CN106064835A - Oil refinery waste acid treatment process - Google Patents
Oil refinery waste acid treatment process Download PDFInfo
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- CN106064835A CN106064835A CN201610582179.5A CN201610582179A CN106064835A CN 106064835 A CN106064835 A CN 106064835A CN 201610582179 A CN201610582179 A CN 201610582179A CN 106064835 A CN106064835 A CN 106064835A
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- manganese
- manganese sulfate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A kind of oil refinery waste acid treatment process, relate to a kind of useless acid treatment process, spent acid is first diluted to waste acid liquor by this technique, natural manganese dioxide powder and adsorbent is added in waste acid liquor, obtaining filtrate and filtering residue after agitation and filtration, filtering residue includes organic impurities and natural manganese dioxide powder, the adsorbent separated out in spent acid, this filtering residue is admixed natural manganese dioxide powder and charcoal and carries out roasting in roaster, natural manganese dioxide powder generates manganese oxide or manganese sulfate, and organic impurities, charcoal participate in roasting as fuel；Add in filtrate and make manganese sulfate ore pulp containing manganese mineral powder, manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid, manganese sulfate qualifying liquid is concentrated to give manganese sulfate, carry out electrolysis and obtain electrolytic manganese or electrolytic manganese dioxide.The present invention can effectively remove organic impurities, has environmental protection, low cost, the reliable feature of process safety, also solves the difficult problem that electrolytic manganese needs to consume a large amount of sulphuric acid, cost pressure is big, and its technical process is simple, easily operated.
Description
Technical field
The present invention relates to a kind of useless acid treatment process, particularly a kind of oil refinery waste acid treatment process.
Background technology
Oil plant the most typically will use concentrated sulphuric acid, concentrated sulphuric acid in use valid density to be gradually lowered,
Organic impurities constantly enters acid phase, and when reaching to a certain degree, the acid in system is just discharged with the form of spent acid.Row due to spent acid
Amount is relatively big, as processed not in time, environment can cause harm greatly.But, the oil refinery waste acid treatment process of current China
There is the biggest defect, spent acid cannot obtain Appropriate application, causes bigger environmental protection to affect.This is because the sulfur in oil plant spent acid
Acid content accounts for about 80%, and organic impurities accounts for about 20%, and how to be removed from sulphuric acid by the organic impurities of about 20% is a disaster
Topic.Some enterprises use spray combustion to process oil plant spent acid, but owing to organic impurity content is the lowest, it is impossible to directly spray combustion, need to add
Fuel, it is relatively costly, simultaneously because spray combustion is concentrated sulphuric acid, processes extremely dangerous.
Additionally, in metallurgy industry, the production process of electrolytic manganese or electrolytic manganese dioxide needs consume substantial amounts of sulphuric acid,
Its cost pressure is bigger.
Summary of the invention
The technical problem to be solved in the present invention is: provides a kind of oil refinery waste acid treatment process, had both solved at existing spent acid
What science and engineering skill existed be difficult to remove organic impurities, cause bigger environmental protection impact, cost is high, process extremely dangerous deficiency it
Place, can solve again electrolytic manganese or electrolytic manganese dioxide needs the difficult problem that consumes a large amount of sulphuric acid, cost pressure is big.
The present invention solves the technical scheme of above-mentioned technical problem: a kind of oil refinery waste acid treatment process, and this technique is first
Spent acid is diluted to waste acid liquor, in waste acid liquor, adds natural manganese dioxide powder and adsorbent, after agitation and filtration, obtain filtrate
And filtering residue, filtering residue includes organic impurities and natural manganese dioxide powder and the adsorbent separated out in spent acid, admixes natural by this filtering residue
Manganese dioxide powder and charcoal carry out roasting in roaster, and natural manganese dioxide powder generates manganese oxide or manganese sulfate, organic impurities,
Charcoal, adsorbent participate in roasting as fuel；Add in described filtrate and make manganese sulfate ore pulp, by sulphuric acid manganese ore containing manganese mineral powder
Slurry carries out purified treatment and obtains manganese sulfate qualifying liquid, manganese sulfate qualifying liquid is concentrated to give manganese sulfate product, to manganese sulfate
Qualifying liquid carries out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product.
The further technical scheme of the present invention is: this technique comprises the following steps:
A, dilution: spent acid is diluted to waste acid liquor；
B, mix and blend: add natural manganese dioxide powder and adsorbent in waste acid liquor, mixing and stirring forms spent acid and mixes
Close liquid；
C, filtration: filtered by spent acid mixed liquor, obtain filtrate and filtering residue, and filtering residue includes organic impurities and the sky separated out in spent acid
So manganese dioxide powder, adsorbent, by filtering residue by the process of step D, by filtrate by the process of step E；
D, filtering residue process: admix natural manganese dioxide powder, charcoal in filtering residue, and put into roaster and carry out roasting, natural titanium dioxide
Manganese powder generates manganese oxide or manganese sulfate product, and organic impurities, charcoal, adsorbent participate in roasting as fuel；
E, filtrate process: add containing manganese mineral powder in filtrate, prepare manganese sulfate ore pulp；
F, manganese sulfate ore pulp purify:
Manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid；
G, concentration: manganese sulfate qualifying liquid is concentrated to give manganese sulfate product；
H, electrolysis:
Manganese sulfate qualifying liquid is carried out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product.
The further technical scheme of the present invention is: in step, uses clear water or manganese sulfate concentrated mother liquor or electrolytic manganese
Spent acid is diluted by spent anolyte or electrolytic manganese dioxide waste liquid.
The further technical scheme of the present invention is: spent acid and clear water or manganese sulfate concentrated mother liquor or electrolytic manganese in step A
Volume ratio between spent anolyte or electrolytic manganese dioxide waste liquid is 1:1～10.
The further technical scheme of the present invention is: in stepb, described adsorbent includes activated carbon or hargil.
The further technical scheme of the present invention is: the sintering temperature in step D is 600～1100 DEG C.
The further technical scheme of the present invention is: the charcoal that the roasting in step D uses is coke or coal.
The further technical scheme of the present invention is: step F includes operation in detail below:
F1, neutralization: in manganese sulfate ore pulp, add alkaline solution be neutralized process；
F2, filtration I: the solution after neutralisation treatment is filtered, obtains filtering residue I and filtrate I, filtering residue I is abandoned, filtrate I is pressed
The process of operation F3；
F3, filtration II: be separately added into iron removing reagent, removing heavy metals agent, strong positive coagulant and adsorbent in filtrate I, filter,
Filtering residue II and filtrate II, abandon filtering residue II, and filtrate II is manganese sulfate qualifying liquid.
The further technical scheme of the present invention is: the alkaline solution in operation F1 is ammonia or lime water.
The further technical scheme of the present invention is: the iron removing reagent in operation F3 is oxidant, and removing heavy metals agent is a huge sum of money
Belonging to ion chelating agent, strong positive coagulant is cation adsorbent and flocculant, and adsorbent is activated carbon or hargil.
Owing to using said structure, compared with prior art, have following has the oil refinery waste acid treatment process of the present invention
Benefit effect:
1. can effectively remove organic impurities:
This technique is first spent acid to be diluted to waste acid liquor, adds natural manganese dioxide powder and adsorbent, stir in waste acid liquor
Obtaining filtrate and filtering residue after mixing filtration, filtering residue includes organic impurities and natural manganese dioxide powder, the adsorbent separated out in spent acid, should
Filtering residue is admixed natural manganese dioxide powder and charcoal and is carried out roasting in roaster, and natural manganese dioxide powder generates manganese oxide or sulphuric acid
Manganese, organic impurities, charcoal, adsorbent participate in roasting as fuel；Add in described filtrate and make sulphuric acid manganese ore containing manganese mineral powder
Slurry, carries out purified treatment by manganese sulfate ore pulp and obtains manganese sulfate qualifying liquid, manganese sulfate qualifying liquid is concentrated to give manganese sulfate
Product, carries out electrolysis to manganese sulfate qualifying liquid and obtains electrolytic manganese or electrolytic manganese dioxide product.Therefore, present invention employs dilute
Release, mix and blend, filter, the step such as purification removes organic impurities, wherein dilution is to allow organic impurities discharge from sulphuric acid
Out, in order to be combined production precipitation with natural manganese dioxide powder, adsorbent；And in mix and blend, natural manganese dioxide powder plays
Participate in chemical removal and the physisorption of part organic impurities in spent acid；Adsorbent then primarily serves participation physical absorption and makees
With, organic impurities absorption is formed deposition removal.Through it is demonstrated experimentally that the method can effectively remove major part molecular weight big
Organic substance and the organic substance of some reproducibilities of oxidation.
2. environmental protection
Due to the present invention by dilution, mix and blend, filter, the step such as purification effectively eliminates the organic impurities in spent acid；Logical
Crossing and filtering residue is admixed natural manganese dioxide powder and charcoal carry out roasting in roaster, natural manganese dioxide powder generates manganese oxide or sulfur
Acid manganese；Add from filtrate and make manganese sulfate ore pulp containing manganese mineral powder, manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate conjunction
Lattice liquid, then manganese sulfate qualifying liquid is concentrated to give manganese sulfate, carry out electrolysis and obtain electrolytic manganese or electrolytic manganese dioxide product；
Therefore, produce without " three wastes " when the present invention processes spent acid, the sulphuric acid in spent acid can be made to obtain Appropriate application, it is to avoid spent acid is direct
The impact discharged and cause, compares environmental protection.
3. low cost
The dilution of this technique, mix and blend, filter, each step such as purification the most simple to operation, and the additive used is equal
It it is additive conventional, lower-cost.During roasting filtering residue, organic impurities, charcoal, adsorbent participate in roasting as fuel
Burn, provide heat energy for roasting, achieve recycling economy to greatest extent.
4. process safety is reliable
The present invention be by dilution, mix and blend, filter, the step such as purification effectively eliminates the organic impurities in spent acid；Without
Using spray combustion to process oil plant spent acid, it is safe and reliable that it processes technics comparing.
5. solve electrolytic manganese or electrolytic manganese dioxide need the difficult problem that consumes a large amount of sulphuric acid, cost pressure is big:
This technique spent acid is diluted, mix and blend, after filtration, add in filtrate and make sulphuric acid manganese ore containing manganese mineral powder
Slurry, carries out manganese sulfate ore pulp purified treatment and obtains manganese sulfate qualifying liquid, then be electrolysed manganese sulfate qualifying liquid, be electrolysed
Manganese or electrolytic manganese dioxide product, thus can realize the sulphuric acid in spent acid is carried out recycling, solve electricity for a long time
Solution manganese or electrolytic manganese dioxide need the difficult problem consuming a large amount of sulphuric acid, cost pressure is big.
6. can improve Faradaic current efficiency and yield
The present invention, during manganese sulfate ore pulp is carried out purified treatment, with the addition of strong positive coagulant, this strong positive coagulation
The addition of agent is key technology, removes little molecule and other organic impurities the most further, thus can improve Faradaic current effect
Rate and yield.
7. technical process is simple, easily operated:
The technical process of the present invention is fairly simple, it is easy to operation.
Below, in conjunction with detailed description of the invention, the technical characteristic of the oil refinery waste acid treatment process of the present invention is made further
Explanation.
Detailed description of the invention
Embodiment one
A kind of oil refinery waste acid treatment process, this technique is first spent acid to be diluted to waste acid liquor, adds sky in waste acid liquor
So manganese dioxide powder and adsorbent, obtains filtrate and filtering residue after agitation and filtration, filtering residue includes organic impurities and the sky separated out in spent acid
So manganese dioxide powder, adsorbent, admix this filtering residue natural manganese dioxide powder and charcoal and carry out roasting, natural dioxy in roaster
Changing manganese powder and generate manganese oxide or manganese sulfate, organic impurities, charcoal, adsorbent participate in roasting as fuel；Add in described filtrate
Enter and make manganese sulfate ore pulp containing manganese mineral powder, manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid, manganese sulfate is closed
Lattice liquid carries out being concentrated to give manganese sulfate product, manganese sulfate qualifying liquid carries out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product
Product.This technique comprises the following steps:
A, dilution: using clear water to be diluted spent acid, the volume ratio between spent acid and clear water is 1:10；
B, mix and blend: add natural manganese dioxide powder and adsorbent in waste acid liquor, mixing and stirring forms spent acid and mixes
Close liquid；Described adsorbent includes activated carbon；
C, filtration: filtered by spent acid mixed liquor, obtain filtrate and filtering residue, and filtering residue includes organic impurities and the sky separated out in spent acid
So manganese dioxide powder, adsorbent, by filtering residue by the process of step D, by filtrate by the process of step E；
D, filtering residue process: admix natural manganese dioxide powder, coke in filtering residue, and put into roaster and carry out roasting, sintering temperature
Being 600 DEG C, natural manganese dioxide powder generates manganese oxide or manganese sulfate product, and organic impurities, coke, adsorbent participate in as fuel
Roasting；
E, filtrate process: add containing manganese mineral powder in filtrate, prepare manganese sulfate ore pulp；
F, manganese sulfate ore pulp purify:
Manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid；
G, concentration: manganese sulfate qualifying liquid is concentrated to give manganese sulfate product；
H, electrolysis:
Manganese sulfate qualifying liquid is carried out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product.
Above-mentioned steps F includes operation in detail below:
F1, neutralization: in manganese sulfate ore pulp, add alkaline solution ammonia be neutralized process；
F2, filtration I: the solution after neutralisation treatment is filtered, obtains filtering residue I and filtrate I, filtering residue I is abandoned, filtrate I is pressed
The process of operation F3；
F3, filtration II: be separately added into iron removing reagent, removing heavy metals agent, strong positive coagulant and adsorbent in filtrate I, filter,
Filtering residue II and filtrate II, abandon filtering residue II, and filtrate II is manganese sulfate qualifying liquid, and described iron removing reagent is oxidant, except weight
Metal agent is heavy metal ion chelating agent, and strong positive coagulant is cation adsorbent and flocculant, and adsorbent is activated carbon.
Embodiment two
A kind of oil refinery waste acid treatment process, this technique is first spent acid to be diluted to waste acid liquor, adds sky in waste acid liquor
So manganese dioxide powder and adsorbent, obtains filtrate and filtering residue after agitation and filtration, filtering residue includes organic impurities and the sky separated out in spent acid
So manganese dioxide powder, adsorbent, admix this filtering residue natural manganese dioxide powder and charcoal and carry out roasting, natural dioxy in roaster
Changing manganese powder and generate manganese oxide or manganese sulfate, organic impurities, charcoal, adsorbent participate in roasting as fuel；Add in described filtrate
Enter and make manganese sulfate ore pulp containing manganese mineral powder, manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid, manganese sulfate is closed
Lattice liquid carries out being concentrated to give manganese sulfate product, manganese sulfate qualifying liquid carries out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product
Product.This technique comprises the following steps:
A, dilution: use manganese sulfate concentrated mother liquor that spent acid is diluted, the volume ratio between spent acid and manganese sulfate concentrated mother liquor
For 1:5；
B, mix and blend: add natural manganese dioxide powder and adsorbent in waste acid liquor, mixing and stirring forms spent acid and mixes
Close liquid；Described adsorbent includes hargil；
C, filtration: filtered by spent acid mixed liquor, obtain filtrate and filtering residue, and filtering residue includes organic impurities and the sky separated out in spent acid
So manganese dioxide powder, adsorbent, by filtering residue by the process of step D, by filtrate by the process of step E；
D, filtering residue process: admix natural manganese dioxide powder, coal in filtering residue, and put into roaster and carry out roasting, sintering temperature
Being 800 DEG C, natural manganese dioxide powder generates manganese oxide or manganese sulfate product, and organic impurities, coal, adsorbent participate in as fuel
Roasting；
E, filtrate process: add containing manganese mineral powder in filtrate, prepare manganese sulfate ore pulp；
F, manganese sulfate ore pulp purify:
Manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid；
G, concentration: manganese sulfate qualifying liquid is concentrated to give manganese sulfate product；
H, electrolysis:
Manganese sulfate qualifying liquid is carried out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product.
Above-mentioned steps F includes operation in detail below:
F1, neutralization: in manganese sulfate ore pulp, add alkaline solution lime water be neutralized process；
F2, filtration I: the solution after neutralisation treatment is filtered, obtains filtering residue I and filtrate I, filtering residue I is abandoned, filtrate I is pressed
The process of operation F3；
F3, filtration II: be separately added into iron removing reagent, removing heavy metals agent, strong positive coagulant and adsorbent in filtrate I, filter,
Filtering residue II and filtrate II, abandon filtering residue II, and filtrate II is manganese sulfate qualifying liquid, and described iron removing reagent is oxidant, except weight
Metal agent is heavy metal ion chelating agent, and strong positive coagulant is cation adsorbent and flocculant, and adsorbent is hargil.
Embodiment three
A kind of oil refinery waste acid treatment process, this technique is first spent acid to be diluted to waste acid liquor, adds sky in waste acid liquor
So manganese dioxide powder and adsorbent, obtains filtrate and filtering residue after agitation and filtration, filtering residue includes organic impurities and the sky separated out in spent acid
So manganese dioxide powder, adsorbent, admix this filtering residue natural manganese dioxide powder and charcoal and carry out roasting, natural dioxy in roaster
Changing manganese powder and generate manganese oxide or manganese sulfate, organic impurities, charcoal, adsorbent participate in roasting as fuel；Add in described filtrate
Enter and make manganese sulfate ore pulp containing manganese mineral powder, manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid, manganese sulfate is closed
Lattice liquid carries out being concentrated to give manganese sulfate product, manganese sulfate qualifying liquid carries out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product
Product.This technique comprises the following steps:
A, dilution: use electrolytic manganese spent anolyte or electrolytic manganese dioxide waste liquid that spent acid is diluted, spent acid and electrolytic manganese sun
Volume ratio between pole waste liquid or electrolytic manganese dioxide waste liquid is 1:1；
B, mix and blend: add natural manganese dioxide powder and adsorbent in waste acid liquor, mixing and stirring forms spent acid and mixes
Close liquid；Described adsorbent includes hargil or other inorganic adsorbents；
C, filtration: filtered by spent acid mixed liquor, obtain filtrate and filtering residue, and filtering residue includes organic impurities and the sky separated out in spent acid
So manganese dioxide powder, adsorbent, by filtering residue by the process of step D, by filtrate by the process of step E；
D, filtering residue process: admix natural manganese dioxide powder, coke or coal in filtering residue, and put into roaster and carry out roasting, roasting
Burning temperature is 1100 DEG C, and natural manganese dioxide powder generates manganese oxide or manganese sulfate product, organic impurities, coke or coal, absorption
Agent participates in roasting as fuel；
E, filtrate process: add containing manganese mineral powder in filtrate, prepare manganese sulfate ore pulp；
F, manganese sulfate ore pulp purify:
Manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid；
G, concentration: manganese sulfate qualifying liquid is concentrated to give manganese sulfate product；
H, electrolysis:
Manganese sulfate qualifying liquid is carried out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product.
Above-mentioned steps F includes operation in detail below:
F1, neutralization: in manganese sulfate ore pulp, add alkaline solution ammonia be neutralized process；
F2, filtration I: the solution after neutralisation treatment is filtered, obtains filtering residue I and filtrate I, filtering residue I is abandoned, filtrate I is pressed
The process of operation F3；
F3, filtration II: be separately added into iron removing reagent, removing heavy metals agent, strong positive coagulant and adsorbent in filtrate I, filter,
Filtering residue II and filtrate II, abandon filtering residue II, and filtrate II is manganese sulfate qualifying liquid, and described iron removing reagent is oxidant, except weight
Metal agent is heavy metal ion chelating agent, and strong positive coagulant is cation adsorbent and flocculant, adsorbent be hargil or its
His inorganic adsorbent.
Claims (10)
1. an oil refinery waste acid treatment process, it is characterised in that: this technique is first spent acid to be diluted to waste acid liquor, toward spent acid
Adding natural manganese dioxide powder and adsorbent in solution, obtain filtrate and filtering residue after agitation and filtration, filtering residue includes precipitation in spent acid
Organic impurities and natural manganese dioxide powder and adsorbent, admix natural manganese dioxide powder and charcoal by this filtering residue and carry out in roaster
Roasting, natural manganese dioxide powder generates manganese oxide or manganese sulfate, and organic impurities, charcoal, adsorbent participate in roasting as fuel；Toward institute
Adding in the filtrate stated and make manganese sulfate ore pulp containing manganese mineral powder, manganese sulfate ore pulp carries out purified treatment, and to obtain manganese sulfate qualified
Liquid, is concentrated to give manganese sulfate product to manganese sulfate qualifying liquid, manganese sulfate qualifying liquid is carried out electrolysis and obtains electrolytic manganese or electricity
Solve manganese dioxide product.
Oil refinery waste acid treatment process the most according to claim 1, it is characterised in that: this technique comprises the following steps:
A, dilution: spent acid is diluted to waste acid liquor；
B, mix and blend: add natural manganese dioxide powder and adsorbent in waste acid liquor, mixing and stirring forms spent acid and mixes
Close liquid；
C, filtration: filtered by spent acid mixed liquor, obtain filtrate and filtering residue, and filtering residue includes organic impurities and the sky separated out in spent acid
So manganese dioxide powder, adsorbent, by filtering residue by the process of step D, by filtrate by the process of step E；
D, filtering residue process: admix natural manganese dioxide powder, charcoal in filtering residue, and put into roaster and carry out roasting, natural titanium dioxide
Manganese powder generates manganese oxide or manganese sulfate product, and organic impurities, charcoal, adsorbent participate in roasting as fuel；
E, filtrate process: add containing manganese mineral powder in filtrate, prepare manganese sulfate ore pulp；
F, manganese sulfate ore pulp purify:
Manganese sulfate ore pulp is carried out purified treatment and obtains manganese sulfate qualifying liquid；
G, concentration: manganese sulfate qualifying liquid is concentrated to give manganese sulfate product；
H, electrolysis:
Manganese sulfate qualifying liquid is carried out electrolysis and obtains electrolytic manganese or electrolytic manganese dioxide product.
Oil refinery waste acid treatment process the most according to claim 2, it is characterised in that: in step, use clear water or sulfur
Spent acid is diluted by acid manganese concentrated mother liquor or electrolytic manganese spent anolyte or electrolytic manganese dioxide waste liquid.
Oil refinery waste acid treatment process the most according to claim 3, it is characterised in that: spent acid and clear water or sulfur in step A
Volume ratio between acid manganese concentrated mother liquor or electrolytic manganese spent anolyte or electrolytic manganese dioxide waste liquid is 1:1～10.
Oil refinery waste acid treatment process the most according to claim 2, it is characterised in that: in stepb, described adsorbent
Including activated carbon or hargil.
Oil refinery waste acid treatment process the most according to claim 2, it is characterised in that: the sintering temperature in step D is 600
～1100 DEG C.
Oil refinery waste acid treatment process the most according to claim 2, it is characterised in that: the charcoal that the roasting in step D uses
For coke or coal.
Oil refinery waste acid treatment process the most according to claim 2, it is characterised in that: step F includes operation in detail below:
F1, neutralization: in manganese sulfate ore pulp, add alkaline solution be neutralized process；
F2, filtration I: the solution after neutralisation treatment is filtered, obtains filtering residue I and filtrate I, filtering residue I is abandoned, filtrate I is pressed
The process of operation F3；
F3, filtration II: be separately added into iron removing reagent, removing heavy metals agent, strong positive coagulant and adsorbent in filtrate I, filter,
Filtering residue II and filtrate II, abandon filtering residue II, and filtrate II is manganese sulfate qualifying liquid.
Oil refinery waste acid treatment process the most according to claim 8, it is characterised in that: the alkaline solution in operation F1 is ammonia
Water or lime water.
Oil refinery waste acid treatment process the most according to claim 8, it is characterised in that: the iron removing reagent in operation F3 is oxygen
Agent, removing heavy metals agent is heavy metal ion chelating agent, and strong positive coagulant is cation adsorbent and flocculant, and adsorbent is
Activated carbon or hargil.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724697A (en) * | 2004-07-19 | 2006-01-25 | 中南大学 | Method of manufacturing electrolytic metal manganese using titanium white waste acid and manganese dioxide ore |
| CN1751984A (en) * | 2004-09-20 | 2006-03-29 | 中国石油天然气股份有限公司 | Treatment technology of producing sulfuric acid from alkylated spent sulfuric acid through high temperature decomposition |
| CN101280431A (en) * | 2008-01-15 | 2008-10-08 | 成都阿斯特克国龙环保工程有限公司 | Pre-desiliconisation system and process for waste acid |
| CN101724281A (en) * | 2009-12-08 | 2010-06-09 | 天津理工大学 | Method for preparing high strength asphalt by utilizing acid residue |
| CN102784491A (en) * | 2012-08-28 | 2012-11-21 | 重庆钢铁(集团)有限责任公司 | Waste acid treatment process |
| CN102942960A (en) * | 2012-10-30 | 2013-02-27 | 陕西高新能源发展有限公司 | Heavy dirty oil recovery method for oil refinery |
| CN103556172A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Method for deeply removing impurities in manganese dioxide electrolyte |
| CN103572055A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of manganese sulfate for electrolytic manganese dioxide |
| CN103710541A (en) * | 2013-12-24 | 2014-04-09 | 柳州豪祥特科技有限公司 | Wet process for producing electrolytic manganese dioxide |
| CN104108777A (en) * | 2014-08-04 | 2014-10-22 | 罗光臣 | Method for treating acidic wastewater or waste acid with cement |
| CN105776139A (en) * | 2016-03-16 | 2016-07-20 | 江苏双能太阳能有限公司 | Waste acid treatment process |
-
2016
- 2016-07-22 CN CN201610582179.5A patent/CN106064835B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724697A (en) * | 2004-07-19 | 2006-01-25 | 中南大学 | Method of manufacturing electrolytic metal manganese using titanium white waste acid and manganese dioxide ore |
| CN1751984A (en) * | 2004-09-20 | 2006-03-29 | 中国石油天然气股份有限公司 | Treatment technology of producing sulfuric acid from alkylated spent sulfuric acid through high temperature decomposition |
| CN101280431A (en) * | 2008-01-15 | 2008-10-08 | 成都阿斯特克国龙环保工程有限公司 | Pre-desiliconisation system and process for waste acid |
| CN101724281A (en) * | 2009-12-08 | 2010-06-09 | 天津理工大学 | Method for preparing high strength asphalt by utilizing acid residue |
| CN102784491A (en) * | 2012-08-28 | 2012-11-21 | 重庆钢铁(集团)有限责任公司 | Waste acid treatment process |
| CN102942960A (en) * | 2012-10-30 | 2013-02-27 | 陕西高新能源发展有限公司 | Heavy dirty oil recovery method for oil refinery |
| CN103556172A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Method for deeply removing impurities in manganese dioxide electrolyte |
| CN103572055A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of manganese sulfate for electrolytic manganese dioxide |
| CN103710541A (en) * | 2013-12-24 | 2014-04-09 | 柳州豪祥特科技有限公司 | Wet process for producing electrolytic manganese dioxide |
| CN104108777A (en) * | 2014-08-04 | 2014-10-22 | 罗光臣 | Method for treating acidic wastewater or waste acid with cement |
| CN105776139A (en) * | 2016-03-16 | 2016-07-20 | 江苏双能太阳能有限公司 | Waste acid treatment process |
Non-Patent Citations (1)
| Title |
|---|
| 张文山等: ""利用钛白粉废酸_二氧化锰矿和硫铁矿制取电解金属锰的研究与开发"", 《中国锰业》 * |
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