CN106829900A - The method that carbide slag is used for phosphoric acid by wet process desulfurization - Google Patents
The method that carbide slag is used for phosphoric acid by wet process desulfurization Download PDFInfo
- Publication number
- CN106829900A CN106829900A CN201710014800.2A CN201710014800A CN106829900A CN 106829900 A CN106829900 A CN 106829900A CN 201710014800 A CN201710014800 A CN 201710014800A CN 106829900 A CN106829900 A CN 106829900A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- desulfurization
- wet process
- slurry
- carbide slag
- 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/265—General methods for obtaining phosphates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
Phosphatic technique is produced the present invention relates to a kind of wet phosphoric acid, a kind of carbide slag is specifically disclosed for the method for phosphoric acid by wet process desulfurization, comprised the following steps：A, toward the mashing that adds water in carbide slag；B, toward adding oxidant in slurry；C, filtering oxidation slurry；D, filter residue is washed；E, toward the mashing that adds water in washing slag；F, washing slurry is added in phosphoric acid by wet process to be desulfurization and carries out desulphurization reaction.It is an advantage of the invention that：1）Propose a kind of recoverying and utilizing method of carbide slag；2）Propose a kind of method of phosphoric acid by wet process desulfurization；3）Realize that Production of PVC technique and phosphate production technique are organically combined.
Description
Technical field
Phosphatic technique is produced the present invention relates to a kind of wet phosphoric acid, it is especially a kind of to utilize Production of PVC mistake
Accessory substance carbide slag in journey is the method for phosphoric acid by wet process desulfurization.
Background technology
Phosphoric acid by wet process is referred to as with sulfuric acid, nitric acid or phosphoric acid obtained in decomposing phosphate rock by chlorhydric acid, and with obtained in sulfuric acid decomposition phosphorus ore
The method of phosphoric acid is most basic method in Wet-process Phosphoric Acid Production.The characteristics of sulfuric acid process is that the product phosphoric acid after ore decomposition is liquid
Phase, byproduct calcium sulfate is the solid phase of solubility very little.Both separation are simple solid-liquor separations, with other processes
Unrivaled superiority.Therefore, Production By Sulfuric Acid Process phosphoric acid process is in leading position in Wet-process Phosphoric Acid Production.
Phosphoric acid by wet process due to containing a large amount of impurity, mainly for the production of high-concentration phosphate compound fertilizerses material, it is necessary to after being purified,
The phosphatic requirement high of production added value can be met.Phosphoric acid by wet process has larger difficulty on purification techniques, at present, in the world only
Have industrialized units few in number operation, it is domestic then be in conceptual phase, not yet realize industrialize.
Phosphate is produced using Wet Processes of Phosphoric Acid, by taking the production of ammonium phosphate product as an example, following steps is typically include：
(1) phosphorus ore defibrination：By rock phosphate in powder it is broken after added water in ball mill and carry out defibrination and obtain ore pulp；
(2) make ore pulp and strong sulfuric acid response, and control the phosphoric acid concentration in reaction solution；
(3) phosphorus ore extraction slurry in turn filtered, one wash and two wash, clear up filter residue, rinse the filtrate that obtains with and wash
Liquid；
(4) phosphoric acid obtained by phosphorus ore extraction slurry filtration and gas ammonia reaction obtained directly being concentrated after phosphorus ammonium mother liquor, sprayed
Mist obtains phosphor ammonium product after drying.
In the production of phosphoric acid by wet process, in order to improve the resolution ratio and control calcium sulfate crystal whiskers of phosphorus ore, generally require to add
Excessive sulfuric acid, therefore often contain 2.0~4.0% excess sulfuric acid in phosphoric acid by wet process.In Wet-process Phosphoric Acid Production phosphate,
Sulfuric acid that certainly will first in removing system, contains excessive sulfate in the phosphate product for otherwise obtaining, have a strong impact on product
Quality.SO4 2-Content is higher in phosphoric acid by wet process, is difficult to eliminate, and the method that each researcher takes is more, but summarizes, mainly
It is by calcium salt or barium salt is added in phosphoric acid by wet process, being allowed to and the SO for dissociating4 2-Reaction, generation acid insoluble calcium sulfate and sulphur
Sour precipitated barium.Selectable desulfurizing agent is inexpensive, be easy to get, and does not cause phosphorus to lose, therefore generally selects and SO4 2-Generation is insoluble
Ground phosphate rock, calcium carbonate, barium carbonate of calcium sulfate and barium sulfate etc. are desulfurizing agent.But logical the producing of phosphorus ore price is 400 yuan/ton, carbon
Sour calcium powder price is 80 yuan/ton, then up to 2500 yuan/ton of barium carbonate price, and price is higher, has had a strong impact on phosphate product
The competitiveness of product.
Acetylene method produces polyvinyl chloride（PVC）, raw material is that the acetylene for producing is hydrolyzed from calcium carbide, and hydrogen chloride gas are being urged
Generation vinyl chloride is reacted in the presence of agent mercury oxide.Polymerisation generation polyvinyl chloride is carried out in polymeric kettle again.Due to me
State has an abundant cheap coal resources, therefore generates calcium carbide calcium carbide with coal and lime stone and then calcium carbide adds water generation second
The production line of alkynes has obvious cost advantage, therefore the current Production of PVC of China is with acetylene method process route
It is main.
Carbide slag, calcium carbide hydrolysis obtains the waste residue with calcium hydroxide as main component after acetylene gas.Acetylene（C2H2）It is base
One of important source material of this organic synthesis industry, with calcium carbide（CaC2）It is raw material, adds water（Wet method）Produce the process is simple of acetylene
Maturation, 1t calcium carbides add water can generate kg acetylene gas more than 300, while generating the industrial wastes of 10t solid contents about 12%, be commonly called as calcium carbide
Slurry, its main chemical reactions formula is as follows：
CaC2+ 2H2O ﹦ C2H2+ Ca(OH)2
In calcium carbide and water reaction simultaneously, impurity also assists in reaction generation calcium hydroxide and other gases in calcium carbide：
CaO + H2O ﹦ Ca (OH)2；
CaS + 2H2O ﹦ Ca (OH)2 + H2S↑；
Ca3N2+6H2O ﹦ 3Ca (OH)2+2NH3↑；
Ca3P2 + 6H2O ﹦ 3Ca (OH)2 + 2PH3↑ ；
Ca(OH)2Solubility is small in water, solid Ca (OH)2Particulate is progressively separated out from solution.Whole system from true solution to
Colloidal solution, coarse dispersion system transition, particulate progressively merge, coalesce, precipitate, again because particle is mutually collided in precipitation process
Hit, extrude, promote particle further knot gather, grow up, dehydration, sediment progressively retrogradation is commonly called as carbide slag slurries.Usual enterprise is by electricity
Rock ballast slurry carries out separation of solid and liquid, obtains carbide slag and carbide slag slurry supernatant（Phosphine containing, sulfide, ammonia nitrogen）, carbide slag presses
Stacked according to national stacking standard.
The content of the invention
To make full use of accessory substance carbide slag resource, and phosphatic production cost is reduced, the invention provides a kind of electricity
The method that rock ballast is used for phosphoric acid by wet process desulfurization.
The technical solution adopted in the present invention is：The method that carbide slag is used for phosphoric acid by wet process desulfurization, comprises the following steps：
A, toward the mashing that adds water in carbide slag, obtain slurry；
B, toward add in slurry it is oxidizing in slurry without PH3And sulfide detection, obtain aoxidizing slurry；
C, filtering oxidation slurry, obtain filtrate and filter residue；
D, filter residue be washed in water lotion without ammonia nitrogen detection, obtain water lotion and washing slag；
E, toward in washing slag plus mashing is beaten with water, obtain washing slurry；
F, will washing slurry be added to by a certain percentage in phosphoric acid by wet process to be desulfurization, carry out desulphurization reaction；
G, sedimentation separation will be carried out by the phosphoric acid by wet process of desulfurization process, obtain supernatant liquor and thick slurry, supernatant liquor is conjunction
The desulfurization phosphoric acid by wet process of lattice.
The main component of carbide slag is calcium hydroxide（Account for about the 60% of gross mass）, in the present invention, inventor proposes, can
Try for carbide slag to be used for phosphoric acid by wet process desulfurization.But because carbide slag is carbide slag slurries filtering gained, therefore, because carbide slag
Liquid is eaten, wherein the also composition containing carbide slag slurry supernatant（Sulfide, hydrogen phosphide, ammonia nitrogen）, these compositions account for the total matter of carbide slag
About the 40% of amount.To ensure phosphatic quality, these harmful components can not enter phosphate production system, therefore the present invention is logical
The analysis to harmful components in carbide slag is crossed, above method is devised to remove the harmful components in carbide slag, and will be purified
The carbide slag for the treatment of is used for phosphoric acid by wet process desulfurization, to widen the purposes of carbide slag.Realize Production of PVC technique and phosphate
The combination of production technology.
As a further improvement on the present invention, using the water lotion in the filtrate in step C and step D as phosphate production
Phosphorus ore refining process water is used in technique.
Phosphate production, main has phosphorus ore pulping water, pump class cooling water or recirculated water, concentration tower shower water with water spot
Deng, but the necessary closed circulation of all waste water of phosphate production, final water is in vapour form into air, therefore phosphatic system
System moisturizing can consider that only phosphorus ore defibrination needs process water for technique productions needs.By adding oxidant in carbide slag
Removal toxicant hydrogen phosphide, may be such that in rear subsequent filtrate and water lotion not phosphine containing, so as to can be used for phosphorus ore defibrination, finally
By enrichment process, moisture evaporation, all salinities enter phosphate product.Wherein, the phosphate radical in filtrate and water lotion is filled
Divide and utilize, be converted into phosphate, nitrogen enters phosphate product in the form of ammonium salt.
More preferably, the phosphate production technique is the production technology of ammonium phosphate fertilizers.Due in filtrate and water lotion
Nitrogen enter phosphate product in the form of ammonium salt, therefore, if filtrate and water lotion to be used for the production work of ammonium phosphate fertilizers
Skill, is capable of achieving effective recovery of ammonia nitrogen resource in carbide slag.
As a further improvement on the present invention, the thick slurry that will be obtained in step G returns to phosphorus ore extraction in phosphate production technique
Take workshop section.Can be reclaimed containing many phosphoric acid in thick slurry, because the calcium sulfate crystal formation generated in sweetening process is poor, therefore directly
Filtering can be difficult to filter, if added to extraction tank by crystallizing again, calcium sulfate crystal grain can be greatly improved, and be easy to
Filter.
As a further improvement on the present invention, the oxidant for being added in step B is hydrogen peroxide.Hydrogen peroxide is cheap, by
Then liquid oxidizer, is easy to be used in actual production, and the reduzate of hydrogen peroxide is water, completely green, will not be introduced new
Impurity.
As a further improvement on the present invention, the water of carbide slag mashing is the work during phosphate production in step A
Skill water.The process water can be vacuum pump circulating water, pump cooling water, hydrogen mother liquor of calcium water etc..
As a further improvement on the present invention, washing slag mashing water is the technique during phosphate production in step E
Water or band desulfurization phosphoric acid by wet process or desulfurization phosphoric acid by wet process.Wherein process water can be vacuum pump circulating water, pump cooling water, hydrogen calcium mother
Liquid water etc..
As a further improvement on the present invention, the addition of washing slag slurry is in step F：Hydrogen in the washing slurry for being added
Calcium oxide is with the mol ratio of sulfate radical in phosphoric acid by wet process to be desulfurization：Ca（OH）2:SO4 2-=1.00~1.05:1.00.Washing slag
Slurry is slight excessive to ensure desulfurization completely, fully.
The beneficial effects of the invention are as follows：1）Propose a kind of recovery profit of accessory substance carbide slag in Production of PVC technique
With method, the purposes of carbide slag has been widened；2）A kind of method of phosphoric acid by wet process desulfurization is proposed, the method can substantially reduce phosphoric acid
The production cost of salt；3）Whole technique remaining reagent in addition to hydrogen peroxide is retrieved from the accessory substance of phosphate production technique, and whole
Accessory substance produced by individual technique can be utilized into phosphate production technique as resource so that Production of PVC technique
Organically combined with phosphate production technique.
Specific embodiment
1st, 100kg carbide slags are weighed, the mashing of 400kg running water is added, slurry is obtained.
2nd, toward addition hydrogen peroxide 100kg in slurry, fully after reaction, hydrogen phosphide and sulfide content in detection slurry,
If there is detection, continue to add a small amount of hydrogen peroxide, duplicate detection, until without the detection of above harmful substance, obtaining aoxidizing slurry.
3rd, filtering oxidation slurry, obtains filtrate and filter residue；Using filtrate as phosphorus ore defibrination in ammophos production technology
Process water is used.
4th, filter residue be washed in water lotion and detected without ammonia nitrogen, obtain water lotion and washing slag；Using water lotion as
Phosphorus ore refining process water is used in ammophos production technology.
5th, toward adding in washing slag phosphoric acid by wet process 1000kg to be desulfurization to be beaten, washing slurry is obtained；In detection washing slurry
Sulfate radical content in calcium hydroxide content and phosphoric acid to be desulfurization.
6th, washing slurry is added in phosphoric acid by wet process to be desulfurization by a certain percentage, additional proportion is the hydrogen washed in slurry
The mol ratio of the sulfate ion in calcium oxide and phosphoric acid by wet process to be desulfurization is：Ca（OH）2:SO4 2-=1.02:1.00；It is fully mixed
After conjunction, injecting the mixture into desulfurization acid storage tank carries out desulphurization reaction.
7th, sedimentation separation will be carried out by the phosphoric acid by wet process of desulfurization process, obtains supernatant liquor and thick slurry, supernatant liquor is
It is qualified desulfurization phosphoric acid by wet process；The area that thick slurry then directly returns into phosphorus ore extraction tank is crystallized again.
Claims (8)
1. the method that carbide slag is used for phosphoric acid by wet process desulfurization, it is characterised in that comprise the following steps：
A, toward the mashing that adds water in carbide slag, obtain slurry；
B, toward add in slurry it is oxidizing in slurry without PH3And sulfide detection, obtain aoxidizing slurry；
C, filtering oxidation slurry, obtain filtrate and filter residue；
D, filter residue be washed in water lotion without ammonia nitrogen detection, obtain water lotion and washing slag；
E, toward in washing slag plus mashing is beaten with water, obtain washing slurry；
F, will washing slurry be added to by a certain percentage in phosphoric acid by wet process to be desulfurization, carry out desulphurization reaction；
G, sedimentation separation will be carried out by the phosphoric acid by wet process of desulfurization process, obtain supernatant liquor and thick slurry, supernatant liquor is conjunction
The desulfurization phosphoric acid by wet process of lattice.
2. the method that carbide slag according to claim 1 is used for phosphoric acid by wet process desulfurization, it is characterised in that：By in step C
Water lotion in filtrate and step D is used as phosphorus ore refining process water in phosphate production technique.
3. the method that carbide slag according to claim 2 is used for phosphoric acid by wet process desulfurization, it is characterised in that：The phosphate life
Production. art is the production technology of ammonium phosphate fertilizers.
4. the method that carbide slag according to claim 1 is used for phosphoric acid by wet process desulfurization, it is characterised in that：To be obtained in step G
To thick slurry return phosphate production technique in phosphorus ore extraction workshop section extraction tank in crystallized again.
5. the method that carbide slag according to claim 1 is used for phosphoric acid by wet process desulfurization, it is characterised in that：Added in step B
Oxidant be hydrogen peroxide.
6. the method that the carbide slag according to any claim in Claims 1 to 5 is used for phosphoric acid by wet process desulfurization, its feature
It is：The water of carbide slag mashing is the process water during phosphate production in step A.
7. the method that the carbide slag according to any claim in Claims 1 to 5 is used for phosphoric acid by wet process desulfurization, its feature
It is：Washing slag mashing water is that process water or phosphoric acid by wet process to be desulfurization during phosphate production or desulfurization are wet in step E
Method phosphoric acid.
8. the method that the carbide slag according to any claim in Claims 1 to 5 is used for phosphoric acid by wet process desulfurization, its feature
It is：The addition of washing slag slurry is in step F：Calcium hydroxide and sulphur in phosphoric acid by wet process to be desulfurization in the washing slurry for being added
The mol ratio of acid group is：Ca（OH）2:SO4 2-=1.00~1.05:1.00.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710014800.2A CN106829900A (en) | 2017-01-10 | 2017-01-10 | The method that carbide slag is used for phosphoric acid by wet process desulfurization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710014800.2A CN106829900A (en) | 2017-01-10 | 2017-01-10 | The method that carbide slag is used for phosphoric acid by wet process desulfurization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106829900A true CN106829900A (en) | 2017-06-13 |
Family
ID=59117362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710014800.2A Pending CN106829900A (en) | 2017-01-10 | 2017-01-10 | The method that carbide slag is used for phosphoric acid by wet process desulfurization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106829900A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240428A (en) * | 2019-06-14 | 2019-09-17 | 武汉理工大学 | A method of α high strength gypsum is prepared using carbide slag modification phosphorus ore |
| CN111646443A (en) * | 2020-07-23 | 2020-09-11 | 湖北祥云(集团)化工股份有限公司 | Desulfurization method and system for wet-process phosphoric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743438A (en) * | 1984-09-27 | 1988-05-10 | Tennessee Valley Authority | Process for producing phosphoric acid from low purity phosphate rock |
| CN104828799A (en) * | 2014-02-12 | 2015-08-12 | 贵州川恒化工有限责任公司 | Process of producing feed-grade calcium dihydrogen phosphate through phosphoric acid circulation impurity removal method |
-
2017
- 2017-01-10 CN CN201710014800.2A patent/CN106829900A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743438A (en) * | 1984-09-27 | 1988-05-10 | Tennessee Valley Authority | Process for producing phosphoric acid from low purity phosphate rock |
| CN104828799A (en) * | 2014-02-12 | 2015-08-12 | 贵州川恒化工有限责任公司 | Process of producing feed-grade calcium dihydrogen phosphate through phosphoric acid circulation impurity removal method |
Non-Patent Citations (2)
| Title |
|---|
| 孟永涛等: "湿法磷酸净化预处理的实验研究", 《广州化工》 * |
| 郭国良等: "脱硫用电石渣浆液中硫化物去除工艺的对比研究", 《工业水处理》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240428A (en) * | 2019-06-14 | 2019-09-17 | 武汉理工大学 | A method of α high strength gypsum is prepared using carbide slag modification phosphorus ore |
| CN111646443A (en) * | 2020-07-23 | 2020-09-11 | 湖北祥云(集团)化工股份有限公司 | Desulfurization method and system for wet-process phosphoric acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101177251A (en) | Method for producing technical grade ribose phosphate, food grade ribose phosphate and industry ammonium diacid phosphate using wet-process ribose phosphate | |
| CN102755829B (en) | A kind of desulfurizing agent and application thereof | |
| CN107879363A (en) | A kind of method that nitric acid decomposes phosphorus mine tailing extracting sulfuric acid calcium pyroborate by-product magnesium hydroxide and ammonium nitrate magnesium | |
| CN110272144B (en) | Treatment method of iron phosphate production wastewater | |
| CN102390868B (en) | Method for producing manganese sulfate from smelting furnace gas | |
| CN111086977B (en) | Method for preparing MCP and MDCP (Madin-Darby Canine phosphate) by using raffinate acid | |
| CN112279227B (en) | Chemical magnesium removal method for collophanite and tailings-free production | |
| CN113460989A (en) | Battery-grade iron phosphate and preparation method thereof | |
| CN102303874A (en) | Method for preparing ammonium sulfate by conversion of phosphogyspum with polycrystalline method | |
| CN109574055A (en) | A kind of method of salt slurry production precipitated calcium carbonate and epsom salt | |
| CN101434386A (en) | Method for producing fine phosphate by using dilute acid to decompose middle and low grade phosphate ore using | |
| CN103466579A (en) | Method for producing full-water-soluble monoammonium phosphate by phosphoric acid by wet process | |
| CN101531384A (en) | Technique for preparing electronic grade magnesium hydrate and ammonium sulphate by cycle serum featuring in flue gas desulfurization by method of magnesium oxidization | |
| CN106829900A (en) | The method that carbide slag is used for phosphoric acid by wet process desulfurization | |
| CN101823745B (en) | Method for producing super-fine light-weighted calcium carbonate, ammonium chloride and carbon powder with waste associated alkali solution and acetylene sludge | |
| CN108557792B (en) | A kind of preparation method of cladded type iron manganese phosphate | |
| CN100402418C (en) | Hydrochloric acid process of producing feed level calcium diphosphate and gypsum coproduct | |
| CN102755828B (en) | Desulfurizer composite and application thereof | |
| CN1376635A (en) | Process for preparing phosphoric acid from waste sulfuric acid as by-product of titanium oxide powder by wet method | |
| CN114560486B (en) | CO with leaching aid capable of being recycled 2 Indirect mineralization method | |
| CN105819415A (en) | Phosphorus ore all-resource utilization production method preparing feed calcium hydrophosphate with hydrochloric acid | |
| CN100396599C (en) | Method for producing phosphorous acid and gypsum using hydrochloric acid method | |
| CN101823744B (en) | Method for producing light-weighted calcium carbonate, ammonium chloride and carbon powder with waste associated alkali solution and acetylene sludge | |
| CN115536046A (en) | Method for co-producing lithium carbonate and lithium hydroxide by lithium-containing solution | |
| CN102092757B (en) | Method for producing fine lightweight calcium carbonate, ammonium chloride and carbon powder by using soda production waste liquor and carbide slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170613 |
|
| RJ01 | Rejection of invention patent application after publication |