CN109019525B - Hydrogen sulfide microreactor and preparation method thereof, and phosphoric acid solution deep dearsenification and heavy metal removal method - Google Patents
Hydrogen sulfide microreactor and preparation method thereof, and phosphoric acid solution deep dearsenification and heavy metal removal method Download PDFInfo
- Publication number
- CN109019525B CN109019525B CN201811183564.8A CN201811183564A CN109019525B CN 109019525 B CN109019525 B CN 109019525B CN 201811183564 A CN201811183564 A CN 201811183564A CN 109019525 B CN109019525 B CN 109019525B
- Authority
- CN
- China
- Prior art keywords
- microreactor
- hydrogen sulfide
- arsenic
- phosphoric acid
- sulfur
- 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.)
- Active
Links
Images
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
- C01B17/16—Hydrogen sulfides
- C01B17/161—Preparation from elemental sulfur
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a hydrogen sulfide microreactor, a preparation method thereof and a method for deeply removing arsenic and heavy metals from a phosphoric acid solution. The hydrogen sulfide microreactor is obtained by calcining excessive iron powder and sulfur in a protective atmosphere. Adding hydrogen sulfide microreactor into arsenic-containing phosphoric acid solution, wherein S can be slowly released from the surface of the hydrogen sulfide microreactor2‑，S2‑With As in phosphoric acid solution3+、As5+And the heavy metal ions react to generate precipitates so as to achieve the effect of deeply purifying arsenic ions and heavy metals in the phosphoric acid solution, the method has the advantages of high arsenic and heavy metal removal efficiency, low usage amount of the vulcanizing agent, low release amount of hydrogen sulfide and the like, and solves the problems of large usage amount, low utilization rate, H and the like of the traditional vulcanizing agent in the using process2S is seriously damaged, and the like, and the method has simple process and convenient operation and meets the requirement of industrial production.
Description
Technical Field
The invention relates to a hydrogen sulfide microreactor, in particular to a hydrogen sulfide microreactor obtained by high-temperature calcination of iron powder and sulfur, and a method for deeply removing arsenic from industrial phosphoric acid solution or deeply purifying arsenic and heavy metals in the phosphoric acid solution by using the hydrogen sulfide microreactor, belonging to the technical field of inorganic chemical industry.
Background
Phosphoric acid is widely used as a basic raw material for chemical industry in various fields such as medicine, chemical industry, food and the like. However, the industrially produced phosphoric acid cannot be applied to fields other than the chemical industry because of its high impurity content. Industrial thermal phosphoric acid is produced by combustion of industrial yellow phosphorus (P) and hydration, e.g. P4+5O2→P4O10；P4O10+6H2O→4H3PO4The arsenic in the prepared phosphoric acid is mostly from the raw material phosphorus for producing yellow phosphorusThe arsenic acid (H) is brought in by the ore and is generated by arsenic in the process of producing thermal phosphoric acid by using yellow phosphorus, wherein the arsenic is enriched in the yellow phosphorus product by 10 times3AsO4) And arsenous acid (H)3AsO3) Coexisting in phosphoric acid.
Along with the refinement of the phosphoric acid production process, both the thermal phosphoric acid production and the wet phosphoric acid production have higher and higher requirements on the purification technology. The low-arsenic phosphoric acid is one of important raw materials for producing food-grade, toothpaste-grade, medicine-grade and feed-grade phosphates, and the demand will be larger and larger along with the continuous improvement of the living standard of people, so that the demand for the low-arsenic high-quality thermal process industrial phosphoric acid will be larger and larger.
The arsenic in the phosphoric acid is arsenous acid H3AsO3The main methods for removing arsenic at present include chemical method, electrochemical method, extraction method and crystallization method. Among them, the most widely used chemical method is to precipitate arsenic in phosphoric acid as arsenic sulfide, usually by adding sodium sulfide aqueous solution, phosphorus pentasulfide solid or hydrogen sulfide gas to phosphoric acid, and the gas-liquid-solid three-phase treatment has various characteristics, no matter what kind of open sulfide is added, it is generally considered that hydrogen sulfide plays a role in arsenic removal by the following reaction:
2H3AsOs+3H2S＝As2S3↓+6H2O
at present, most of the industries adopt a sulfide sedimentation method to remove arsenic, and the main equipment comprises a reaction tank, a sedimentation tank, a filter and the like. But at present, the method has several problems that (1) the sulfide slag contains low arsenic and has large yield, the arsenic grade of the slag is below 30 percent, and the method is not beneficial to the recycling of arsenic resources; (2) the usage of vulcanizing agent (such as sodium sulfide) is more, the reaction is not thorough, and a large amount of H is generated in the treatment process2S escapes, which not only increases the processing cost and the equipment compliance, but also causes environmental pollution. Therefore, how to increase S2-High efficiency utilization of (1) and reduction of H2The escape of S is critical for the processing of arsenic in phosphoric acid. Therefore, the development of an efficient, low-cost and safe arsenic removal technology is urgently needed.
Disclosure of Invention
Aiming at the problems of high cost, low efficiency and H existing in the method for removing the arsenic component in the phosphoric acid solution in the prior art2S is harmful greatly, and the like, and the first aim of the invention is to provide a sustained-release high-activity S2-And S is2-High utilization, no H2The hydrogen sulfide microreactor harmed by S is particularly suitable for deep removal of trace arsenic and heavy metal ions in phosphoric acid solution.
The second purpose of the invention is to provide a method for preparing the hydrogen sulfide microreactor with simple operation and low cost.
The third purpose of the invention is to provide an application of the hydrogen sulfide microreactor, which is used for slowly releasing high-activity S2-The method has the characteristics that arsenic can be deeply removed from the phosphoric acid solution with high efficiency and low cost, the consumption of the vulcanizing agent is reduced compared with the existing vulcanizing agent, the cost is saved, the problem that hydrogen sulfide pollutes the environment is solved, the arsenic content in the phosphoric acid can be reduced to be below 0.5ppm, and the food-grade requirement is met.
The fourth purpose of the invention is to provide a method for removing heavy metal or arsenic in phosphoric acid solution by using a hydrogen sulfide microreactor, and the hydrogen sulfide microreactor is used for slowly releasing high-activity S2-Compared with the existing vulcanizing agent, the consumption of the vulcanizing agent is reduced, the cost is saved, the problem that hydrogen sulfide pollutes the environment is reduced, and the content of arsenic and heavy metal in the phosphoric acid solution can be reduced to be less than 0.5 ppm.
In order to achieve the technical purpose, the invention provides a preparation method of a hydrogen sulfide microreactor, which comprises the step of calcining excessive iron powder and sulfur in a protective atmosphere to obtain the hydrogen sulfide microreactor.
In a preferable scheme, the molar ratio of the iron powder to the sulfur is 1.2-1.5: 1. The excessive iron powder can ensure that the iron powder mainly generates ferrous sulfide in the high-temperature reaction process. The hydrogen sulfide microreactor of the invention is a black solid particle.
In a preferable scheme, the purity of the iron powder is more than 90%, and the mass percentage of the iron powder in the size fraction of-400 meshes accounts for more than 80%.
In a preferable scheme, the purity of the sulfur is more than 90%, and the mass percentage of the sulfur in the size fraction of-400 meshes accounts for more than 80%.
Preferably, the calcining temperature is 300-600 ℃, and the calcining time is until the whole reactant is red hot.
Preferably, the protective atmosphere is nitrogen or an inert atmosphere.
The invention provides a hydrogen sulfide microreactor prepared by the preparation method.
The hydrogen sulfide microreactor can slowly release active S from the surface in an acidic solution system2-, S-due to the lower solubility product of ferrous sulfide2Preferentially reacts with arsenic ions in the solution to generate arsenic sulfide and arsenic sulfide precipitate phases, the reaction of the arsenic sulfide and arsenic sulfide precipitate phases with acid can be effectively reduced, the generation of hydrogen sulfide is reduced, the redundant small amount of ferrous ions and phosphoric acid in the solution are subjected to complexation precipitation and filtration to be removed, the solution does not contain impurity ions basically, and deep purification is achieved.
The invention also provides an application of the hydrogen sulfide microreactor, which is used as a sulfur slow-release agent for deep purification of arsenic ions in industrial phosphoric acid.
The industrial sulfuric acid is hot phosphoric acid or wet phosphoric acid, and the content of arsenic in the industrial phosphoric acid is 20-100 ppm. Can be reduced to below 5ppm after being deeply removed by the hydrogen sulfide micro-reactor.
According to the preferable scheme, the hydrogen sulfide microreactor is added into industrial phosphoric acid containing arsenic ions, and the reaction is carried out at the temperature of 80-90 ℃ to generate arsenic sulfide precipitates. The reaction time is preferably 0.5-1 h. Under the temperature condition, the surface of the hydrogen sulfide microreactor can be ensured to slowly release active S2While facilitating rapid precipitation of arsenic.
In a preferable scheme, the dosage of the hydrogen sulfide microreactor is 1.5-2.0 times of the theoretical molar quantity of sulfur negative ions required for converting arsenic ions in a phosphoric acid solution into corresponding arsenic sulfides; the hydrogen sulfide microreactor is metered with sulfur anions it contains.
The invention also provides a method for deeply removing arsenic and heavy metals from a phosphoric acid solution by using the hydrogen sulfide microreactor, which comprises the steps of adding the hydrogen sulfide microreactor into the phosphoric acid solution containing arsenic ions and/or heavy metal ions, reacting at the temperature of 80-90 ℃, settling, and carrying out solid-liquid separation to obtain a first-stage slag phase and a first-stage purifying solution; carrying out magnetic separation on the first-stage slag phase, wherein a magnetic product is a hydrogen sulfide microreactor, and a non-magnetic product is arsenic sulfide and/or heavy metal sulfide; and mechanically activating the obtained magnetic product, returning the magnetic product to the first-stage purifying solution, reacting at the temperature of 80-90 ℃, settling, and carrying out solid-liquid separation to obtain a second-stage purifying solution and a second-stage slag phase.
In the preferable scheme, the consumption of the hydrogen sulfide microreactor is 1.5-5.0 times of the theoretical total molar quantity of negative sulfur ions required for converting arsenic ions and heavy metal ions in a phosphoric acid solution into corresponding arsenic-sulfur compounds and heavy metal sulfides; the hydrogen sulfide microreactor is metered with sulfur anions it contains.
In the preferred scheme, the mechanical activation adopts a stirring mill, and the ore milling time is 10-15 min. The magnetic product is the hydrogen sulfide micro-reactor which is not completely reacted and can be returned for reuse after being mechanically activated by a stirring mill, so that the utilization efficiency of the hydrogen sulfide micro-reactor is improved, the dearsenification reaction is more thorough, and the dearsenification effect is better.
In the preferred scheme, the nonmagnetic products obtained from the second-stage slag and the first-stage slag are combined and comprehensively treated; the arsenic content in the obtained second-stage purifying liquid can be controlled below 0.5 ppm.
The invention discloses a method for purifying arsenic in an acidic solution by using a hydrogen sulfide microreactor, which comprises the following steps:
1) adding a hydrogen sulfide microreactor into a phosphoric acid solution containing arsenic ions according to a ratio, reacting for 0.5-1 h at the temperature of 80-90 ℃, settling (a flocculating agent can be added to accelerate the settling), and carrying out solid-liquid separation to obtain a first-stage slag phase and a first-stage purifying solution; the dosage of the hydrogen sulfide microreactor is 1.5-2.0 times of the theoretical molar quantity of sulfur negative ions required by generating corresponding sulfides by arsenic ions in a phosphoric acid solution;
2) and (3) carrying out primary magnetic separation on the first-stage slag phase (the magnetic field intensity is 500-1000 GS), separating out magnetic and non-magnetic products, mechanically activating the magnetic products, putting the magnetic products into the first-stage purified liquid, continuously reacting at 80-90 ℃, settling, and carrying out solid-liquid separation to obtain a second-stage purified liquid and a second-stage slag phase.
The method for deeply purifying arsenic and heavy metals in phosphoric acid solution comprises the following specific steps:
the method comprises the following steps: preparation of hydrogen sulfide microreactor
Putting excessive iron powder and sulfur into a reaction furnace, calcining under the protection of nitrogen at the temperature of 300-600 ℃, heating until the whole reactant is red hot, and stopping heating to obtain black solid particles, namely a hydrogen sulfide microreactor;
step two: slow release sulfuration of arsenic in phosphoric acid solution
Adding a hydrogen sulfide microreactor into a phosphoric acid solution containing arsenic ions and heavy metal ions, wherein the dosage of the added hydrogen sulfide microreactor is 1.5-5.0 times of the theoretical amount, stirring and reacting for 0.5-1 h, the reaction temperature is 80-90 ℃, after the reaction is finished, adding a flocculating agent for rapid sedimentation, and filtering and separating to obtain a first-stage slag phase, namely high-arsenic heavy metal slag, and a filtrate is a first-stage purified solution;
step three: magnetic separation of first stage slag
Carrying out primary magnetic separation on the first-stage slag phase to separate out magnetic and non-magnetic products, wherein the magnetic field intensity adopted in the magnetic separation process is 500-1000 GS, the non-magnetic product is an arsenic slag precipitated phase which is completely reacted, and the magnetic product is a hydrogen sulfide microreactor which is not fully reacted;
step four: deep purification of phosphoric acid solutions
Carrying out primary magnetic separation on the first-stage slag phase to separate out magnetic and non-magnetic products, mechanically activating the magnetic products through a stirring mill, putting the magnetic products into the first-stage purified liquid, continuously reacting at the temperature of 80-90 ℃, settling, and carrying out solid-liquid separation to obtain a second-stage purified liquid and a second-stage slag phase; the second-stage slag is merged into the first-stage slag for comprehensive utilization or safe treatment, and the arsenic content in the second-stage purifying liquid can be reduced to below 0.5 ppm.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the hydrogen sulfide microreactor of the present invention has a sustained release of S in a strongly acidic solution2-Can reduce H2S, the utilization rate of the vulcanizing agent is improved, the use cost of the vulcanizing agent can be reduced, and the harm to the environment is reduced; solves the problems of large consumption of the vulcanizing agent, low utilization rate and H in the process of vulcanizing and removing arsenic by the vulcanizing agents such as sodium sulfide and the like in the prior art2The S is seriously damaged and the like,
2) the hydrogen sulfide microreactor has the advantages of simple preparation method and wide raw material source, and is favorable for industrial production.
3) The hydrogen sulfide microreactor is used for arsenic in industrial phosphoric acid solution, has good effect of deeply purifying the arsenic, reduces the release of hydrogen sulfide gas, reduces the usage amount of vulcanizing agents and meets the application requirements of the existing industry.
4) The method for deeply purifying the arsenic and the heavy metal in the phosphoric acid solution can realize deep removal of the arsenic and the heavy metal in the phosphoric acid solution, realize high-efficiency separation and recovery, greatly improve the grade of the arsenic in a slag phase, simultaneously reduce the consumption of a vulcanizing agent, reduce the emission of harmful gases such as hydrogen sulfide and the like, and is favorable for industrial production.
Drawings
FIG. 1 is a flow chart of dearsenification of industrial phosphoric acid.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention.
Example 1
The process for treating certain industrial phosphoric acid comprises the following specific steps of taking a certain amount of industrial phosphoric acid (H)3PO4105 percent of content and 50ppm of arsenic), taking a certain amount of iron powder and sulfur, calcining the iron powder and the sulfur to form black solid particles under the protection of nitrogen at 300 ℃, setting the molar ratio of the iron powder to the sulfur to be 1.2, setting the particle sizes of the iron powder and the sulfur to be less than 38 microns and accounting for 90 percent, pouring the prepared hydrogen sulfide microreactor into a reactor, setting the temperature to be 85 ℃, stirring the reactor at 150r/min, fully reacting for one hour, setting the adding amount of the hydrogen sulfide microreactor to be 3 times of the theoretical calculated value, and filtering the reactor after the reaction to obtain a productSectional precipitated slag and sectional purified liquid. And then carrying out wet magnetic separation on the first-stage sediment to separate out a magnetic product and a non-magnetic product, wherein the magnetic field intensity is 500 GS. Activating the magnetic product by stirring and grinding for 10min, and putting the magnetic product into the first section of the purified liquid to continue to react for half an hour under the same reaction conditions. And then filtering to obtain second-stage slag and second-stage purification liquid, and merging the second-stage slag and the first-stage slag for safe treatment.
The arsenic content in the two-stage purification liquid is 0.1ppm, the arsenic removal rate is 99.8 percent, and the requirement of 0.5ppm of food phosphoric acid is met.
Example 2
The process for treating certain industrial phosphoric acid comprises the following specific steps of taking a certain amount of industrial phosphoric acid (H)3PO4109% of content and 85ppm of arsenic), calcining a certain amount of iron powder and sulfur at 500 ℃ under the protection of nitrogen to form black solid particles, setting the molar ratio of the iron powder to the sulfur to be 1.2, setting the particle sizes of the iron powder and the sulfur to be less than 38 microns and accounting for 90%, pouring the prepared hydrogen sulfide microreactor into a reactor, setting the temperature to be 90 ℃, stirring at 300r/min, fully reacting for one hour, wherein the adding amount of the hydrogen sulfide microreactor is 2 times of the theoretical calculated value, and filtering after the reaction to obtain a first-stage precipitation slag and a first-stage purifying liquid. And then carrying out wet magnetic separation on the first-stage sediment to separate a magnetic product and a non-magnetic product, wherein the magnetic field intensity is 750 GS. Activating the magnetic product by stirring and grinding for 15min, and putting the magnetic product into the first section of the purified liquid to continue to react for half an hour under the same reaction conditions. And then filtering to obtain second-stage slag and second-stage purification liquid, and merging the second-stage slag and the first-stage slag for safe treatment.
The arsenic content in the two-stage purification liquid is 0.3ppm, the arsenic removal rate is 99.65%, and the requirement of 0.5ppm of food phosphoric acid is met.
Example 3
The process for treating certain industrial phosphoric acid comprises the following specific steps of taking a certain amount of industrial phosphoric acid (H)3PO4115 percent of arsenic and 20ppm of arsenic), taking a certain amount of iron powder and sulfur, calcining the iron powder and the sulfur to black solid particles under the protection of nitrogen at the temperature of 600 ℃, wherein the molar ratio of the iron powder to the sulfur is 1.5, the particle sizes of the iron powder and the sulfur are both less than 38 microns and account for 90 percent, pouring the prepared hydrogen sulfide microreactor into the reactor,setting the temperature at 80 ℃, stirring at 150r/min, fully reacting for one hour, adding hydrogen sulfide into the microreactor at 5 times of the theoretical calculated value, and filtering after reaction to obtain a first-stage precipitation slag and a first-stage purifying liquid. And then carrying out wet magnetic separation on the first-stage sediment to separate a magnetic product and a non-magnetic product, wherein the magnetic field intensity is 1000 GS. The magnetic product is stirred, milled and activated for 12min and put into a section of purified liquid to continue to react for half an hour under the same reaction conditions. And then filtering to obtain second-stage slag and second-stage purification liquid, and merging the second-stage slag and the first-stage slag for safe treatment.
The arsenic content in the two-stage purification liquid is 0.07ppm, the arsenic removal rate is 99.85 percent, and the requirement of 0.5ppm of food phosphoric acid is met.
Example 4
The process for treating certain industrial phosphoric acid comprises the following specific steps of taking a certain amount of industrial phosphoric acid (H)3PO4The content is 115 percent, the arsenic content is 70ppm, the copper content is 50ppm, and the lead content is 45ppm), a certain amount of iron powder and sulfur are calcined to black solid particles under the protection of nitrogen at the temperature of 600 ℃, the molar ratio of the iron powder to the sulfur is 1.5, the particle sizes of the iron powder and the sulfur are both less than 38 microns and account for 90 percent, the prepared hydrogen sulfide microreactor is poured into the reactor, the temperature is set to be 80 ℃, the stirring speed is 150r/min, the reaction is fully carried out for one hour, the adding amount of the hydrogen sulfide microreactor is 5 times of the theoretical calculated value, and a first-stage precipitated slag and a first-stage purified liquid are obtained by filtering. And then carrying out wet magnetic separation on the first-stage sediment to separate a magnetic product and a non-magnetic product, wherein the magnetic field intensity is 1000 GS. The magnetic product is stirred, milled and activated for 12min and put into a section of purified liquid to continue to react for half an hour under the same reaction conditions. And then filtering to obtain second-stage slag and second-stage purification liquid, and merging the second-stage slag and the first-stage slag for safe treatment.
The arsenic content in the two-stage purification liquid is 0.12ppm, the arsenic removal rate is 99.83%, the requirement of food phosphoric acid is met, the copper content is 0.32ppm, the lead content is 0.89ppm, and the purpose of removing heavy metals is achieved.
Comparative example 1
The process for treating certain industrial phosphoric acid comprises the following specific steps of taking a certain amount of industrial phosphoric acid (H)3PO4105 percent of iron powder and 98ppm of arsenic), calcining a certain amount of iron powder and sulfur at 600 ℃ under the protection of nitrogen to form black solid particles, setting the molar ratio of the iron powder to the sulfur to be 1.5, setting the particle sizes of the iron powder and the sulfur to be less than 38 micrometers and accounting for 90 percent, pouring the prepared hydrogen sulfide microreactor into a reactor, setting the temperature to be normal temperature (25 ℃), setting the stirring speed to be 150r/min, fully reacting for one hour, setting the adding amount of the hydrogen sulfide microreactor to be 2 times of the theoretical calculated value, and filtering after the reaction to obtain first-stage precipitation slag and first-stage purifying liquid. And then carrying out wet magnetic separation on the first-stage sediment to separate a magnetic product and a non-magnetic product, wherein the magnetic field intensity is 1000 GS. The magnetic product is activated by stirring and grinding for 10min and put into a section of purified liquid to continue to react for half an hour under the same reaction conditions. And then filtering to obtain second-stage slag and second-stage purification liquid, and merging the second-stage slag and the first-stage slag for safe treatment.
The arsenic content in the second-stage purification liquid is 32ppm, the arsenic removal rate is 67.35%, and the requirement of 0.5ppm of food phosphoric acid is not met.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (6)
1. The application of the hydrogen sulfide microreactor is characterized in that: the sulfur slow-release agent is applied to the deep purification of arsenic ions in industrial phosphoric acid; adding a hydrogen sulfide microreactor into industrial phosphoric acid containing arsenic ions, and reacting at the temperature of 80-90 ℃ to generate arsenic sulfide precipitates; the dosage of the hydrogen sulfide microreactor is 1.5-2.0 times of the theoretical molar quantity of the sulfur negative ions required for converting arsenic ions in the phosphoric acid solution into corresponding arsenic sulfides; the hydrogen sulfide microreactor is metered by sulfur anions contained in the hydrogen sulfide microreactor;
the hydrogen sulfide microreactor is prepared by the following method: calcining excessive iron powder and sulfur in a protective atmosphere to obtain the iron powder; the molar ratio of the iron powder to the sulfur is 1.2-1.5: 1; the calcining temperature is 300-600 ℃, and the calcining time is until the whole reactant is red hot.
2. Use of a hydrogen sulfide microreactor according to claim 1, wherein: the purity of the iron powder is more than 90%, and the mass percentage of the iron powder in the size fraction of-400 meshes is more than 80%; the purity of the sulfur is more than 90 percent, and the mass percentage of the sulfur in the grade which meets the grade of-400 meshes accounts for more than 80 percent.
3. A method for deeply removing arsenic and/or heavy metal from phosphoric acid solution by using a hydrogen sulfide microreactor is characterized by comprising the following steps: adding a hydrogen sulfide microreactor into a phosphoric acid solution containing arsenic ions and/or heavy metal ions, reacting at the temperature of 80-90 ℃, settling, and carrying out solid-liquid separation to obtain a first-stage slag phase and a first-stage purifying liquid; carrying out magnetic separation on the first-stage slag phase, wherein a magnetic product is a hydrogen sulfide microreactor, and a non-magnetic product is arsenic sulfide and/or heavy metal sulfide; mechanically activating the obtained magnetic product, returning the magnetic product to the first-stage purifying solution, reacting at the temperature of 80-90 ℃, settling, and carrying out solid-liquid separation to obtain a second-stage purifying solution and a second-stage slag phase;
the hydrogen sulfide microreactor is prepared by the following method: calcining excessive iron powder and sulfur in a protective atmosphere to obtain the iron powder; the molar ratio of the iron powder to the sulfur is 1.2-1.5: 1; the calcining temperature is 300-600 ℃, and the calcining time is until the whole reactant is red hot.
4. The method for deeply removing arsenic and/or heavy metals from phosphoric acid solution by using the hydrogen sulfide microreactor as claimed in claim 3, wherein the hydrogen sulfide microreactor comprises: the usage amount of the hydrogen sulfide microreactor is 1.5-5.0 times of the theoretical total molar amount of negative sulfur ions needed by converting arsenic ions and heavy metal ions in the phosphoric acid solution into corresponding arsenic-sulfur compounds and heavy metal sulfides; the hydrogen sulfide microreactor is metered with sulfur anions it contains.
5. The method for deeply removing arsenic and/or heavy metals from phosphoric acid solution by using the hydrogen sulfide microreactor as claimed in claim 3, wherein the hydrogen sulfide microreactor comprises: the mechanical activation adopts a stirring mill, and the ore milling time is 10-15 min.
6. The method for deeply removing arsenic and/or heavy metals from phosphoric acid solution by using the hydrogen sulfide microreactor as claimed in claim 3, wherein the hydrogen sulfide microreactor comprises: the purity of the iron powder is more than 90%, and the mass percentage of the iron powder in the size fraction of-400 meshes is more than 80%; the purity of the sulfur is more than 90 percent, and the mass percentage of the sulfur in the grade which meets the grade of-400 meshes accounts for more than 80 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811183564.8A CN109019525B (en) | 2018-10-11 | 2018-10-11 | Hydrogen sulfide microreactor and preparation method thereof, and phosphoric acid solution deep dearsenification and heavy metal removal method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811183564.8A CN109019525B (en) | 2018-10-11 | 2018-10-11 | Hydrogen sulfide microreactor and preparation method thereof, and phosphoric acid solution deep dearsenification and heavy metal removal method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109019525A CN109019525A (en) | 2018-12-18 |
| CN109019525B true CN109019525B (en) | 2020-12-22 |
Family
ID=64616223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811183564.8A Active CN109019525B (en) | 2018-10-11 | 2018-10-11 | Hydrogen sulfide microreactor and preparation method thereof, and phosphoric acid solution deep dearsenification and heavy metal removal method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109019525B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690699B (en) * | 2012-05-25 | 2017-03-29 | 上海中方宝达纺织智能仪器有限公司 | A kind of full sulfur of coal quickly processes the apparatus and method for generating Filter Tuber For Clean Coal |
| CN103991853A (en) * | 2014-05-29 | 2014-08-20 | 龚家竹 | Method for producing sanitary phosphate fertilizer with low heavy metal content |
| CN106744761A (en) * | 2016-12-28 | 2017-05-31 | 云南磷化集团有限公司 | The technology of heavy metal in a kind of removing wet dilute phosphoric acid |
| CN106830275A (en) * | 2017-02-22 | 2017-06-13 | 天津工业大学 | A kind of method of ferrous sulfide (FeS) oxidation dissolution removal water body middle and high concentration As (III) |
-
2018
- 2018-10-11 CN CN201811183564.8A patent/CN109019525B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 热硫化条件下铁硫比值对黄铁矿形成的影响;高文元等;《地学前缘》;20130531;第20卷(第3期);第131-137页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109019525A (en) | 2018-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111924817B (en) | Method for comprehensively utilizing waste lithium iron phosphate anode material | |
| CN112645299A (en) | Preparation method and application of iron phosphate | |
| WO2022242186A1 (en) | Method for preparing high-purity iron phosphate by using ferrophosphorus waste | |
| CN103397209B (en) | Method for extracting vanadium from high-calcium and high-phosphorus vanadium slag | |
| CN109500059B (en) | Transformation and microcapsule curing stabilization method for arsenic sulfide slag | |
| CN113353907A (en) | Ferric phosphate precursor and preparation method and application thereof | |
| CN114684801B (en) | Method for preparing high-purity ferric phosphate by using pyrite cinder | |
| CN106564957A (en) | A method of preparing battery-grade high-purity manganese sulfate by utilizing low-grade manganese ore | |
| CN103833156B (en) | A kind for the treatment of process of cold rolling chlorohydric acid pickling spent acid | |
| CN109019525B (en) | Hydrogen sulfide microreactor and preparation method thereof, and phosphoric acid solution deep dearsenification and heavy metal removal method | |
| CN102925899A (en) | Method for refining copper chloride etching waste liquor | |
| CN113753874B (en) | Method for recovering active substances from PVDF-containing lithium iron phosphate positive electrode material | |
| CN115196609B (en) | Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof | |
| CN106395925A (en) | A method of preparing a polyferricsulfate water purifier | |
| CN115441029A (en) | Vanadium electrolyte and preparation method and application thereof | |
| CN111573890B (en) | Comprehensive utilization method of ammonium chloride wastewater | |
| CN103952534A (en) | Method for preparing sodium molybdate from nickel-molybdenum ore | |
| CN108328592A (en) | A kind of technique for using phosphoric acid by wet process to produce magnesium monohydrogen phosphate for raw material | |
| CN110482513B (en) | Method for recovering granular ferric orthophosphate from chemical nickel plating waste liquid | |
| US20210395857A1 (en) | Methods for recovering metals from metal-containing materials | |
| CN107662909B (en) | Preparation method of phosphate | |
| CN110562947A (en) | Cationic metal impurity removing agent and application thereof | |
| CN109824090A (en) | A method of it is prepared using titanium white by product object high-purity iron oxide red | |
| CN110371944B (en) | Method for purifying phosphoric acid raffinate acid and recovering magnesium ammonium phosphate hexahydrate | |
| CN113979417B (en) | Preparation method of low-sulfur high-purity ferric phosphate in sulfuric acid system |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |