CN1274590C - Production process of ordinary superphosphate with titanium white and waste acid - Google Patents
Production process of ordinary superphosphate with titanium white and waste acid Download PDFInfo
- Publication number
- CN1274590C CN1274590C CN 03125193 CN03125193A CN1274590C CN 1274590 C CN1274590 C CN 1274590C CN 03125193 CN03125193 CN 03125193 CN 03125193 A CN03125193 A CN 03125193A CN 1274590 C CN1274590 C CN 1274590C
- Authority
- CN
- China
- Prior art keywords
- acid
- titanium white
- complex acid
- acid solution
- liquid
- 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 - Lifetime
Links
Landscapes
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Fertilizers (AREA)
Abstract
The present invention relates to a method for producing ordinary superphosphate with waste acid of titanium white. The waste acid of titanium white can be used as dilute solution for secondary acid preparation to carry out acid preparation, a flocculating agent is added, and flocculating precipitates are removed; one part of the purified acid liquor is used as the dilute solution of primary acid preparation of concentrated sulphuric acid, the other part is mixed with phosphate powder, and the mixture is stirred, formed and slaked to obtain an ordinary superphosphate product. As ferrous sulfate heptahydrate is removed, the side effect of the ferrous sulfate heptahydrate on the phosphatic fertiliser production is effectively prevented. The purified liquor of the secondary acid preparation is used as the dilute solution of the primary acid preparation, the cooling effect of a graphite heat exchanger is ensured, the use quantity of the waste acid of titanium white is improved, and the production cost of the ordinary superphosphate is reduced.
Description
Technical field
The present invention relates to the method for utilizing of by product titanium white waste acid in the sulfuric acid method titanium pigment production technique, specifically a kind ofly produce the method that general calcium is calcium superphosphate with titanium white waste acid.
Background technology
At present, adopt Titanium White Production By Sulfuric Acid Process, 1 ton of titanium dioxide by-product of every production titanium white waste acid 8-10 ton, the main component in the titanium white waste acid is that weight percent concentration is about 18% sulfuric acid.And in the general calcium of dry production, weight percent concentration is that 93% or 98% the vitriol oil needs and water carries out the dilute sulphuric acid that the secondary complex acid is diluted to the required suitable concentration of decomposing rock phosphate with hydrogen, generally between 62%-70%, the calcium superphosphate product is produced in reaction to this concentration with ground phosphate rock again.Making the thinner of the vitriol oil with the titanium white waste acid place of water, is a kind of comparatively ideal approach of titanium white waste acid comprehensive utilization.But, owing to contain the ferrous sulfate of having an appointment about 5-8% in the titanium white waste acid, and in the formation process and maturing process of sulfuric acid and ground phosphate rock, Fe wherein
2O
3And FeSO
4Can change into the Fe that is insoluble in water
3(PO
4)
2.2H
2O and FePO
4.2H
2O causes the degeneration of general calcium available phosphorus.In order to prevent the influence of ferrous sulfate to phosphate fertilizer, the common solubleness that adopts vacuum-evaporation to improve the concentration of titanium white waste acid or reduce ferrous sulfate by cryogenic freezing, the ferrous sulfate crystallization is separated out, reduce the ferrous sulfate content in the titanium white waste acid, the shortcoming of these class methods is that not only facility investment is bigger, and when operation the energy consumption height, the cost of handling spent acid is higher.
Summary of the invention
In order to solve the high problem of cost that the treatment facility investment of removing ferrous sulfate in the above-mentioned method of utilizing titanium white waste acid to produce general calcium as the thinner of the vitriol oil is big, handle, the invention provides a kind of lower-cost method of utilizing titanium white waste acid to produce general calcium of removing ferrous sulfate.
A kind of method of producing general calcium with titanium white waste acid of the present invention comprises the steps:
A, the acid solution that titanium white waste acid is obtained through complex acid as diluent and the vitriol oil is mixed carries out the secondary complex acid, obtains secondary complex acid liquid;
B, in above-mentioned secondary complex acid liquid, add the flocculation agent polyacrylamide;
C, above-mentioned secondary complex acid liquid is carried out solid-liquid separation, remove the flocculating settling thing in the acid solution, be purified acid solution;
D, above-mentioned purification acid solution and ground phosphate rock is mixed obtains desired product through stirring, changing into slaking.
In order to improve the processing and utilizing amount of titanium white waste acid, the purification acid solution that obtains with above-mentioned steps C is as the diluent of a complex acid of the vitriol oil.
When secondary complex acid liquid concentration is higher than 65%, purify the fine setting of acid solution dilute with water concentration is reduced to about 65%, react with ground phosphate rock again.
Described flocculation agent polyacrylamide add-on is the 0.0005%-0.001% of secondary complex acid liquid weight.
Because the present invention adopts the ferrous sulfate in the flocculation agent removal sulfuric acid liquid, prevented that effectively ferrous sulfate to the side effect that phosphate fertilizer produces, making titanium white waste acid to be utilized well.Owing to adopt secondary complex acid scavenging solution as a complex acid diluent, make the ferrous sulfate in the complex acid liquid be undersaturated condition, make graphite heat exchanger can not stop up, guaranteed the cooling performance of graphite heat exchanger effectively, can reduce the running cost of interchanger because of the ferrous sulfate crystallization; And the diluent of a complex acid of purification acid solution effect of employing secondary complex acid; can replace water fully and make diluent; the utilization of titanium white waste acid is improved greatly; save the consumption of the vitriol oil; reduce the production cost of general calcium; therefore the present invention needs newly added equipment successfully to utilize hardly except increasing solid-liquid separating equipment on the basis of original dry technology for production and handles titanium white waste acid effectively, thus the protection environment.
Embodiment
Embodiment 1: elder generation is diluted to 80% concentration with complex acid of vitriol oil water of 93% or 98%, be cooled to 70 ℃ Celsius by graphite heat exchanger, add again and contain 18% vitriolic titanium white waste acid secondary complex acid to the required suitable concentration of decomposing rock phosphate with hydrogen, the required suitable concentration in this ore deposit is 65% in this example, and the acid temperature is at 90-95 ℃; Add polyacrylamide in secondary complex acid liquid, the add-on of polyacrylamide is 0.0005% of a secondary complex acid liquid weight, disperses in acid for the ease of polyacrylamide, can earlier polyacrylamide be dissolved in water and make solution, adds in the secondary complex acid liquid again; Stir, make ferrous sulfate precipitate flocculating settling, carry out solid-liquid separation again and remove the flocculating settling thing, be purified acid solution; Purify the diluent of a part of retrieval system place of water of acid solution as a complex acid of the vitriol oil, another part goes to decompose and contains P
2O
520-30%, fineness are 100 purpose ground phosphate rock, through mixing, changing into and slaking, obtain general calcium product.After testing, the available phosphorus P in the product
2O
5Content is greater than 12%, and available phosphorus does not have degradation phenomena, and product does not have caking.
Embodiment 2: method is the same, and wherein a complex acid concentration is 85%, 65 ℃ of acid temperature; Secondary complex acid concentration is 70%, and the acid temperature is at 80-85 ℃; The add-on of polyacrylamide is 0.001% of a secondary complex acid liquid weight, finely tunes with the purification acid solution dilute with water of ground phosphate rock reaction to make concentration reduce to 65%, and the acid temperature goes decomposition to contain P at 90-95 ℃ again
2O
520-30%, fineness are 100 purpose ground phosphate rock, through mixing, changing into and slaking, obtain general calcium product.The available phosphorus P of products obtained therefrom
2O
5Content is greater than 12%, and available phosphorus does not have degradation phenomena, and product does not have caking.Owing to purify acid strength a little more than decomposing rock phosphate with hydrogen suitable concentration 65%, can accurately regulate acid strength by the dilute with water fine setting.
Claims (4)
1, a kind of method of producing general calcium with titanium white waste acid comprises the steps:
A, the acid solution that titanium white waste acid is obtained through complex acid as diluent and the vitriol oil is mixed carries out the secondary complex acid, obtains secondary complex acid liquid;
B, in above-mentioned secondary complex acid liquid, add the flocculation agent polyacrylamide;
C, above-mentioned secondary complex acid liquid is carried out solid-liquid separation, remove the flocculating settling thing in the acid solution, be purified acid solution;
D, above-mentioned purification acid solution and ground phosphate rock is mixed obtains desired product through stirring, changing into slaking.
2, method according to claim 1 is characterized in that the purification acid solution that obtains with the step C diluent as a complex acid of the vitriol oil.
3, method according to claim 2 is characterized in that when secondary complex acid liquid concentration is higher than 65%, purifies the fine setting of acid solution dilute with water concentration is reduced to about 65%, reacts with ground phosphate rock again.
4,, it is characterized in that described polyacrylamide add-on is the 0.0005%-0.001% of secondary complex acid liquid weight according to claim 1 or 2 or 3 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03125193 CN1274590C (en) | 2003-05-13 | 2003-05-13 | Production process of ordinary superphosphate with titanium white and waste acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03125193 CN1274590C (en) | 2003-05-13 | 2003-05-13 | Production process of ordinary superphosphate with titanium white and waste acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1548363A CN1548363A (en) | 2004-11-24 |
| CN1274590C true CN1274590C (en) | 2006-09-13 |
Family
ID=34321852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03125193 Expired - Lifetime CN1274590C (en) | 2003-05-13 | 2003-05-13 | Production process of ordinary superphosphate with titanium white and waste acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1274590C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115210B (en) * | 2010-12-31 | 2012-10-17 | 谢善情 | Method for producing ferrous nitrate and calcium sulfate from waste acid generated during titanium dioxide production through sulfuric acid method |
| CN102674278B (en) * | 2012-05-25 | 2013-09-25 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorus rock by titanium dioxide waste acid |
| CN106315521B (en) * | 2016-08-18 | 2018-10-23 | 四川龙蟒钛业股份有限公司 | The recoverying and utilizing method of titanium white waste acid |
| CN110577203A (en) * | 2019-09-29 | 2019-12-17 | 贵州胜威福全化工有限公司 | Process for producing calcium superphosphate by using titanium dioxide byproduct waste acid |
-
2003
- 2003-05-13 CN CN 03125193 patent/CN1274590C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1548363A (en) | 2004-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110482512A (en) | A kind of preparation method of battery-grade iron phosphate | |
| CN102887535A (en) | Method for recycling high-purity fluorine and phosphorus from wastewater of phosphogypsum residue field | |
| CA1261116A (en) | Process of removing cationic impurities from wet process phosphoric acid | |
| CN101007626A (en) | Method for producing phosphate by wet method phosphoric acid purification and hydrochloric acid decomposition for phosphate ore | |
| CN107827113B (en) | Method for recovering fluorine in industrial monoammonium phosphate neutralized slag slurry | |
| CN114906829A (en) | Method for preparing battery-grade iron phosphate by adopting agricultural-grade wet-process phosphoric acid | |
| CN101434386A (en) | Method for producing fine phosphate by using dilute acid to decompose middle and low grade phosphate ore using | |
| CN102838097A (en) | Method for removing magnesium oxide in phosphate concentrate through phosphatic fertilizer and phosphorus chemical industry acid wastewater | |
| CN100528743C (en) | Process for preparing high purity phosphoric acid-ammonium by titanium dioxide waste acid | |
| CN115536042A (en) | Method for co-producing sodium bicarbonate and ammonium sulfate from SDS (sodium dodecyl sulfate) dry-process desulfurized fly ash | |
| CN1274590C (en) | Production process of ordinary superphosphate with titanium white and waste acid | |
| CN107416863A (en) | The method that the waste water of ferric phosphate production prepares technical grade ammonium salt | |
| CN1376635A (en) | Process for preparing phosphoric acid from waste sulfuric acid as by-product of titanium oxide powder by wet method | |
| CN110217769B (en) | Method for producing calcium ammonium nitrate byproduct feed-grade DCP | |
| CN111533099A (en) | Production method of water-soluble monoammonium phosphate | |
| CN101734634A (en) | Method for producing monopotassium phosphate | |
| CN107640778B (en) | A method of the low cost recycling sodium sulphate from leaded desulfurization waste liquor | |
| CN113772647B (en) | High-purity iron phosphate and method for preparing high-purity iron phosphate by adopting multistage purification method | |
| CN1363511A (en) | Process for preparing fluorine compound and SiO2 from sodium fluosilicate | |
| CN116639670A (en) | Method for preparing battery-grade ferric phosphate by adopting fertilizer-grade monoammonium phosphate | |
| CN106829900A (en) | The method that carbide slag is used for phosphoric acid by wet process desulfurization | |
| CN118255336B (en) | Method for preparing ferric phosphate based on ferric phosphate production wastewater and pyrite cinder | |
| CN112250052B (en) | Method for producing industrial monoammonium phosphate and magnesium ammonium phosphate slow release fertilizer by wet phosphoric acid | |
| CN115724453B (en) | Purification and recovery method of ferric phosphate mother liquor | |
| CN116692795A (en) | Potassium removal method for fertilizer grade monoammonium phosphate and application of product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: ANHUI ANNADA SCHORLOMITE CO., LTD. Free format text: FORMER OWNER: TONGLING CITY TONGGUANSHAN CHEMICAL CO., LTD. Effective date: 20060428 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20060428 Address after: 244000 Anhui city of Tongling province Tongguan Avenue South No. 1288 Applicant after: Anhui Annada Titanium Industry Co.,Ltd. Address before: 244000 Jin Shan Road, Anhui, Tongling Applicant before: Tongling Tongguanshan Chemical Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060913 |