CN1986390A - Process of purifying and recovering waste sulfuric acid containing organic impurity - Google Patents
Process of purifying and recovering waste sulfuric acid containing organic impurity Download PDFInfo
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- CN1986390A CN1986390A CN 200610022651 CN200610022651A CN1986390A CN 1986390 A CN1986390 A CN 1986390A CN 200610022651 CN200610022651 CN 200610022651 CN 200610022651 A CN200610022651 A CN 200610022651A CN 1986390 A CN1986390 A CN 1986390A
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Abstract
The process of purifying and recovering waste sulfuric acid containing organic impurity includes the following steps: distilling waste sulfuric acid with water vapor to depolymerize and separate out the organic impurity, extracting waste sulfuric acid with organic solvent to separate out its organic matter, filtering to eliminate solid grains and to obtain deep brown liquid, and adsorbing the deep brown liquid in a multistage adsorption tower for decolorizing to obtain colorless purified sulfuric acid. The treated sulfuric acid is used directly as industrial material or further concentrated for reuse in the production section. The present invention has short technological process, high processing efficiency, low running cost and other advantages.
Description
Technical field
The present invention relates to the sulfur waste acid recovery process, be specifically related to contain the sulfur waste acid purification recovery technology of organic impurity.
Background technology
1.4-butyleneglycol is important fine chemical product, there are many production plants to adopt the Reppe method of Reppe method or improvement at present, need to adopt sulfuric acid that the acetylene gas that calcium carbide produces is handled and purified in this production process route, be beneficial to the reaction of follow-up alkynes aldehyde condensation workshop section, in the process that adopts vitriol oil processing acetylene gas, the sulfuric acid more and more thickness that becomes, at last can not be again with and must change, throughput produces about 3 tons of sulfur waste acid every day at 2.5 ten thousand tons/year device.In anthraquinone is produced, reactant is pressed in the decomposition pot, add the vitriol oil, and steam remaining benzene with water vapour, reactant dilute with water, gained o-benzoylbenzoic acid after filtration, put into dehydration pot after the washing add the vitriol oil or oleum, making its dehydration closed-loop is anthraquinone, and yield is 95% of a theoretical yield.Anthraquinone per ton (folding 100%) consumes (99.7%) 765 kilogram of phthalic anhydride, (98.5%) 1500 kilogram of aluminum chloride, 620 kilograms of purified petroleum benzin (industrial goods), (100%) 765 kilogram in sulfuric acid, therefore to produce a large amount of sulfur waste acid aborning, formed sulfur waste acid colourity is profound, about 30000 mg/L of COD concentration.China produces per year more than phthalocyanine blue 15:0 series product 1.5 ten thousand t, all adopts the molten or sour method technology that rises of acid, by product mean consumption 4-7t sulfuric acid per ton (98%), and the annual spent acid that produces about 100,000 tons.The a large amount of sulfur waste acid that produce in the titanium white production are not as being used; also can cause the waste of resource and to the severe contamination of environment; or the like, formed sulfur waste acid must be handled and reclaim in similar industrial production, is beneficial to the comprehensive utilization of environment protection and resource.
After adopting sulfuric acid that acetylene gas is handled, form the dense thick semi-fluid hydrodynamic body material of black, viscosity is bigger.Acetylene gas is in the process of using vitriolization, because the acetylene gas temperature is higher, produce partially polymerized and oxidizing reaction, acetylene is carried a part of calcium hydroxide secretly after generation simultaneously, these generations and the material of carrying secretly are followed the vitriolic washing process and are entrained by the vitriol oil, thereby because of the enrichment gradually of these materials, it is more and more thicker that sulfuric acid becomes in treating processes, do not cause sulfuric acid treated and can not use again.This acid is more owing to containing impurity, and other purposes of tool if directly discharge, or through the neutralizing treatment discharging, will not cause very big pollution to environment.Therefore, utilizing after the spent acid that processing forms to acetylene must be handled, is to alleviate environmental pollution again, realizes the inevitable requirement of resources circulation comprehensive utilization.Equally, in anthraquinone was produced, because the vitriol oil plays the effect of dewatering agent and oxygenant, the sulfuric acid color darkened because of the coloring matter enrichment that material dewatering produced, and concentration is thinning, must be recycling through the recycling rear.
Chinese patent CN1354127 relates to a kind of sulphuric acid concentration that concentration in carrying out the wafer cleaning process can have been reduced and reaches the sulphuric acid recovery device of the degree of can recycling.This sulphuric acid recovery device can reclaim by sulfuric acid and superoxol and mix sulfuric acid in the prepared wafer scavenging solution.This device comprises reactive tank, and it has at least one suction port and two openings of a relief outlet, and concentrates the sulfuric acid from the wafer cleaning waste liquid of finishing the wafer cleaning process that suction port is introduced, and then the vitriol oil that obtains is discharged from relief outlet.This device also comprises the wafer process groove of processed wafer and the vitriol oil is supplied with the supply equipment of wafer process groove.Chinese patent CN2829862 utilizes industrial gaseous waste to concentrate the dilute sulphuric acid retrieving arrangement, the heat exchange scatterer that it is characterized in that the spent acid circulation groove communicates with it, the heat exchange scatterer has a high-temp waste gas import at left end, the upper right side of heat exchange scatterer communicates with gasifier, has shower to enter heat exchange scatterer and gasifier respectively on the drain pipe of corrosion-resistant circulation submerged pump.But above-mentioned patent all can not solve the organism that is rich in the sulfur waste acid, can not carry out efficient recovery to containing organic sulfur waste acid.
Summary of the invention
Technical problem to be solved by this invention is how a kind of useless vitriolic cleaning and recovering process of organic impurity that contains is provided, mainly provide and recycle adopting sulfuric acid to make the organic gas purification treatment media and adopting sulfuric acid to do the formed sulfur waste acid of reaction medium, the sulfuric acid of Xing Chenging can directly be applied to other industrial production as raw material after treatment, also can carry returning production workshop section after dense and utilizing.It has advantages such as flow process weak point, reduced investment, processing efficiency height, working cost are low, the renewable use repeatedly of sorbent material.
Technical problem proposed by the invention is to solve like this: a kind of useless vitriolic cleaning and recovering process of organic impurity that contains is provided, it is characterized in that, may further comprise the steps:
(1) adopts water vapor that steam distillation is carried out in sulfur waste acid, the organism depolymerization that is mixed in the waste sulfuric acid is distillated;
(2) adopt organic solvent again extraction treatment to be carried out in sulfur waste acid, separate the organism that wherein contains;
(3) feed liquid that above-mentioned steps is obtained is filtered, and removes solid particulate matter wherein, obtains Vandyke brown liquid;
(4) Vandyke brown liquid is sent to absorption workshop section, after the decolouring of multistage adsorption tower continuous adsorption is handled, obtained colourless purification sulfuric acid.
According to the useless vitriolic cleaning and recovering process of organic impurity that contains provided by the present invention, it is characterized in that described sulfur waste acid is from adopting sulfuric acid to do in the technology of gas processing purification medium or adopting sulfuric acid to do in the technology of catalyzer or reaction medium.
According to the useless vitriolic cleaning and recovering process of organic impurity that contains provided by the present invention, it is characterized in that the water vapor that is adopted can be the waste hot steam in factory's general facilities low-pressure steam or the factory.
According to the useless vitriolic cleaning and recovering process of organic impurity that contains provided by the present invention, it is characterized in that the filter type in the described step (3) can be membrane filtration or ceramic filter or centrifuging.
According to the useless vitriolic cleaning and recovering process of organic impurity that contains provided by the present invention, it is characterized in that the progression of described multistage adsorption tower can be 1～5 grade.
According to the useless vitriolic cleaning and recovering process of organic impurity that contains provided by the present invention, it is characterized in that the progression of described multistage adsorption tower is 3 grades.
According to the useless vitriolic cleaning and recovering process of organic impurity that contains provided by the present invention, it is characterized in that the sorbing material that described multistage adsorption tower is adopted can be one or more in gac, silica gel, quartz sand, diatomite, the atlapulgite.
According to the useless vitriolic cleaning and recovering process of organic impurity that contains provided by the present invention, it is characterized in that, after reclaiming gained sulfuric acid and mixing up ratio, can raw material directly as industrial application or propose the application of returning production workshop section after dense.
Compared with the prior art, the present invention has following advantage: 1, technology is flexible, looks recovery back vitriolic purposes and can take different processing technology routines; 2, the steam steam distillation treatment effect of Cai Yonging is good, effectively reduces useless vitriolic viscosity, and low to the steam class requirement; 3, after the steam distillation of carrying out leading portion, filtration treatment, the adsorption medium treatment effect greatly improves, institute's reclaim(ed) sulfuric acid quality better, as have lighter color, foreign matter content low, can directly apply to characteristics such as industrial production.
Embodiment
Be further described below in conjunction with embodiment the present invention.
Target of the present invention is to provide and recycles adopting sulfuric acid to make the organic gas purification treatment media and adopting sulfuric acid to do the formed sulfur waste acid of reaction medium, after treatment the recycling processing technology routine of the sulfuric acid of Xing Chenging.Formed sulfuric acid can directly be applied to other industrial production as raw material, also can carry returning production workshop section after dense and utilizing.
The sulfur waste acid that will form during the present invention will produce, adopt low-pressure steam or factory's waste hot steam to carry out the water vapor steam distillation, carry out depolymerization and distillate being entrained in polymkeric substance in the sulfuric acid waste, also mainly material to be carried out viscosity decreasing thick for this process simultaneously, make it have good flowability, be convenient to next step operation.The material that to handle is again introduced and is filtered workshop section, remove the solid impurity that contains in the waste liquid, the solid impurity that filters out is black solid material (as carbon black, an inorganic salts etc.), liquid after the filtration is Vandyke brown liquid, this liquid is introduced efficient adsorption treatment tower, after multistage adsorption tower continuous adsorption is handled, obtain colourless purified sulphuric acid soln, this sulphuric acid soln is after deployed ratio, can directly apply to production, as produce producers such as ferrous sulfate, also can carry and return production workshop section after dense and utilize again.
This sulfur waste acid recovery process technology is applicable to the producer that adopts sulfuric acid to make the gas processing purification medium, and adopts sulfuric acid to do the producer of catalyzer and reaction medium.The water vapor that is adopted can be factory's general facilities low-pressure steam, also can be the waste hot steam of factory.The filter type that is adopted can be a membrane filtration, also can be ceramic filter, centrifuging etc., adopts different filter types according to different processing requirements, at the present invention, is more preferably employing centrifuging.Adopt the decolouring of multistage adsorption tower, the progression of multistage adsorption tower between 1～5, best progression be 3 wherein the sorbing material that adopts of adsorption tower can be a kind of in the following material: gac, silica gel, quartz sand, diatomite, atlapulgite.
Following example has been enumerated the sulfur waste acid recovery process characteristic of this invention in further detail:
Embodiment one:
Take by weighing black stoste sulfur waste acid 444g, fed low-pressure steam 5 hours, decompose wherein polymkeric substance, cooling is weighed, obtain the 918g mixture, the material after the processing filters, washs through polymeric membrane, obtains filtrate and filter cake respectively, filtrate is handled through the decolouring of 3 grades of filling gel adsorption towers, obtains colourless pure content and be 35.12% sulphuric acid soln; Filter cake oven dry back weighing obtains the 67.4g black solid, and after 3 hours, residue weight is 0.4g 600-650 ℃ of calcination.
Embodiment two:
Take by weighing black stoste 522g, feed low-pressure steam heating 6 hours, decompose the acid of steam distillation sulfur waste and carry organism secretly, cooling is weighed and is obtained the 948g mixture, this mixture is carried out centrifuging, and washing leaching cake, obtain Vandyke brown filtrate and black solid filter cake, filtrate is filled the decolouring of atlapulgite adsorption towers through 3 grades and is handled that to obtain colourless content be 44.17% sulphuric acid soln, filter cake is obtaining solid 90.1g after the oven dry under 100-105 ℃ the temperature, after 5 hours, its residue weight is 0.5g 600-650 ℃ of calcination.
Embodiment three:
With the silica gel of embodiment after absorption, oven dry back weight is 77.1g, under 650 ℃ condition, silica gel is put into the retort furnace calcination after 5 hours, the cooling weighing, and silica gel weight is 65.2g, the silica gel saturated extent of adsorption is 11.9g.Take by weighing the silica gel 45.4g after the calcination, carry out saturated absorption again after, drying claims that its weight is 55.5g again, its saturated extent of adsorption is 10.1g.
Embodiment four:
With the atlapulgite of embodiment two after absorption, oven dry back weight is 59.3g, under 600 ℃ condition, silica gel is put into the retort furnace calcination after 4 hours, the cooling weighing, and silica gel weight is 49.1g, the carclazyte saturated extent of adsorption is 10.2g.Take by weighing the carclazyte 64.7g after the calcination, carry out saturated absorption again after, drying claims that its weight is 81.2g again, its saturated extent of adsorption is 16.5g.
Embodiment five:
With the dilute sulphuric acid among the embodiment one adopt vacuum hydro-extraction carry dense after, obtain about 98% the colourless vitriol oil.
Claims (9)
1. one kind contains the useless vitriolic cleaning and recovering process of organic impurity, it is characterized in that, may further comprise the steps:
(1) adopts water vapor that steam distillation is carried out in sulfur waste acid, the organism depolymerization that is mixed in the waste sulfuric acid is distillated;
(2) adopt organic solvent again extraction treatment to be carried out in sulfur waste acid, separate the organism that wherein contains:
(3) feed liquid that above-mentioned steps is obtained is filtered, and removes solid particulate matter wherein, obtains Vandyke brown liquid;
(4) Vandyke brown liquid is sent to absorption workshop section, after the decolouring of multistage adsorption tower continuous adsorption is handled, obtained colourless purification sulfuric acid.
2. a kind of useless vitriolic cleaning and recovering process of organic impurity that contains according to claim 1 is characterized in that described sulfur waste acid is from adopting sulfuric acid to do in the technology of gas processing purification medium or adopting sulfuric acid to do in the technology of catalyzer or reaction medium.
3. a kind of useless vitriolic cleaning and recovering process of organic impurity that contains according to claim 1 is characterized in that the water vapor that is adopted can be the waste hot steam in factory's general facilities low-pressure steam or the factory.
4. a kind of useless vitriolic cleaning and recovering process of organic impurity that contains according to claim 1 is characterized in that the filter type in the described step (3) can be membrane filtration or ceramic filter or centrifuging.
5. a kind of useless vitriolic cleaning and recovering process of organic impurity that contains according to claim 1 is characterized in that the progression of described multistage adsorption tower can be 1～5 grade.
6. a kind of useless vitriolic cleaning and recovering process of organic impurity that contains according to claim 5 is characterized in that the progression of described multistage adsorption tower is 3 grades.
7. according to claim 1,5,6 arbitrary described a kind of useless vitriolic cleaning and recovering process of organic impurity that contain, it is characterized in that the sorbing material that described multistage adsorption tower is adopted can be one or more in gac, silica gel, quartz sand, diatomite, the atlapulgite.
8. according to the arbitrary described a kind of useless vitriolic cleaning and recovering process of organic impurity that contains of claim 1～6, it is characterized in that, after reclaiming gained sulfuric acid and mixing up ratio, can raw material directly as industrial application or propose the application of returning production workshop section after dense.
9. a kind of useless vitriolic cleaning and recovering process of organic impurity that contains according to claim 7 is characterized in that the sorbing material that described multistage adsorption tower is adopted can be one or more in gac, silica gel, quartz sand, diatomite, the atlapulgite.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610022651 CN1986390A (en) | 2006-12-26 | 2006-12-26 | Process of purifying and recovering waste sulfuric acid containing organic impurity |
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| CN 200610022651 CN1986390A (en) | 2006-12-26 | 2006-12-26 | Process of purifying and recovering waste sulfuric acid containing organic impurity |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786036A (en) * | 2012-08-08 | 2012-11-21 | 刘立文 | Method for discoloring sulfuric acid by using potassium permanganate |
| CN103072954A (en) * | 2013-01-08 | 2013-05-01 | 刘立文 | Method for producing colourless sulphuric acid by utilizing calcium sulfate |
| CN103224222A (en) * | 2013-05-08 | 2013-07-31 | 周长祥 | Apparatus for purifying organic matters in waste sulfuric acid |
| CN103224223A (en) * | 2013-05-10 | 2013-07-31 | 刘立文 | Sulfuric acid decolorant |
| CN103482587A (en) * | 2013-09-17 | 2014-01-01 | 四川泸天化股份有限公司 | Purification recovery process of waste sulfuric acid rich in organic impurity |
| CN104445441A (en) * | 2014-11-14 | 2015-03-25 | 河南省煤气（集团）有限责任公司 | Method for producing polymeric aluminium ferric sulfate solution from industrial waste sulfuric acid generated during purification of acetylene gas and red mud |
| TWI481549B (en) * | 2013-06-04 | 2015-04-21 | Chang Chun Plastics Co Ltd | Method for producing sulfur trioxide from recycled sulfuric acid waste material and apparatus for continuous preparing sulfur trioxide |
| CN104627967A (en) * | 2013-11-13 | 2015-05-20 | 雷永诚 | System and method of normal temperature recovery of waste sulfuric acid |
| CN105731395A (en) * | 2016-05-16 | 2016-07-06 | 瓮福（集团）有限责任公司 | Method for recycling purified contrast agent intermediate waste sulfuric acid |
| CN109721035A (en) * | 2019-03-18 | 2019-05-07 | 南京蓝胜环保科技有限公司 | A kind of purification extracting and concentrating technology of useless dilute sulfuric acid |
| CN111888831A (en) * | 2020-06-24 | 2020-11-06 | 刘发业 | Waste sulfuric acid recovery processing device and application thereof |
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2006
- 2006-12-26 CN CN 200610022651 patent/CN1986390A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786036A (en) * | 2012-08-08 | 2012-11-21 | 刘立文 | Method for discoloring sulfuric acid by using potassium permanganate |
| CN103072954B (en) * | 2013-01-08 | 2016-04-27 | 刘立文 | A kind of method utilizing calcium sulfate to produce colourless sulfuric acid |
| CN103072954A (en) * | 2013-01-08 | 2013-05-01 | 刘立文 | Method for producing colourless sulphuric acid by utilizing calcium sulfate |
| CN103224222A (en) * | 2013-05-08 | 2013-07-31 | 周长祥 | Apparatus for purifying organic matters in waste sulfuric acid |
| CN103224223A (en) * | 2013-05-10 | 2013-07-31 | 刘立文 | Sulfuric acid decolorant |
| CN103224223B (en) * | 2013-05-10 | 2016-02-03 | 刘立文 | A kind of Sulfuric acid decolorant |
| TWI481549B (en) * | 2013-06-04 | 2015-04-21 | Chang Chun Plastics Co Ltd | Method for producing sulfur trioxide from recycled sulfuric acid waste material and apparatus for continuous preparing sulfur trioxide |
| CN103482587A (en) * | 2013-09-17 | 2014-01-01 | 四川泸天化股份有限公司 | Purification recovery process of waste sulfuric acid rich in organic impurity |
| CN104627967A (en) * | 2013-11-13 | 2015-05-20 | 雷永诚 | System and method of normal temperature recovery of waste sulfuric acid |
| CN104445441A (en) * | 2014-11-14 | 2015-03-25 | 河南省煤气（集团）有限责任公司 | Method for producing polymeric aluminium ferric sulfate solution from industrial waste sulfuric acid generated during purification of acetylene gas and red mud |
| CN105731395A (en) * | 2016-05-16 | 2016-07-06 | 瓮福（集团）有限责任公司 | Method for recycling purified contrast agent intermediate waste sulfuric acid |
| CN109721035A (en) * | 2019-03-18 | 2019-05-07 | 南京蓝胜环保科技有限公司 | A kind of purification extracting and concentrating technology of useless dilute sulfuric acid |
| CN111888831A (en) * | 2020-06-24 | 2020-11-06 | 刘发业 | Waste sulfuric acid recovery processing device and application thereof |
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