CN109694043A - A kind of method that Waste Sulfuric Acid integrated treatment recycles - Google Patents
A kind of method that Waste Sulfuric Acid integrated treatment recycles Download PDFInfo
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- CN109694043A CN109694043A CN201811606246.8A CN201811606246A CN109694043A CN 109694043 A CN109694043 A CN 109694043A CN 201811606246 A CN201811606246 A CN 201811606246A CN 109694043 A CN109694043 A CN 109694043A
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- sulfuric acid
- waste sulfuric
- recycles
- integrated treatment
- reduced pressure
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000011282 treatment Methods 0.000 title claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 239000005416 organic matter Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000000066 reactive distillation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000005562 Glyphosate Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 2
- 229940097068 glyphosate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229940057306 hemihydrate calcium sulfate Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/905—Removal of organic impurities
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods that Waste Sulfuric Acid integrated treatment recycles, and the method is the following steps are included: hydrolysis: the Waste Sulfuric Acid that mass fraction is 70%~85% being hydrolyzed with water and is reacted；Level-one steam stripping at reduced pressure: being delivered to stripper for the sulfuric acid mixture liquid after hydrolysis in step (a) and strip, and removes organic matter and partial moisture；Second depressurized concentration: the sulfuric acid mixture liquid after stripping in step (b) is delivered in decompressor and is concentrated under reduced pressure；Oxidative decoloration: being added oxidant in the sulfuric acid mixture liquid after step (c) reduced pressure or activated carbon adsorption removes remaining organic impurities and decoloration, is disposed up to black sulfuric acid；The present invention is successively arranged level-one steam stripping at reduced pressure, second depressurized concentration and oxidative decoloration step, can be fully by the volatile organic matter and soluble organic impurities in Waste Sulfuric Acid, and does not need to be heated at high temperature, and greatly reduces energy consumption when recycling.
Description
Technical field
The present invention relates to technical field of environmental protection in chemical industry, recycle more particularly to a kind of Waste Sulfuric Acid integrated treatment
Method.
Background technique
The subsequent purification processing use of the recycling of byproduct chloromethanes and chloromethanes synthesis in glyphosate production at present
It is all concentrated sulfuric acid drying process, concentrated sulfuric acid drying process production process includes washing, alkali cleaning, is dehydrated, compresses and liquefies several processes,
Wherein dehydration procedure needs to consume a large amount of concentrated sulfuric acid, and to become concentration after lower and containing large amount of organic for the concentrated sulfuric acid
Waste Sulfuric Acid.One ton of qualified chloromethanes of every production can generate about 100~300kg when wherein glyphosate production byproduct chloromethane recycles
Waste Sulfuric Acid, one ton of chloromethanes of chloromethanes cleaning up can generate about 50~100kg Waste Sulfuric Acid；Sulfuric acid content is 70 in the Waste Sulfuric Acid
~85%, COD are 5~25%, are had compared with penetrating odor, appearance is in pale yellow or brown, and processing difficulty is larger.From documents and materials
It sees, currently, there are three types of the main processing approach of Waste Sulfuric Acid: first is that directly being utilized during producing other products, such as productionization
Fertile general calcium etc.；Second is that such as producing hemihydrate calcium sulfate crystal whisker using neutralisation treatments such as lime；Third is that producing three oxygen by Pintsch process
Change sulphur；Above-mentioned approach carries out Sulphur ressource and recycles, and all there is a problem of that energy consumption is larger.And as country supervises harmful influence
The increase of dynamics, and the enhancing to Hazardous Wastes Management dynamics, a large amount of Waste Sulfuric Acids that enterprise generates directly send the peace of processing outside
Full hidden danger will be constantly amplified, if processing links go wrong, certainly will be will affect enterprise and normally be produced, so Waste Sulfuric Acid is controlled
Reason seriously restricts the development of chemical company；In order to fundamentally solve the problem of outlet of Waste Sulfuric Acid, eliminate safe hidden trouble, it is domestic
The integrated treatment research work of a large amount of Waste Sulfuric Acid is carried out.
Patent CN201210398498 discloses the cleaning treatment system and method for a kind of Waste Sulfuric Acid, and this method is to pass through heat
Air blows out whole Analysis of Volatile Organic Impurity in Waste Sulfuric Acid, most of soluble organic impurities, some oligomers.Illustrate this
The volatile material of method blowout being dissolved in sulfuric acid, not can solve and has been formed by after chemically reacting with sulfuric acid
Machine impurity；Patent CN102897721A discloses a kind of method of dilute sulfuric acid concentration, and this method temperature in economizer bank reaches 338
DEG C, and subsequent technique temperature is both needed to control at 300 DEG C, it is higher to temperature and equipment requirement, while the patent is not gone explicitly
Except the technique of large amount of organic in Waste Sulfuric Acid.
Summary of the invention
The targeted Waste Sulfuric Acid of the present invention is generated by-product in chloromethanes recycling or purification process, sulphur in Waste Sulfuric Acid
Acid mass fraction is 70%~85%, and content of organics is 50000~250000mg/l；The organic matter include 0.1%~
The first of the methanol of 5.0wt%, the dimethyl ether of 0.1%~12wt%, the chloromethanes of 0.1%~5.0wt%, 0.1%~5.0wt%
Acetal, 0.1%~2.0wt% one methyl esters of sulfuric acid/dimethyl suflfate in it is several.
The purpose of the present invention is to solve the above the deficiencies in the prior art, propose a kind of Waste Sulfuric Acid integrated treatment recycling
The method utilized, the method the following steps are included:
(a) hydrolysis: the Waste Sulfuric Acid that mass fraction is 70%~85% is hydrolyzed with water and is reacted；
(b) level-one steam stripping at reduced pressure: being delivered to stripper for the sulfuric acid mixture liquid after hydrolysis in step (a) and strip, and takes off
Except organic matter and partial moisture；
(c) second depressurized is concentrated: the sulfuric acid mixture liquid after stripping in step (b) being delivered in decompressor and is depressurized
Concentration；
(d) oxidative decoloration: oxidant is added in the sulfuric acid mixture liquid after step (c) reduced pressure or activated carbon adsorption removes
Remaining organic impurities and decoloration are gone, is disposed up to black sulfuric acid.
Preferably, control hydrolysising reacting temperature is 80~135 DEG C in the step (a), hydrolysis time is 0.5~
The mass ratio of 5h, Waste Sulfuric Acid and water is 1:0.5~2.0.
Preferably, control reaction temperature is 50~100 DEG C in the step (d), and oxidation time is 1~3h.
Preferably, the level-one steam stripping at reduced pressure temperature is 100~240 DEG C, and control level-one throttled steam strips vacuum degree
For -0.1MPa~-0.01MPa.
Preferably, the second depressurized striking point temperature be 180~240 DEG C, control decompressor vacuum degree be-
0.1MPa~-0.085MPa.
Preferably, stripping mode is dry drum bubble stripping or the tower stripping of reactive distillation in the step (b).
Preferably, the oxidant is hydrogen peroxide, and the mass fraction of the hydrogen peroxide is 30%, the use of hydrogen peroxide
Amount is the 0.5%~2% of sulfuric acid mixture liquid quality.
Preferably, the active carbon usage amount is the 0.5%~2% of sulfuric acid mixture liquid quality.
Beneficial effects of the present invention are as follows:
(1) present invention be successively arranged hydrolysis, level-one steam stripping at reduced pressure, second depressurized concentration and oxidative decoloration step, hydrolysis can
It is that Waste Sulfuric Acid hydrolyzes it in small organic molecule, such as the application by some hydrolysis of organic matter post-processed that are difficult in Waste Sulfuric Acid
After have the evolution of a large amount of dimethyl ether, then being concentrated by subsequent level-one steam stripping at reduced pressure and second depressurized fully will be in Waste Sulfuric Acid
Volatile organic matter and soluble organic impurities remove, entire step does not need to be heated at high temperature, when greatly reducing recycling
Energy consumption.
(2) black sulfuric acid content is 93% or more, and content of organics is 1000mg/l hereinafter, color is light yellow or colourless
Transparency liquid, 1,2,3 grade recycling sulfuric acid is back to use in chloromethanes level Four drying system, the 4th grade of drying still uses 98%
The fresh concentrated sulfuric acid carry out the quality of chloromethanes and check on, to realize the comprehensive reutilization of sulfuric acid, reduce the acid of pickling enterprise
Wash cost, fully achieve zero-emission, not only realize the recycling of resource and will not generation environment pollution.
(3) black sulfuric acid obtained through present invention process is cleaner, can be used for the life of other sulfate or sulfenyl fertilizer
It produces such as: magnesium sulfate, ammonium sulfate, potassium sulfate, sodium sulphate, ferric sulfate, aluminum sulfate, calcium sulfate, general calcium, to realize Waste Sulfuric Acid
Comprehensive reutilization realizes optimum economic benefit, solves the bottleneck of enterprise's production development, really realizing turns waste into wealth.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, the embodiment
For explaining only the invention, it is not intended to limit the scope of the present invention..
Embodiment 1
Waste Sulfuric Acid and water are heated into hydrolysis by the mass ratio of 1:1 after mixing, 100 DEG C of hydrolysis temperature, hydrolysis time 2h；
Level-one steam stripping at reduced pressure is carried out after having hydrolyzed again, control vacuum degree is -0.085MPa, and stripping temperature is 180 DEG C；Then second level is carried out
It is concentrated under reduced pressure, control vacuum degree is -0.085MPa, and outlet temperature is 230 DEG C, and activity is added after concentration in sulfuric acid solution
Charcoal carries out decolorization, and active carbon usage amount is the 0.5% of sulfuric acid solution, reacts 1h at 60 DEG C, is disposed up to regeneration sulphur
Acid；As follows through analysis result: black sulfuric acid concentration is 95%, content of organics 888mg/l.
Embodiment 2
Waste Sulfuric Acid and water are heated into hydrolysis by the mass ratio of 1:2 after mixing, 80 DEG C of hydrolysis temperature, hydrolysis time 1h；
Level-one steam stripping at reduced pressure is carried out after having hydrolyzed again, control vacuum degree is -0.080MPa, and stripping temperature is 200 DEG C；Then second level is carried out
It is concentrated under reduced pressure, control vacuum degree is -0.085MPa, and outlet temperature is 240 DEG C, and quality is added after concentration in sulfuric acid solution
The hydrogen peroxide that score is 30%, hydrogen peroxide usage amount are the 0.5% of sulfuric acid solution, react 2h at 80 DEG C, are disposed up to again
Raw sulfuric acid；As follows through analysis result: black sulfuric acid concentration is 94.2%, content of organics 612mg/l.
Embodiment 3
Waste Sulfuric Acid and water are heated into hydrolysis by the mass ratio of 1:0.8 after mixing, 120 DEG C of hydrolysis temperature, hydrolysis time
3h；Level-one steam stripping at reduced pressure is carried out after having hydrolyzed again, control vacuum degree is -0.088MPa, and stripping temperature is 150 DEG C；Then it carries out
Second depressurized concentration, control vacuum degree are -0.090MPa, and outlet temperature is 200 DEG C, are added in sulfuric acid solution after concentration
The hydrogen peroxide that mass fraction is 30%, hydrogen peroxide usage amount are the 1% of sulfuric acid solution, react 2h at 90 DEG C, are disposed to obtain the final product
Black sulfuric acid；As follows through analysis result: black sulfuric acid concentration is 93.5%, content of organics 944mg/l.
Embodiment 4
Waste Sulfuric Acid and water are heated into hydrolysis by the mass ratio of 1:0.6 after mixing, 135 DEG C of hydrolysis temperature, hydrolysis time
3h；Level-one steam stripping at reduced pressure is carried out after having hydrolyzed again, control vacuum degree is -0.095MPa, and stripping temperature is 230 DEG C；Then it carries out
Second depressurized concentration, control vacuum degree are -0.095MPa, and outlet temperature is 240 DEG C, are added in sulfuric acid solution after concentration
The hydrogen peroxide that mass fraction is 30%, hydrogen peroxide usage amount are the 1% of sulfuric acid solution, react 3h at 100 DEG C, are disposed to obtain the final product
Black sulfuric acid；As follows through analysis result: black sulfuric acid concentration is 94.3%, content of organics 979mg/l.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method that Waste Sulfuric Acid integrated treatment recycles, which is characterized in that the method the following steps are included:
(a) hydrolysis: the Waste Sulfuric Acid that mass fraction is 70%~85% is hydrolyzed with water and is reacted；
(b) level-one steam stripping at reduced pressure: the sulfuric acid mixture liquid after hydrolysis in step (a) is delivered to stripper and is stripped, removing has
Machine object and partial moisture；
(c) second depressurized is concentrated: the sulfuric acid mixture liquid after stripping in step (b) is delivered in decompressor depressurize it is dense
Contracting；
(d) oxidative decoloration: being added oxidant in the sulfuric acid mixture liquid after step (c) reduced pressure or activated carbon adsorption is removed and remained
Remaining organic impurities and decoloration are disposed up to black sulfuric acid.
2. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that described is useless
Sulfuric acid is generated by-product in chloromethanes recycling or purification process, and sulfuric acid mass fraction is 70%~85% in Waste Sulfuric Acid,
Content of organics is 50000~250000mg/l；The organic matter include the methanol of 0.1%~5.0wt%, 0.1%~
The dimethyl ether of 12wt%, the chloromethanes of 0.1%~5.0wt%, the dimethoxym ethane of 0.1%~5.0wt%, 0.1%~2.0wt%
It is several in one methyl esters of sulfuric acid/dimethyl suflfate.
3. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that the step
Suddenly control hydrolysising reacting temperature is 80~135 DEG C in (a), and hydrolysis time is 0.5~5h.
4. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that the step
Suddenly the mass ratio of Waste Sulfuric Acid and water is 1:0.5~2.0 in (a).
5. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that the step
Suddenly control reaction temperature is 50~100 DEG C in (d), and oxidation time is 1~3h.
6. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that described one
Grade steam stripping at reduced pressure temperature is 100~240 DEG C, and control level-one throttled steam stripping vacuum degree is -0.1MPa~-0.01MPa.
7. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that described two
It is 180~240 DEG C that outlet temperature, which is concentrated under reduced pressure, in grade, and control decompressor vacuum degree is -0.1MPa~-0.085MPa.
8. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that the step
Suddenly stripping mode is dry drum bubble stripping or the tower stripping of reactive distillation in (b).
9. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that the oxygen
Agent is hydrogen peroxide, and the mass fraction of the hydrogen peroxide is 30%, and the usage amount of hydrogen peroxide is sulfuric acid mixture liquid quality
0.5%~2%.
10. the method that a kind of Waste Sulfuric Acid integrated treatment according to claim 1 recycles, which is characterized in that described
Active carbon usage amount is the 0.5%~2% of sulfuric acid mixture liquid quality.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357045A (en) * | 2019-05-24 | 2019-10-22 | 南京鹳山化工科技有限公司 | A kind of method that organosilicon waste acid resource utilizes |
| CN110371933A (en) * | 2019-07-27 | 2019-10-25 | 哈尔滨师范大学 | A kind of method of purification of spent acid |
| CN111214842A (en) * | 2020-02-19 | 2020-06-02 | 宁波巨化化工科技有限公司 | Process and device for removing light components in by-product sulfuric acid |
| CN111517289A (en) * | 2020-06-11 | 2020-08-11 | 常州清立环能化工科技有限公司 | Waste sulfuric acid treatment system and treatment method |
| CN111573629A (en) * | 2020-05-29 | 2020-08-25 | 盛隆资源再生（无锡）有限公司 | Recovery treatment method of sulfuric acid waste acid |
| CN111792627A (en) * | 2020-07-08 | 2020-10-20 | 江西蓝星星火有机硅有限公司 | Method for recovering sulfuric acid waste liquid in chloromethane production process |
| CN112441872A (en) * | 2019-08-31 | 2021-03-05 | 浙江工业大学 | Method for treating waste sulfuric acid generated in industrial production of glyphosate by using glycine method |
| CN113666799A (en) * | 2021-08-30 | 2021-11-19 | 聊城鲁西氯甲烷化工有限公司 | System, process and application for concentrating and regenerating chloromethane byproduct dilute sulfuric acid |
| CN113683478A (en) * | 2021-08-13 | 2021-11-23 | 扬中市润宏高分子材料科技有限公司 | Process for drying water and dimethyl ether by using sulfuric acid without producing dilute sulfuric acid and dimethyl ester |
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| CN113683478A (en) * | 2021-08-13 | 2021-11-23 | 扬中市润宏高分子材料科技有限公司 | Process for drying water and dimethyl ether by using sulfuric acid without producing dilute sulfuric acid and dimethyl ester |
| CN113666799A (en) * | 2021-08-30 | 2021-11-19 | 聊城鲁西氯甲烷化工有限公司 | System, process and application for concentrating and regenerating chloromethane byproduct dilute sulfuric acid |
| CN114314526A (en) * | 2021-12-24 | 2022-04-12 | 山东久日化学科技有限公司 | Method for recovering waste sulfuric acid |
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