CN100396733C - Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white - Google Patents
Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white Download PDFInfo
- Publication number
- CN100396733C CN100396733C CNB021484287A CN02148428A CN100396733C CN 100396733 C CN100396733 C CN 100396733C CN B021484287 A CNB021484287 A CN B021484287A CN 02148428 A CN02148428 A CN 02148428A CN 100396733 C CN100396733 C CN 100396733C
- Authority
- CN
- China
- Prior art keywords
- ammonia
- iron
- ferric oxide
- oxidation
- iron vitriol
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a method for producing ferric oxide red pigments by waste byproduct ferrous sulphate of titanium white. The hydrolysis is controlled for six hours to ten hours by the reduction of ferric sheets at a moderate temperature (from 50 DEG C to 70 DEG C), refining ferrous sulfate heptahydrate is prepared by flocculation and settlement separation, and the recovery rate reaches 95% to 98%. A crystalloid crystal seed of ferric oxide red is prepared by neutralization of ammonia by using a low concentration ferrous solution, and ammonia is used for neutralizing atmospheric oxygen to be synthesized into a ferric oxide red pigment. An oxidizing barrel is provided with a heating coil so as to ensure uniform mass transfer and heat transmission in industrial production. A byproduct ammonia sulfate solution is recovered, concentrated and crystallized to be used for producing compound fertilizers. The method is suitable for industrialization without secondary pollution.
Description
Technical field
The present invention relates to a kind of titanium white ferrous sulfate as side product and produce the method for ferric oxide red colorant.
Background technology
Titanium white is a kind of high-grade silene.Along with economy constantly develops, demand improves constantly, and only depends on import far can not meet the demands.China mainly adopts the Production By Sulfuric Acid Process titanium white at present.4 tons of ferrous sulfate of the about by-product of 1 ton of titanium white of the every product of this method.Because this ferrous sulfate can directly use, and also can discard, so again it is called ferrous sulfate as side product traditionally.Titanium white output in 2002 will reach 400,000 tons according to statistics, and ferrous sulfate as side product output will reach 1,600,000 tons.Like this a large amount of useless by product, as still adopting original stacking mode, shared place is big and the influence of environment all seriously restricted the titanium white industrial expansion.Though also had the people that the titanium white ferrous sulfate as side product is used to do iron catalyst, water purification agent, fodder additives, soil improvement agent etc., the quantity of treatable titanium white ferrous sulfate as side product seldom in the past.And it is the most effective to utilize the titanium white ferrous sulfate as side product to prepare iron oxide pigment, can digest ferrous sulfate as side product in a large number on the one hand, iron oxide pigment per ton approximately can consume 4 tons of ferrous sulfate as side product, and the P/C of iron oxide pigment is than good on the other hand, market outlet is good, and demand is big.Especially red iron oxide and iron oxide yellow.Once made many research-and-development activitys in this respect in the past.Once the someone adopts dry production iron oxide red and sulfuric acid in early days, but because institute's sulfuric acid concentration that produces is low, and iron oxide red is of low quality, and in course of industrialization, the very difficult solution of problems such as equipment corrosion.One of most critical issue that adopts the wet production ferric oxide red colorant is to remove a large amount of titanics contained in the titanium white ferrous sulfate as side product and a small amount of ferric iron.Chinese invention patent application 93101780.7 discloses the method for refining titanium white by product ferrous sulfate, and this method adopts pursues repeatedly soak acid-cleaning of pond, filtering and impurity removing, and high pressure, pyrohydrolysis refilter separating impurity then.The ferrous sulfate rate of recovery is 90%.But because of adopting high temperature, highly pressured hydrolysis, production cost height, industrializing implementation difficulty are big.Though Chinese invention patent application 93105994.1 has been done improvement to above-mentioned patented technology, but still there are complex treatment process, problem that production cost is high, the also difficult suitability for industrialized production that realizes.In the Chinese invention patent application 00113589.9 disclosed method with titanium white ferrous sulfate as side product production high-purity magnetic iron oxide, when purifying, after the ferrous sulfate as side product dissolving, adopt freezing and crystallizing to remove partial impurities earlier, be dissolved into solution again, use sulfuric acid and iron sheet hydrolysis method POV ferrous then.The freezing removal of impurity in this method is few to removing the titanium effect, has increased operation again, and cost is high and only be applicable to the production high-purity magnetic iron oxide, and can't handle ferrous sulfate as side product in a large number.In the Chinese invention patent application 94105891.3 disclosed process for refining, adopt sulfuric acid and reduced iron powder, 55～80 ℃ of insulations were hydrolyzed in 2～3 hours, and the colloidal titanium compound that contains in the solution after the hydrolysis adopts filter method to separate.Because this method do not consider the influence of hydrolysis rate to impurity hydrolysis degree and hydrolyzate form, so not only the incomplete removal of impurity efficient of hydrolysis is low, and the hydrolyzate strainability is poor, and making that separation efficiency is low can't industrialization.Adopting another key of wet production ferric oxide red colorant is crystal seed.The crystal seed that tradition sulfuric acid process and mixed acid process make is unformed particulate, and it is comparatively serious to flocculate, thereby has had a strong impact on the dispersiveness of final ferric oxide red colorant.
Summary of the invention
The objective of the invention is to, provide a kind of titanium white ferrous sulfate as side product to produce the method for ferric oxide red colorant.This method can be a raw material with the titanium white ferrous sulfate as side product, goes out to meet the ferric oxide red colorant of national standard and can not cause secondary pollution with technology and device fabrication that can suitability for industrialized production.
Realize the technical scheme of the object of the invention: a kind of titanium white ferrous sulfate as side product is produced the method for ferric oxide red colorant, the production stage of present method comprises that refining, the crystal seed preparation of ferrous sulfate, oxidation are synthetic, filters, washing, oven dry, pulverize, packing, it is characterized in that:
A) ferrous sulfate is refining
The useless secondary iron vitriol of dissolving titanium white, with the sulfuric acid adjust pH is 1.0～1.5, and press 1% of iron vitriol weight and add iron sheet, temperature is controlled at 50～70 ℃, and hydrolysis reached pH3.0～4.5 in about 6～10 hours, and being diluted to iron vitriol concentration is 350～450g/L, add flocculation agent, stirring, standing sedimentation 4～6 hours, supernatant liquid are refining iron vitriol solution, for preparation crystal seed and the synthetic usefulness of oxidation; Bottom residual precipitate thing enters in the useless vice processing pond of ferric oxide red colorant in producing, and focuses on qualified discharge;
B) crystal seed preparation
In traditional seed tank, ammonia and above-mentioned refining iron vitriol solution, at 10～25 ℃, with the air reaction that feeds from the seed tank bottom, through 2～3 hours, system pH reaches 9.5～9.7 scopes, promptly make reddish-brown crystalloid red iron oxide crystal seed, wherein, by weight the ammonia consumption be the reaction of ammonia and iron vitriol theoretical consumption 120～180%, reacting initial iron vitriol concentration is 15～30g/L, and initial pH is 9.6～9.9;
C) oxidation is synthetic
In the conventional oxidation bucket, the device heating coil, add above-mentioned crystal seed in the bucket, be warmed up in 60～95 ℃ of scopes and keep this temperature, system pH transfers in 2.0～5.0 scopes, add above-mentioned purified iron vitriol solution, air and ammonia simultaneously continuously, maintenance system pH value is in 2.0～5.0 scopes, iron vitriol concentration is in 10～45g/L scope, oxidation 40～130 hours, promptly make the red iron oxide slurry, the slurry form and aspect increase by slight yellow tinge, are with the red-purple phase change redly in opposite directions with oxidization time;
D) filter, wash, dry, pulverize, pack
The red iron oxide of pressing after currently known methods and equipment synthesize oxidation is starched, and filters successively, washes, dries, pulverizes and pack promptly to make the finished product ferric oxide red colorant;
E) reclaim(ed) sulfuric acid ammonium
With step D) in mother liquor after filtering reclaim and store, heating concentrates, cooling, crystallization, separation, makes ammonia sulfate crystal.
In the aforesaid method, step B) and step C) used ammonia is ammoniacal liquor, or ammonia.
In the aforesaid method, at step B) and step C) in, when using ammonia, from the bottom of seed tank and oxidation bucket through sparger feeding system; When using ammoniacal liquor, from the top adding system of seed tank and oxidation bucket.
In the aforesaid method, in steps A) in, used flocculation agent is a polyacrylamide, and its molecular weight is 3,000,000, and the flocculation agent consumption is 0.005～0.01% of iron vitriol weight by 100% polyacrylamide.
Technique effect of the present invention: it is that raw material is with the industrial-scale production ferric oxide red colorant that the inventive method has realized with the titanium white ferrous sulfate as side product.In the titanium white ferrous sulfate as side product, the impurity that mainly contains is Ti
+ 4And small amount of Fe
+ 3The existence of these impurity has a strong impact on the quality of pigment.Therefore, can thoroughly separate Ti
+ 4And Fe
+ 3Impurity becomes the key that the titanium white ferrous sulfate as side product is used to produce ferric oxide red colorant.According to Ti
+ 4And Fe
+ 3PH value during hydrolysis is different, and control pH value can reach isolating purpose.As everyone knows, Ti
+ 4Hydrolysis pH be 0.5～2.0, Fe
+ 3Be pH2.2～3.5, Fe
+ 2Be pH4.5～9.5.The pH value of the strict hierarchy of control can only make Ti
+ 4And Fe
+ 3Hydrolysis produces precipitation, and Fe
+ 2Hydrolysis can not take place again, thereby improve separating effect and improve the rate of recovery of ferrous sulfate.Method of the present invention, when POV was ferrous, initial pH value was 1.0～1.5, and 50～70 ℃ of reactions, control hydrolysis is for up to 6～10 hours, terminal point pH3.0～4.5.Compare with prior art (94105891.3), following advantage is arranged: 1. lesser temps prolongs hydrolysis time down, guarantees Ti
+ 4And Fe
+ 3Slowly hydrolysis and hydrolysis are complete; 2. replace reduced iron powder with iron sheet, not only production cost reduces, and because iron sheet and sulfuric acid reaction are slow, the pH value of system rises slower, guarantees Ti
+ 4And Fe
+ 3Hydrolysis is more abundant, and the removal of impurity is more thorough, easier, and don't can make Fe
+ 2Hydrolysis; 3. adopt the flocculation agent of suitable concentration, hydrolysate can adopt settlement separate, rather than filtering separation, like this, in industrial production, overcome the inefficient problem of filtering separation that causes because of hydrolysate filterableness difference, guaranteed the quality of POV ferrous iron solution again.Facts have proved that the ferrous sulfate rate of recovery can reach 95～98%, the titaniferous amount of iron vitriol is lower than 0.01%, meets the requirement of producing qualified ferric oxide red colorant.
In oxidation is synthetic, owing in the conventional oxidation bucket, added steam heating coil, thus guaranteed the industrializing implementation of this technology, compare with the conventional oxidation bucket simultaneously, solved mass transfer in the suitability for industrialized production, heat transfer problem better.Speed of reaction is more steady, and like this, when oxidation was synthetic, product pellet was grown up and evenly and not flocculated.Improve very favourable to quality product.The inventive method can be at 80m
3The oxidation bucket in carry out the production of ferric oxide red colorant.Single barrel of throughput can reach 600 tons/year.
Because crystal seed of the present invention preparation and oxidation all use ammonia as alkaline matter in synthesizing, prepared crystal seed has certain crystal formation (γ-FeOOH), uniform crystal particles.Adopt ammonia to make alkaline matter when oxidation is synthetic, make the growth of ferric oxide red colorant particle steadily even.Guaranteed the finished product excellent dispersion, the purity height.In addition, owing to use ammonia as alkaline matter, the by product of Sheng Chenging is an ammonium sulfate in process of production, can reclaim as composite fertilizer, can not produce secondary pollution to environment.
The a little amount of titanium that is produced when POV is ferrous, iron precipitate can be handled together with other waste residue, waste water in the ferric oxide red colorant production, and do not need to set up treatment unit separately for using the titanium white ferrous sulfate as side product to produce ferric oxide red colorant.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
Raw material
1, ferrous sulfate is the sulfate process titanium dioxide ferrous sulfate as side product, its FeSO
47H
2O content 86～92%, impurity titanium (Ti
+ 4) content 0.2～1.0%, iron (Fe
+ 3) content 0.1～1.0%;
2, sulfuric acid is the technical grade vitriol oil, H
2SO
4Content 93～98%;
3, iron sheet is cold rolled sheet (1.0mm is following) leftover bits;
4, flocculation agent is a polyacrylamide, its concentration 20%, molecular weight 3,000,000;
5, ammonia is a technical grade liquefied ammonia;
6, ammoniacal liquor is technical grade, ammonia content 15～25%;
Making with extra care of embodiment 1 ferrous sulfate
At volume is 10m
3Corrosion-resistant groove in, add 7.0m
3Water adds 7.0 tons of titanium white ferrous sulfate as side product (90%) again, this moment, the iron vitriol strength of solution was 700g/L, add the 112kg vitriol oil (98%), the initial pH of system is 1.0～1.5, add the 63kg iron sheet, logical steam keeps system temperature at 60 ℃, keeps 8 hours and surveys system pH in 3.0～4.5 scopes.Squeeze into 20m with pump then
3Settling vat in, add water to cumulative volume 16.5m
3, the iron vitriol concentration dilution is to 400g/L, and adding 2.2kg concentration is 20% polyacrylamide flocculant, and its consumption is about 0.007% of iron vitriol weight, stirs 10 minutes, leaves standstill 6 hours, can isolate supernatant liquid 15.8m
3, being purified iron vitriol solution, its concentration is 400g/L, titanium content is 0.005%.The iron vitriol 312kg that deduction is generated by the 63kg iron sheet, the yield of actual titanium white ferrous sulfate as side product are 400 * 15.8-312/0.9 * 7000=95.4%.Can repeat to make multiple batches of with aforesaid method according to the requirement of actual production.For preparation crystal seed and the synthetic use of oxidation; Above-mentioned 20m
3The throw out of settling vat bottom, be discharged in ferric oxide red colorant other useless vice processing ponds in producing, after focusing on, qualified discharge.
Embodiment 2 crystal seeds preparations (employing ammonia)
Present embodiment adopts traditional seed tank, and volume is 40m
3Air or the ammonia pipe at the bottom of the bucket enters seed tank and through the ventilating pit of air-distributor is evenly distributed to reaction system in the bucket.
In above-mentioned seed tank, inject 30m earlier
3Water feeds the 146.7kg ammonia from the seed tank bottom again, and hierarchy of control temperature adds 2m at 20 ℃
3Iron vitriol concentration is 25g/L in the refining iron vitriol solution (400g/L) that is made by embodiment 1, this moment bucket, pH value about 9.8, and the ammonia consumption is 150% of the theoretical consumption that reacts of ammonia and iron vitriol.System pH was reached in 9.5～9.7 scopes in about 2 hours from bucket bottom bubbling air then.Promptly make reddish-brown crystalloid red iron oxide crystal seed 230.2kg (with Fe this moment
2O
3Meter), use is combined in oxygen supply;
Embodiment 3 crystal seeds preparations (directly adopting ammoniacal liquor)
The seed tank that present embodiment adopted, except that the ammoniacal liquor scale tank is equipped with on seed tank top, all the other are all with embodiment 2.
In the above-mentioned seed tank, add ammoniacal liquor (20%) with the ammoniacal liquor scale tank, its amount is 733.5kg, and following steps and dosage are all with embodiment 2.Use is combined in the reddish-brown crystalloid red iron oxide crystal seed oxygen supply that makes.
The method of present embodiment is particularly suitable for selecting for use near the user of ammoniacal liquor factory.
Embodiment 4 oxidations are synthetic
The oxidation bucket that present embodiment adopts, removing volume is 80m
3, and be equipped with outside the heating coil, all the other are identical with the conventional oxidation bucket.
The red iron oxide crystal seed 230.2kg that adding embodiment 2 or 3 makes in above-mentioned oxidation bucket is (with Fe
2O
3Meter), in heating coil, feed steam, be warming up to 70～85 ℃, and keep this temperature, add sulfuric acid and transfer to pH3.5, maintenance system iron vitriol concentration is 15～20g/L scope.Adding concentration is the refining iron vitriol solution of 400g/L, pipe from oxidation bucket bottom adds ammonia through air-distributor simultaneously, with maintenance system pH value 3.0～4.5 scope oxidations 90 hours, make form and aspect and be the slurry that red-purple contains red iron oxide 8400kg, consume the refining iron vitriol of 28390kg altogether.According to the difference that the user requires the product form and aspect, oxidization time can be slightly different.
With prepared red iron oxide slurry, existing technology and the equipment of producing ferric oxide red colorant of employing filters successively, washes, dries, pulverizes and packing makes ferric oxide red colorant 7980kg.
By the foregoing description as can be known, adopt the inventive method to produce finished product ferric oxide red colorant 7980kg, consume (90%) 32.33 ton of titanium white ferrous sulfate as side product.Amount to one ton of ferric oxide red colorant of every production and can handle 4.05 tons of titanium white ferrous sulfate as side product.
The mother liquid obtained recovery of above-mentioned filtration operation is stored, and delivers to heat in the vaporizer to concentrate, and reaches 118 ℃ until temperature and stops heating, obtains ammonia sulfate crystal through cooling, crystallization, separation.Can be used as composite fertilizer.
Embodiment 5 product quality inspections
Embodiment 4 gained ferric oxide red colorants are pressed the national standard method check, and the result reaches the HO of GB1863-89
01-04First grade.
Embodiment 6 is the feedstock production ferric oxide red colorant with pickling sulfur waste ferrous iron solution
Adopt known method with pickling sulfur waste acid ferrous iron solution refining after, adopt embodiment 2 or 3 and the ferric oxide red colorant that makes of the same procedure of embodiment 4, press national standard method and check, the result reaches the HO of GB1863-89
01-04First grade.
Embodiment 7 prepares ferric oxide red colorant with the ferrous sulfate of iron sheet and sulfuric acid preparation
Adopt known method to make copperas solution earlier with iron sheet and sulfuric acid, adopt then embodiment 2 or 3 and the same procedure of embodiment 4 make ferric oxide red colorant.Press the national standard method check, the result reaches the HO of GB1863-89
01-04First grade.
Claims (4)
1. a titanium white ferrous sulfate as side product is produced the method for ferric oxide red colorant, the production stage of present method comprises that refining, the crystal seed preparation of ferrous sulfate, oxidation are synthetic, filters, washing, oven dry, pulverize, packing, it is characterized in that:
A) ferrous sulfate is refining
The useless secondary iron vitriol of dissolving titanium white, with the sulfuric acid adjust pH is 1.0～1.5, and press 1% of iron vitriol weight and add iron sheet, temperature is controlled at 50～70 ℃, and hydrolysis reached pH3.0～4.5 in 6～10 hours, and being diluted to iron vitriol concentration is 350～450g/L, add flocculation agent, stirring, standing sedimentation 4～6 hours, supernatant liquid are refining iron vitriol solution, for preparation crystal seed and the synthetic usefulness of oxidation; Bottom residual precipitate thing enters in the useless vice processing pond of ferric oxide red colorant in producing, and focuses on qualified discharge;
B) crystal seed preparation
In traditional seed tank, ammonia and above-mentioned refining iron vitriol solution, at 10～25 ℃, with the air reaction that feeds from the seed tank bottom, through 2～3 hours, system pH reaches 9.5～9.7 scopes, promptly make reddish-brown crystalloid red iron oxide crystal seed, wherein, by weight the ammonia consumption be the reaction of ammonia and iron vitriol theoretical consumption 120～180%, reacting initial iron vitriol concentration is 15～30g/L, and initial pH is 9.6～9.9;
C) oxidation is synthetic
In the conventional oxidation bucket, the device heating coil, add above-mentioned crystal seed in the bucket, be warmed up in 60～95 ℃ of scopes and keep this temperature, system pH transfers in 2.0～5.0 scopes, add above-mentioned purified iron vitriol solution, air and ammonia simultaneously continuously, maintenance system pH value is in 2.0～5.0 scopes, iron vitriol concentration is in 10～45g/L scope, oxidation 40～130 hours, promptly make the red iron oxide slurry, the slurry form and aspect increase by slight yellow tinge, are with the red-purple phase change redly in opposite directions with oxidization time;
D) filter, wash, dry, pulverize, pack
Press currently known methods and equipment to oxidation the red iron oxide slurry after synthetic, filter successively, wash, dry, pulverize and pack and promptly make the finished product ferric oxide red colorant;
E) reclaim(ed) sulfuric acid ammonium
With step D) in mother liquor after filtering reclaim and store, heating concentrates, cooling, crystallization, separation, makes ammonia sulfate crystal.
2. method according to claim 1 is characterized in that: step B) and step C) used ammonia is ammoniacal liquor, or ammonia.
3. method according to claim 1 and 2 is characterized in that: at step B) and step C) in, when using ammonia, from the bottom of seed tank and oxidation bucket through sparger feeding system; When using ammoniacal liquor, from the top adding system of seed tank and oxidation bucket.
4. method according to claim 1 is characterized in that: in steps A) in, used flocculation agent is a polyacrylamide, and its molecular weight is 3,000,000, and the flocculation agent consumption is 0.005～0.01% of iron vitriol weight by 100% polyacrylamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021484287A CN100396733C (en) | 2002-12-04 | 2002-12-04 | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021484287A CN100396733C (en) | 2002-12-04 | 2002-12-04 | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415665A CN1415665A (en) | 2003-05-07 |
| CN100396733C true CN100396733C (en) | 2008-06-25 |
Family
ID=4751413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021484287A Expired - Fee Related CN100396733C (en) | 2002-12-04 | 2002-12-04 | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100396733C (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318518C (en) * | 2005-05-27 | 2007-05-30 | 华南理工大学 | Process for preparing iron oxide red by using sulfuric acid crystal seed mixed acid method and products thereby |
| CN100357361C (en) * | 2005-08-23 | 2007-12-26 | 奚长生 | Method for preparing high purity iron oxide yellow and iron oxide red using titanium dioxide byproduct ferrous sulfate |
| CN100484881C (en) * | 2006-08-10 | 2009-05-06 | 攀枝花锐龙冶化材料开发有限公司 | Method of producing iron oxide red using ferrous sulphate |
| CN101607741B (en) * | 2008-06-19 | 2011-02-02 | 张晓东 | Method for preparing iron oxide red by byproduct ferrous sulfate of titanium dioxide |
| CN102092794B (en) * | 2010-12-08 | 2012-08-08 | 浙江大学 | Preparation method of nano iron oxide yellow or nano iron oxide red |
| CN103145197B (en) * | 2011-12-06 | 2015-04-08 | 北京三聚环保新材料股份有限公司 | Refining method of titanium dioxide by-product ferrous sulphate |
| CN102976413B (en) * | 2012-10-29 | 2014-06-25 | 中国有色集团（广西）平桂飞碟股份有限公司 | Two-step oxidation production method for iron oxide red pigment |
| CN104016418B (en) * | 2014-06-27 | 2016-01-20 | 四川金沙纳米技术有限公司 | Titanium dioxide waste residue ferrous sulfate is utilized to prepare the method for iron oxide black fast |
| CN104129816B (en) * | 2014-07-31 | 2016-03-30 | 襄阳龙蟒钛业有限公司 | The method of a kind of titanium white gelled acid deironing |
| CN104310489B (en) * | 2014-10-10 | 2016-09-07 | 升华集团德清华源颜料有限公司 | A kind of preparation method of iron oxide red without ammonium oxidation |
| CN104556243B (en) * | 2014-12-22 | 2016-06-29 | 上海宝钢磁业有限公司 | The technique that pigment iron oxide red is prepared in the iron oxide red post processing of a kind of steel mill |
| CN105217694A (en) * | 2015-08-26 | 2016-01-06 | 昆明理工大学 | A kind of method preparing red iron oxide and ammonium chloride |
| CN105753068A (en) * | 2016-02-04 | 2016-07-13 | 河北爱德斯蒂尔环保科技有限公司 | Method for preparing iron oxide red through steel acid pickling waste liquor |
| CN106115793B (en) * | 2016-06-21 | 2018-01-02 | 阳山景润陶瓷色料实业有限公司 | A kind of ferric oxide red colorant and preparation method thereof |
| CN106800314B (en) * | 2016-12-23 | 2019-01-29 | 天津理工大学 | Method of the lateritic nickel ore pickle liquor except iron while wet production ferric oxide red colorant |
| CN108640162B (en) * | 2018-07-10 | 2024-01-09 | 河南省睿博环境工程技术有限公司 | Alkali circulation iron-containing solid waste iron oxide pigment production equipment system |
| CN108640163A (en) * | 2018-07-12 | 2018-10-12 | 佛山市信利成机电设备有限公司 | Iron oxide red production system and apply its iron-oxide red production method |
| CN109354072B (en) * | 2018-09-25 | 2021-05-28 | 河南省睿博环境工程技术有限公司 | Process for harmlessly producing iron oxide red pigment by alkali circulation method |
| CN109824090A (en) * | 2019-04-01 | 2019-05-31 | 中钢集团南京新材料研究院有限公司 | A method of it is prepared using titanium white by product object high-purity iron oxide red |
| CN109896550B (en) * | 2019-04-29 | 2021-06-22 | 中钢集团南京新材料研究院有限公司 | Method for preparing iron oxide red by recycling ternary precursor waste liquid |
| CN113929150A (en) * | 2021-09-06 | 2022-01-14 | 江苏宇星科技有限公司 | Production process for preparing iron oxide red serving as precursor of lithium iron phosphate by hydrothermal method of ferrous sulfate serving as titanium dioxide byproduct |
-
2002
- 2002-12-04 CN CNB021484287A patent/CN100396733C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1415665A (en) | 2003-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100396733C (en) | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN100396734C (en) | Method for producing the yellow pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN101792185B (en) | Method for preparing lamellar ferric oxide by ferreous solution ammonia precipitation method | |
| CN101792187B (en) | Method for producing feed grade ferrous sulfate monohydrate from titanium pigment waste acid condensed slag | |
| CN102583575B (en) | Method for producing pigment-level iron oxide red by using titanium dioxide waste residue ferrous sulfate | |
| CN104016418A (en) | Method for rapidly preparing black iron oxide from ferrous sulfate as titanium dioxide waste residue | |
| CN110540246A (en) | Method for preparing high-purity ferrous sulfate heptahydrate from sulfuric acid method titanium dioxide wastewater | |
| CN102602974A (en) | Method for producing less-barium fine strontium salts from celestite | |
| CN108862393A (en) | A method of manganese carbonate is prepared using Mn-bearing waste water | |
| CN109835951B (en) | System and method for producing powdered vanadium by chlorination process | |
| CN106348334A (en) | Feed-level copper sulfate and production technology thereof | |
| CN111661966A (en) | Titanium dioxide hydrolysis waste acid resource utilization treatment process | |
| CN1386710A (en) | Process for preparing superfine iron oxide | |
| CN109354072B (en) | Process for harmlessly producing iron oxide red pigment by alkali circulation method | |
| CN108569812B (en) | Treatment system and treatment method for wastewater containing low-concentration sulfuric acid | |
| CN101559986A (en) | Method for producing iron oxide black | |
| AU2016318839B2 (en) | Recycling process of wastewater containing ammonium ion and preparation method of metal oxide | |
| CN108640162B (en) | Alkali circulation iron-containing solid waste iron oxide pigment production equipment system | |
| CN1254023A (en) | Leaching-out method for extracting vanadium from vanadium-containg ore calcines and its application in stone-coal calcination-direct vanadium-extracting process | |
| CN101913656A (en) | Method for preparing iron oxide yellow pigment by using titanium white by-product of ferrous sulfate | |
| CN102115207B (en) | Method for producing ferrous carbonate and ammonium sulfate by using waste acid obtained during production of titanium pigment by adopting sulfuric acid process | |
| CN100484881C (en) | Method of producing iron oxide red using ferrous sulphate | |
| CN1156406C (en) | Process of producing high-purity magnetic iron oxide with ferous sulfate as by-product of titanium white production | |
| CN102115209B (en) | Method for producing ferrous nitrate and barium sulfate by using waste acid obtained by producing titanium white by sulfuric acid method | |
| CN100375716C (en) | Method of recovering V2O5 from Bayer process mother liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CNOOC CHANGZHOU PAINT + COATINGS INDUSTRY RESEARCH Free format text: FORMER OWNER: CHANGZHOU INST OF PAINT CHEMICAL, CHINESE CHEMICAL BUILDING CORP. Effective date: 20120910 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20120910 Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC Changzhou Paint & Coatings Industry Research Institute Address before: 213016 Airport Road, Jiangsu, Changzhou Patentee before: Changzhou Inst of Paint Chemical, Chinese Chemical Building Corp. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080625 Termination date: 20181204 |