.
Pyrolyzer high-temperature flue gas out enters acid making system after cooling, produces the vitriol oil, sulfuric acid concentration > 92%, the tail gas SO of emptying
2emission concentration < 140ppm.
Common spent acid cracking is incomplete due to fuel combustion, brings problem such as knot carbon, sublimed sulphur etc., serious in generating CO, even sets off an explosion at acid making system.The present invention does not only affect lysis efficiency, also can increase substantially efficiency of combustion, thus the economic benefit brought is obviously; And improve the security of system.
The invention has the beneficial effects as follows:
The spent acid cracking technology of oxygen-enriched combustion-supporting provided by the invention, utilizes oxygen-rich air minor betterment combustion conditions, ensures the efficiency of combustion of fuel, does not destroy again the weak oxygen atmosphere required for cracking simultaneously, improves the security of system.
Accompanying drawing explanation
Fig. 1 is equipment schematic diagram of the present invention.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiments and the drawings, set forth the present invention further, but following embodiment being only the preferred embodiments of the present invention, and not all.Based on the embodiment in embodiment, those skilled in the art under the prerequisite not making creative work obtain other embodiment, all belong to protection scope of the present invention.
As shown in Figure 1, the spent acid cracking apparatus of oxygen-enriched combustion-supporting, comprises pyrolyzer 3, and the side of pyrolyzer 3 is provided with burner 1 and spent acid spray gun 2, and the opposite side of pyrolyzer 3 is exhanst gas outlet 6, and exhanst gas outlet 6 connects heat sink 4 and acid making system 5 successively; Burner 1 is provided with fuel gas entrance, normal air entrance and oxygen-enriched inlet simultaneously, and fuel gas and normal air pass into from outer tube, and oxygen-rich air passes into from interior pipe, and interior pipe inserts in outer tube, and the center of flame is directly led in the outlet of interior pipe.
For the alkylation spent acid cracker of 20,000 tons/year of scales.Oxygen concn be the oxygen-rich air of more than 25% through burner, enter the flame kernel of fuel combustion, facilitate the burning of fuel greatly.Control pyrolyzer outlet oxygen level below 6% by oxygen table, what control entirety adds air capacity, thus controls the weak oxygen atmosphere in stove simultaneously.Spent acid sprays in stove by spent acid spray gun, under the condition of 1000 ~ 1100 DEG C, carry out cracking; The high-temperature flue gas going out pyrolyzer is lowered the temperature through heat sink, simultaneously per hour can byproduct steam 2.5 tons; Flue gas after cooling enters acid making system, often produces 1.8 ten thousand tons, the sulfuric acid of more than 98% concentration per year.Whole system produces without waste residue, the equal qualified discharge of waste water, waste gas.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets is only preference of the present invention; be not used for limiting the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (6)
1. the spent acid cracking technology of an oxygen-enriched combustion-supporting, it is characterized in that: low-purity oxygen plant obtains the oxygen-rich air of more than oxygen concentration 25% (volume), direct supplied burner, burner burns in pyrolyzer, and the high-temperature flue gas that burning produces is used for spent acid cracking; Simultaneously keep weak oxygen atmosphere in pyrolyzer, the flue gas after cracking is come out of the stove and after cooling, is entered acid making system produce the vitriol oil.
2. the spent acid cracking technology of oxygen-enriched combustion-supporting according to claim 1, is characterized in that: pass into fuel gas, normal air and oxygen-rich air in described burner, oxygen-rich air amount is enter air total amount 1% ~ 5% simultaneously.
3. the spent acid cracking technology of oxygen-enriched combustion-supporting according to claim 2, it is characterized in that: described oxygen-rich air supplements the flame kernel entering burner, combustion-supporting scope is at flame kernel.
4. the spent acid cracking technology of oxygen-enriched combustion-supporting according to claim 1, is characterized in that: described weak oxygen atmosphere keeps oxygen concentration content in kiln gas to be no more than 6% (volume).
5. the spent acid cracking technology of oxygen-enriched combustion-supporting according to claim 1, is characterized in that: the flue gas after described cracking enters the concentration > 92% (quality) that acid making system produces the vitriol oil.
6. a spent acid cracking apparatus for oxygen-enriched combustion-supporting, is characterized in that: comprise pyrolyzer, and the side of described pyrolyzer is provided with burner and spent acid spray gun, and the opposite side of described pyrolyzer is exhanst gas outlet, and exhanst gas outlet connects heat sink and acid making system successively; Described burner is provided with fuel gas entrance, normal air entrance and oxygen-enriched inlet simultaneously, and described fuel gas and normal air pass into from outer tube, and described oxygen-rich air passes into from interior pipe, and described interior pipe inserts in outer tube.
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| CN201510185566.0A CN104876190A (en) | 2015-04-17 | 2015-04-17 | Oxygen-enriched combustion-supporting waste acid cracking process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629631A (en) * | 2017-01-03 | 2017-05-10 | 扬州嘉明环保科技有限公司 | Oxygen-enriched combustion-assistance waste sulfuric acid lytic system and technology |
| CN109647294A (en) * | 2019-01-21 | 2019-04-19 | 湛江中冠石油化工有限公司 | A kind of quantitative feeding device of waste acid treatment pyrolysis furnace |
| CN113237065A (en) * | 2021-01-13 | 2021-08-10 | 姚燕 | Intelligent control waste acid cracking furnace and waste sulfuric acid cracking process |
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| CN201647995U (en) * | 2010-02-26 | 2010-11-24 | 中国石油化工集团公司 | Cracking furnace of production device for preparing concentrated sulfuric acid by cracking waste sulfuric acid |
| CN102175038A (en) * | 2011-03-17 | 2011-09-07 | 北京沃克能源科技有限公司 | Rich oxygen or pure oxygen supply high-temperature air combustion system |
| CN102320579A (en) * | 2011-07-01 | 2012-01-18 | 上海科洋科技发展有限公司 | Technical method for preparing sulfuric acid from hydrogen sulfide |
| CN204151068U (en) * | 2014-09-18 | 2015-02-11 | 中石化南京工程有限公司 | A kind of waste sulfuric acid from alkylation process sulphur new device |
-
2015
- 2015-04-17 CN CN201510185566.0A patent/CN104876190A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201647995U (en) * | 2010-02-26 | 2010-11-24 | 中国石油化工集团公司 | Cracking furnace of production device for preparing concentrated sulfuric acid by cracking waste sulfuric acid |
| CN102175038A (en) * | 2011-03-17 | 2011-09-07 | 北京沃克能源科技有限公司 | Rich oxygen or pure oxygen supply high-temperature air combustion system |
| CN102320579A (en) * | 2011-07-01 | 2012-01-18 | 上海科洋科技发展有限公司 | Technical method for preparing sulfuric acid from hydrogen sulfide |
| CN204151068U (en) * | 2014-09-18 | 2015-02-11 | 中石化南京工程有限公司 | A kind of waste sulfuric acid from alkylation process sulphur new device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629631A (en) * | 2017-01-03 | 2017-05-10 | 扬州嘉明环保科技有限公司 | Oxygen-enriched combustion-assistance waste sulfuric acid lytic system and technology |
| CN106629631B (en) * | 2017-01-03 | 2019-01-22 | 扬州嘉明环保科技有限公司 | A kind of the sulfur waste cleavage systems and technique of oxygen-enriched combustion-supporting |
| CN109647294A (en) * | 2019-01-21 | 2019-04-19 | 湛江中冠石油化工有限公司 | A kind of quantitative feeding device of waste acid treatment pyrolysis furnace |
| CN113237065A (en) * | 2021-01-13 | 2021-08-10 | 姚燕 | Intelligent control waste acid cracking furnace and waste sulfuric acid cracking process |
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Application publication date: 20150902 |