CN104555949A - Titanium white waste acid concentration process - Google Patents
Titanium white waste acid concentration process Download PDFInfo
- Publication number
- CN104555949A CN104555949A CN201410825568.7A CN201410825568A CN104555949A CN 104555949 A CN104555949 A CN 104555949A CN 201410825568 A CN201410825568 A CN 201410825568A CN 104555949 A CN104555949 A CN 104555949A
- Authority
- CN
- China
- Prior art keywords
- concentration
- acid
- upper strata
- layering
- acid solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
-
- 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
- C01B17/88—Concentration of sulfuric acid
-
- 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
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
- C01B17/902—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids by dialysis
Abstract
The invention discloses a titanium white waste acid concentration process. During the process, sulfuric acid with relatively high concentration is added into waste acid firstly, so as to enable ferrite to be separated out partly, an acid liquor and the separated out ferrite are separated, ozone is introduced into the acid liquor, ferrous ions are oxidized to be ferric ions, then the ferric ions are taken out through extraction and reextraction, and finally, the sulfuric acid with the concentration of 75 to 85 percent is obtained through atmospheric distillation and reduced pressure distillation. The titanium white waste acid concentration process provided by the invention is not required to be conducted in a high temperature environment, is free from high energy consumption, and is simple in process, low in cost and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of titanium white waste acid concentration technology, belong to useless acid-treated technical field.
Background technology
At present, the global titanium dioxide output value about 11,000,000,000 dollars, be the third-largest inorganic chemical product being only second to synthetic ammonia, phosphoric acid, titanium dioxide is widely used in the industries such as coating, paint, papermaking, rubber, and the clothing, food, lodging and transportion--basic necessities of life of people are closely bound up.Titanium dioxide is all classified as the critical product affecting the national economic development by many countries, and titanium dioxide consumption is also looked at the important indicator of a reflection national economic development level per capita.
Corresponding is, titanium white production mainly adopts sulfuric acid process, chlorination process and hydrochloric acid method three kinds of methods, all adopt Production By Sulfuric Acid Process at the titanium dioxide of China 95% and obtain, spent acid can be produced in production process of titanium pigment, often produce 1t titanium white and will discharge spent acid 8-10t, containing sulfuric acid, ferrous sulfate inorganic salt etc. in spent acid, its complex treatment process, difficulty are large.Current China has become world's second largest titanium white production state, whole industry common property goes out spent acid amount and is about 8000kt/a, how to process and recycle the very big concern that these spent acid cause insider, titanium white waste acid concentrates reuse not only makes waste acid resource be utilized effectively, and save a large amount of waste acid treatment expenses, economic benefit and the social benefit of highly significant can be obtained.Also many waste acid concentration methods have been there is at present, comparatively commonly submerged combustion, spray concentration technology, Finland Norma (Rauma-Repola) technology etc., submerged combustion is that the high-temperature gas of about 1200 DEG C in combustion chamber is directly sprayed into spent acid, moisture content in spent acid rapid evaporation in high-temperature medium, improves the concentration of sulfuric acid, the FeSO in spent acid
47H
2o is with FeSO
4h
2the form of O is separated out.But this method, because needing the gas of comparatively high temps, consumes energy high.Spray concentration technology adopts air directly in spraying concentration tower, to carry out counter current contact with the spent acid through spray concentration 20%, through heating, evaporation concentration, the acid solution going out tower again through cooling, after being separated the inorganic salts in spent acid etc. and get final product.Finland Norma (Rauma-Repola) technology adopts spent acid through steam level Four evaporation and concentrating technology, is improved by rare acid-spending strength and get final product.But these methods all need to need again crystallisation by cooling at a lower temperature after comparatively high temps evaporation, require higher to reaction environment like this, higher to equipment requirements, and acid easily etching apparatus, consume energy high, the sour cost of ton is high, multistage steam is concentrated because containing impurity in spent acid, is easy to cause well heater to block, therefore, a kind of power consumption of research is low, and the waste acid concentration technique that after concentrating, acid-spending strength is high has realistic meaning.
Summary of the invention
The object of this invention is to provide a kind of titanium white waste acid concentration technology.Dense environment required for the present invention, below 100 DEG C, does not need hot environment, consumes energy low, and technique is simple, and cost is low, and after concentrated by this technique, sulfuric acid concentration can reach 75%-85%.
Technical scheme of the present invention: a kind of titanium white waste acid concentration technology, comprises the following steps:
(1) to concentration be 20%-23% spent acid in add the sulfuric acid that concentration is 60%-90%, the concentration of sulfuric acid in spent acid is adjusted to 35%-60%;
(2) by concentration be the spent acid of 35%-60% under 40 DEG C of-80 DEG C of conditions, leave standstill, until ferrous sulfate crystallization is no longer separated out;
(3) ferrous sulfate crystal is separated with acid solution, gets acid solution, under normal temperature, add oxygenant, until the Fe in acid solution
2+all be oxidized to Fe
3+;
(4) in separating funnel, add acid solution, the hydrochloric acid of concentration 1.0g/L-6.0g/L and concentration after oxidation is successively the extraction agent of 20%-60%, and vibration leaves standstill, layering, gets the upper strata extracting phase after layering, adds the extraction agent that concentration is 20%-60%, vibration, leaves standstill, layering;
(5) get the upper strata extracting phase after above-mentioned layering, in upper strata extracting phase: the volume ratio of distilled water be the ratio of 1:3-6 to adding distil water in the extracting phase of upper strata, vibration, leaves standstill, layering; Get upper strata extraction phase first after air distillation 2-5h, then distill 3-5h under 0.4MPa-0.7 MPa condition, obtain the sulfuric acid that concentration is 75%-85%.
Aforementioned titanium white waste acid concentration technology, comprises the following steps:
(1) to concentration be 20%-23% spent acid in add the sulfuric acid that concentration is 60%-90%, the concentration of sulfuric acid in spent acid is adjusted to 35%-60%;
(2) by concentration be the spent acid of 35%-60% under 50-60 DEG C of condition, leave standstill, until ferrous sulfate crystallization is no longer separated out;
(3) ferrous sulfate crystal is separated with acid solution, gets acid solution, under normal temperature, add oxygenant, until the Fe in acid solution
2+all be oxidized to Fe
3+;
(4) in separating funnel, add acid solution, the hydrochloric acid of concentration 3.5g/L and concentration after oxidation is successively the extraction agent of 20%-60%, vibration, and leave standstill, layering, gets the upper strata extracting phase after layering, adds the extraction agent that concentration is 20%-60%, and vibration leaves standstill, layering;
(5) get the upper strata extracting phase after above-mentioned layering, in upper strata extracting phase: the volume ratio of distilled water be the ratio of 1:4.5 to adding distil water in the extracting phase of upper strata, vibration, leaves standstill, layering; Get upper strata extraction phase first after air distillation 3h, then distill 4h under 0.5MPa condition, obtain the sulfuric acid that concentration is 75%-85%.
In aforementioned titanium white waste acid concentration technology, described spent acid is the spent acid solution that Titanium White Production By Sulfuric Acid Process produces.
In aforementioned titanium white waste acid concentration technology, described step (3) described oxygenant is ozone.
In aforementioned titanium white waste acid concentration technology, in described step (4), the volume ratio of acid solution and extraction agent is 1:1.5, and the volume ratio of acid solution and hydrochloric acid is 1:3, and the volume ratio of upper strata extracting phase and extraction agent is 1:1.5.
In aforementioned titanium white waste acid concentration technology, described step (4) described extraction agent is methyl iso-butyl ketone (MIBK).
The present invention first adds the sulfuric acid that concentration is 60%-90% in the spent acid of Production By Sulfuric Acid Process titanium white generation, and the concentration of sulfuric acid in spent acid is adjusted to 35%-60%.Because the solubleness of the ferrous salt in spent acid in sulfuric acid is relevant with the concentration of sulfuric acid, when sulfuric acid concentration is at 35%-60%, the solubleness of ferrous salt is tending towards minimum, the ferrous salt can effectively gone out in original waste acid like this, other salts due to saltout and coprecipitated precipitating action be also removed major part simultaneously.Then acid solution is separated with crystalline material, so both can have removed the most of ferrous salt in original waste acid.Then at normal temperatures, ozone is passed in acid solution, oxidation of divalent iron ion in acid solution is become ferric ion, acid solution is added again in separating funnel, hydrochloric acid and extraction agent, extract, vibration, leave standstill, after layering, get the remaining phase of extraction, add extraction agent again to extract, finally get extracting phase again, add distilled water to strip, because adding hydrochloric acid in acid solution, the complex ability of hydrochloric acid and ferric ion is very strong, remain in the hydrochloric acid in extraction phase, available simple distillation and concentration method can be recycled, so not only the percentage extraction of ferric ion increases, in addition, after extracting like this and stripping, by acid solution after normal pressure and underpressure distillation, the acid strength of gained is up to 75%-85%, can again be used for producing titanium dioxide or sale, cost-saved like this.In whole concentration technology, do not have high temperature requirement, capable of reducing energy consumption like this, not easily damage equipment, can effective surplus cost.
Compared with the prior art, the present invention's dense environment required for the present invention, below 100 DEG C, does not need hot environment, consumes energy low, and technique is simple, and cost is low, can reach 75%-85%, reach goal of the invention with the acid-spending strength after this technique concentrates.
Further illustrate the present invention by the following examples, but not as limitation of the present invention.
embodiment:
Embodiment 1.
A kind of titanium white waste acid concentration technology, comprises the following steps:
1, the concentration produced to Titanium White Production By Sulfuric Acid Process is add the sulfuric acid that concentration is 75% in the spent acid of 20%-23%, and the concentration of sulfuric acid in spent acid is adjusted to 55%;
2, by concentration be the spent acid of 55% under 55 DEG C of conditions, leave standstill, until ferrous sulfate crystallization is no longer separated out;
3, ferrous sulfate crystal is separated with acid solution, gets acid solution, under normal temperature, add ozone, until the Fe in acid solution
2+all be oxidized to Fe
3+;
4, in separating funnel, add acid solution, the hydrochloric acid of concentration 3.5g/L and concentration after oxidation is successively the methyl iso-butyl ketone (MIBK) of 40%, and vibration leaves standstill, layering, gets the upper strata extracting phase after layering, adds the methyl iso-butyl ketone (MIBK) that concentration is 40%, vibration, leaves standstill, layering;
5, get the upper strata extracting phase after above-mentioned layering, in upper strata extracting phase: the volume ratio of distilled water be the ratio of 1:4.5 to adding distil water in the extracting phase of upper strata, vibration, leaves standstill, layering; Get upper strata extraction phase first after air distillation 3h, then distill 4h under 0.5MPa condition, obtain the sulfuric acid that concentration is 75%-85%.
In step 4, the volume ratio of acid solution and extraction agent is 1:1.5, and the volume ratio of acid solution and hydrochloric acid is 1:3, and the volume ratio of upper strata extracting phase and methyl iso-butyl ketone (MIBK) is 1:1.5.
Embodiment 2.
A kind of titanium white waste acid concentration technology, comprises the following steps:
1, to concentration be 20%-23% spent acid in add the sulfuric acid of concentration 90%, the concentration of sulfuric acid in spent acid is adjusted to 60%;
2, by concentration be the spent acid of 60% under 80 DEG C of conditions, leave standstill, until ferrous sulfate crystallization is no longer separated out;
3, ferrous sulfate crystal is separated with acid solution, gets acid solution, under normal temperature, add ozone, until the Fe in acid solution
2+all be oxidized to Fe
3+;
4, in separating funnel, add acid solution, the hydrochloric acid of concentration 6.0g/L and concentration after oxidation is successively the methyl iso-butyl ketone (MIBK) of 60%, and vibration leaves standstill, layering, gets the upper strata extracting phase after layering, adds the methyl iso-butyl ketone (MIBK) that concentration is 60%, vibration, leaves standstill, layering;
5, get the upper strata extracting phase after above-mentioned layering, in upper strata extracting phase: the volume ratio of distilled water be the ratio of 1:6 to adding distil water in the extracting phase of upper strata, vibration, leaves standstill, layering; Get upper strata extraction phase first after air distillation 5h, then distill 5h under 0.7 MPa condition, obtain the sulfuric acid that concentration is 75%-85%.
In step 4, the volume ratio of acid solution and extraction agent is 1:1.5, and the volume ratio of acid solution and hydrochloric acid is 1:3, and the volume ratio of upper strata extracting phase and methyl iso-butyl ketone (MIBK) is 1:1.5.
Embodiment 3.
A kind of titanium white waste acid concentration technology, comprises the following steps:
1, to concentration be 20%-23% spent acid in add the sulfuric acid that concentration is 60%, the concentration of sulfuric acid in spent acid is adjusted to 35%;
2, by concentration be the spent acid of 35% under 40 DEG C of conditions, leave standstill, until ferrous sulfate crystallization is no longer separated out;
3, ferrous sulfate crystal is separated with acid solution, gets acid solution, under normal temperature, add ozone, until the Fe in acid solution
2+all be oxidized to Fe
3+;
4, in separating funnel, add acid solution, the hydrochloric acid of concentration 1.0g/L-6.0g/L and concentration after oxidation is successively the methyl iso-butyl ketone (MIBK) of 20%-60%, and vibration leaves standstill, layering, gets the upper strata extracting phase after layering, adds the methyl iso-butyl ketone (MIBK) that concentration is 20%-60%, vibration, leaves standstill, layering;
5, get the upper strata extracting phase after above-mentioned layering, in upper strata extracting phase: the volume ratio of distilled water be the ratio of 1:3 to adding distil water in the extracting phase of upper strata, vibration, leaves standstill, layering; Get upper strata extraction phase first after air distillation 2h, then distill 3h under 0.4MPa condition, obtain the sulfuric acid that concentration is 75%-85%.
In step 4, the volume ratio of acid solution and extraction agent is 1:1.5, and the volume ratio of acid solution and hydrochloric acid is 1:3, and the volume ratio of upper strata extracting phase and methyl iso-butyl ketone (MIBK) is 1:1.5.
Claims (6)
1. a titanium white waste acid concentration technology, is characterized in that: comprise the following steps:
(1) to concentration be 20%-23% spent acid in add the sulfuric acid that concentration is 60%-90%, the concentration of sulfuric acid in spent acid is adjusted to 35%-60%;
(2) by concentration be the spent acid of 35%-60% under 40 DEG C of-80 DEG C of conditions, leave standstill, until ferrous sulfate crystallization is no longer separated out;
(3) ferrous sulfate crystal is separated with acid solution, gets acid solution, under normal temperature, add oxygenant, until the Fe in acid solution
2+all be oxidized to Fe
3+;
(4) in separating funnel, add acid solution, the hydrochloric acid of concentration 1.0g/L-6.0g/L and concentration after oxidation is successively the extraction agent of 20%-60%, and vibration leaves standstill, layering, gets the upper strata extracting phase after layering, adds the extraction agent that concentration is 20%-60%, vibration, leaves standstill, layering;
(5) get the upper strata extracting phase after above-mentioned layering, in upper strata extracting phase: the volume ratio of distilled water be the ratio of 1:3-6 to adding distil water in the extracting phase of upper strata, vibration, leaves standstill, layering; Get upper strata extraction phase first after air distillation 2-5h, then distill 3-5h under 0.4MPa-0.7 MPa condition, obtain the sulfuric acid that concentration is 75%-85%.
2. titanium white waste acid concentration technology as claimed in claim 1, is characterized in that: comprise the following steps:
(1) to concentration be 20%-23% spent acid in add the sulfuric acid that concentration is 60%-90%, the concentration of sulfuric acid in spent acid is adjusted to 35%-60%;
(2) by concentration be the spent acid of 35%-60% under 50-60 DEG C of condition, leave standstill, until ferrous sulfate crystallization is no longer separated out;
(3) ferrous sulfate crystal is separated with acid solution, gets acid solution, under normal temperature, add oxygenant, until the Fe in acid solution
2+all be oxidized to Fe
3+;
(4) in separating funnel, add acid solution, the hydrochloric acid of concentration 3.5g/L and concentration after oxidation is successively the extraction agent of 20%-60%, vibration, and leave standstill, layering, gets the upper strata extracting phase after layering, adds the extraction agent that concentration is 20%-60%, and vibration leaves standstill, layering;
(5) get the upper strata extracting phase after above-mentioned layering, in upper strata extracting phase: the volume ratio of distilled water be the ratio of 1:4.5 to adding distil water in the extracting phase of upper strata, vibration, leaves standstill, layering; Get upper strata extraction phase first after air distillation 3h, then distill 4h under 0.5MPa condition, obtain the sulfuric acid that concentration is 75%-85%.
3. titanium white waste acid concentration technology as claimed in claim 1 or 2, is characterized in that: described spent acid is the spent acid solution that Titanium White Production By Sulfuric Acid Process produces.
4. titanium white waste acid concentration technology as claimed in claim 1 or 2, is characterized in that: described step (3) described oxygenant is ozone.
5. titanium white waste acid concentration technology as claimed in claim 1 or 2, is characterized in that: in described step (4), the volume ratio of acid solution and extraction agent is 1:1.5, and the volume ratio of acid solution and hydrochloric acid is 1:3; The volume ratio of upper strata extracting phase and extraction agent is 1:1.5.
6. titanium white waste acid concentration technology as claimed in claim 5, is characterized in that: described step (4) described extraction agent is methyl iso-butyl ketone (MIBK).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410825568.7A CN104555949A (en) | 2014-12-28 | 2014-12-28 | Titanium white waste acid concentration process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410825568.7A CN104555949A (en) | 2014-12-28 | 2014-12-28 | Titanium white waste acid concentration process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104555949A true CN104555949A (en) | 2015-04-29 |
Family
ID=53073161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410825568.7A Pending CN104555949A (en) | 2014-12-28 | 2014-12-28 | Titanium white waste acid concentration process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104555949A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564863A (en) * | 2016-11-15 | 2017-04-19 | 四川龙蟒钛业股份有限公司 | Hydrogen peroxide addition level control equipment for concentrated waste acid iron removal process |
| CN107915253A (en) * | 2017-11-29 | 2018-04-17 | 广西雅照钛白有限公司 | A kind of production method of titanium dioxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072154A (en) * | 1991-11-08 | 1993-05-19 | 日铁矿业株式会社 | The method of reclaim(ed) sulfuric acid from the sulfur waste acid of containing metal vitriol |
| CN102515114A (en) * | 2011-11-13 | 2012-06-27 | 山东鲁北企业集团总公司 | High-value and high-efficiency titanium white waste acid utilization method |
| CN103011272A (en) * | 2012-12-14 | 2013-04-03 | 四川龙蟒钛业股份有限公司 | Method for concentrating and purifying titanium dioxide waste acid by using complex acid |
-
2014
- 2014-12-28 CN CN201410825568.7A patent/CN104555949A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072154A (en) * | 1991-11-08 | 1993-05-19 | 日铁矿业株式会社 | The method of reclaim(ed) sulfuric acid from the sulfur waste acid of containing metal vitriol |
| CN102515114A (en) * | 2011-11-13 | 2012-06-27 | 山东鲁北企业集团总公司 | High-value and high-efficiency titanium white waste acid utilization method |
| CN103011272A (en) * | 2012-12-14 | 2013-04-03 | 四川龙蟒钛业股份有限公司 | Method for concentrating and purifying titanium dioxide waste acid by using complex acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564863A (en) * | 2016-11-15 | 2017-04-19 | 四川龙蟒钛业股份有限公司 | Hydrogen peroxide addition level control equipment for concentrated waste acid iron removal process |
| CN107915253A (en) * | 2017-11-29 | 2018-04-17 | 广西雅照钛白有限公司 | A kind of production method of titanium dioxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105039989B (en) | A kind of acid chlorization system copper-containing etching waste solution electrodeposition decopper(ing) and regeneration method | |
| CN102603000B (en) | Process for preparing high-purity vanadium pentoxide by adopting ammonium metavanadate as raw material | |
| CN103864153B (en) | PCB factory acidic etching liquid replacement extraction copper and the method preparing poly-ferric chloride | |
| CN103224261B (en) | Method for extracting inorganic salt in industrial wastewater and method for recycling industrial wastewater | |
| CN104911596A (en) | Device and method for cyclic regeneration and copper extraction of etching liquid | |
| CN104818385A (en) | Energy-saving, environmental-protection and zero-discharge technology of acidic waste etching solution resource recycling treatment | |
| CN102002595B (en) | Recovery method of lithium in waste battery | |
| CN103043759A (en) | Method for preparing polyaluminium ferric chloride flocculating agent by pickling waste liquid and waste aluminium material | |
| CN104555949A (en) | Titanium white waste acid concentration process | |
| CN104787946A (en) | Steel rolling waste acid complete resource recycling method | |
| CN104555948A (en) | Concentration technology for waste acid | |
| CN103014316A (en) | Novel method for processing lepidolite material | |
| CN104711636B (en) | Method for processing acidic etching waste solution of printed circuit board | |
| CN102627306A (en) | Novel method for preparing solid aluminum sulfate by using waste | |
| CN103964660B (en) | The acid wastewater treatment of acid-base neutralisation precipitator method process iron content produces the recovery process of mud | |
| CN106521159B (en) | Based on lithium in the extraction system extraction bittern containing Fe (III) and the method for recycling Fe (III) | |
| CN108217739A (en) | It is a kind of to prepare the method for manganese sulfate and its product obtained with troilite | |
| CN104058523B (en) | A kind for the treatment of process of vanadium oxide manufacture waste water | |
| CN103803631B (en) | The cupric micro-etching solution of circuit board etching is utilized to produce the method for copper sulfate | |
| CN108220995A (en) | The method of novel ammonium sulfate electrolysis production ammonium persulfate | |
| CN103319527A (en) | Production process for 1-hydroxy ethylidene-1,1-diphosphonic acid and acetylchloride | |
| CN107758719A (en) | A kind of environmentally friendly extracting process of high-purity ceria | |
| CN103979625A (en) | Mixing method for treating acid and alkaline etching waste liquid and nitric acid stripping waste liquid of printed-circuit boards | |
| CN104045063B (en) | A kind for the treatment of process of waste sulfuric acid solution | |
| CN108217747A (en) | It is a kind of to prepare the method for high purity manganese sulfate and its product obtained with manganese carbonate ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150429 |
|
| RJ01 | Rejection of invention patent application after publication |