CN103539209A - Method for preparation of ferrous disulfide and coproduction of sulfuric acid - Google Patents
Method for preparation of ferrous disulfide and coproduction of sulfuric acid Download PDFInfo
- Publication number
- CN103539209A CN103539209A CN201310554864.3A CN201310554864A CN103539209A CN 103539209 A CN103539209 A CN 103539209A CN 201310554864 A CN201310554864 A CN 201310554864A CN 103539209 A CN103539209 A CN 103539209A
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- gas
- ferrous disulfide
- iron
- gaseous state
- 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.)
- Granted
Links
Landscapes
- Treating Waste Gases (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparation of ferrous disulfide and coproduction of sulfuric acid, belonging to the technical field of the preparation method of inorganic compounds. The method specifically comprises the following steps: a, placing sulfate or iron oxide of iron at a temperature of 300 DEG C-700 DEG C, and ventilating gas-state sulfur to react for 20 minutes-120 minutes to prepare ferrous disulfide and a sulfur dioxide gas; and b, preparing sulfuric acid by using the sulfur dioxide gas obtained in the step a. According to the method for preparation of ferrous disulfide and coproduction of sulfuric acid, conversion rate of materials generally reaches over 90%, and purity of the obtained ferrous disulfide can reach over 80wt%. Besides, the method disclosed by the invention is not only low in energy consumption and high in degree of reduction, but also simple in process, short in production period, easy to control and convenient to popularize.
Description
Technical field
The present invention relates to a kind of method of preparing ferrous disulfide co-producing sulfuric acid, belong to mineral compound preparation method field.
Background technology
Ferrous disulfide is a kind of important industrial chemicals, in the industry such as rubber, papermaking, weaving, food, match, battery and agricultural, all has important use.Ferrous disulfide mainly exists with sulfurous iron ore form at occurring in nature, and China's sulfurous iron ore is low-grade as main in mainly take, and average grade is 15%～18%, and because its purity is lower, application is also subject to a lot of restrictions.China's sulfurous iron ore exploitation purposes is generally two kinds: the one, and the chemical change technique of comprehensively having been closed, the sulphur of production is mainly for the production of sulfuric acid and industrial chemicals, and this method sulphur resource utilization is low, and environmental pollution is serious; The 2nd, by washing, become pyrite concentrate as gas washing in SA production raw material, but in washing process, discharge a large amount of mine tailings (sulfur-bearing 3%～8%) high grade kaolinite and washing waste liquid, this not only wastes resource, causes severe contamination to Its Adjacent Waters and surrounding enviroment simultaneously.
For a long time, China's sulfuric acid industry be take sulfurous iron ore as main raw material, and pyrite-based sulfuric acid production mainly comprises roasting, gas sweetening, conversion and dry four parts that absorb.The every production of pyrite-based sulfuric acid production 1t sulfuric acid will produce 0.8～0.9t pyrite cinder, wherein contains abundant iron resources, but because it is impure more, recycles difficulty large, causes waste and the pollution to environment of resource.
Summary of the invention
For above-mentioned defect, the invention provides a kind of method of preparing ferrous disulfide co-producing sulfuric acid, utilize more than the purity of the method gained ferrous disulfide generally can reach 80wt%, transformation efficiency can reach more than 95%.
Technical scheme of the present invention:
The invention provides a kind of method of preparing ferrous disulfide co-producing sulfuric acid, concrete steps comprise:
A in 300～700 ℃ of temperature, passes into gaseous state sulphur by the vitriol of iron or ferriferous oxide, reacts 20～120min, makes ferrous disulfide and sulfur dioxide gas.
The sulfur dioxide gas of b step a gained is for the preparation of sulfuric acid.
The sulphate of iron of the iron in described step a is at least one in ferrous sulfate or ferric sulphate.
Ferriferous oxide in described step a is ferric oxide, Z 250 (Fe
3o
4) or iron protoxide (FeO) at least one.
The vitriol of iron or the water content≤15wt% of ferriferous oxide in described step a.
Preferably, the method that in described step a, the vitriol of iron or ferriferous oxide are controlled its water content≤15wt% is: dry 10～120min at 50～300 ℃.
Preferably, also pass into the gas formation mixed gas that reductibility is less than gaseous sulfur in described step a, wherein, volume ratio >=15% of gaseous state sulphur and mixed gas, is 100ml/min under the gas speed mark condition of mixed gas.
Preferred, the volume ratio of described gaseous state sulphur and mixed gas is 15～85%.
The gas that described reductibility is less than gaseous state sulphur is at least one in nitrogen, gaseous sulfur, carbonic acid gas or sulfurous gas.
Beneficial effect of the present invention:
1, the method that the present invention prepares ferrous disulfide adopts the vitriol of gaseous state sulphur and iron or ferriferous oxide to react to prepare ferrous disulfide, and the method step of preparation process is simple, easy to control, and production efficiency is high, is convenient to popularization.
What 2, adopt due to the present invention is gaseous state sulphur and raw material reaction, and no matter from the contact area between theory reaction occurrence temperature or reactant, reaction all more easily occurs; The transformation efficiency of raw material of the present invention generally can reach more than 90%, more than product purity generally also can reach 80wt%.
What 3, the present invention adopted is gas-solid reaction mechanism, reacted solid product can not brought other impurity except raw material into, thereby the ferrous disulfide quality producing is high, and the sulfur dioxide gas of its by-product (its concentration is >=10vol%) can be used double conversion and double absorption explained hereafter sulfuric acid.
Therefore not only energy consumption is low in the present invention, and reduction ratio is high, and technique is simple, with short production cycle, is easy to control, and is convenient to promote.
Embodiment
The invention provides a kind of method of preparing ferrous disulfide co-producing sulfuric acid, comprise the steps:
A in 300～700 ℃ of temperature, passes into gaseous state sulphur by the vitriol of iron or ferriferous oxide, reacts 20～120min, makes ferrous disulfide and sulfur dioxide gas; In this step, if temperature is crossed low reaction, be difficult to carry out, the high and ferrous disulfide of excess Temperature energy consumption easily decomposes under comparatively high temps; Reaction times, too short feed stock conversion can be lower, and long words energy consumption of reaction times is also high;
The sulfur dioxide gas of b step a gained is for the preparation of sulfuric acid.
The vitriol of iron or the water content≤15wt% of ferriferous oxide in described step a; Because can produce SO in system
2, the water yield is too high can etching apparatus.
Preferably, the method that in described step a, the vitriol of iron or ferriferous oxide are controlled its water content≤15wt% is: dry 10～120min at 50～300 ℃.
Preferably, in described step a, also pass into the gas formation mixed gas that reductibility is less than gaseous state sulphur, wherein, volume ratio >=15% of gaseous state sulphur and mixed gas, why described method carries out in reductibility is less than the atmosphere of gaseous sulfur, is mainly that sulphur needs some gases to drive, moreover for two kinds of considerations, the one, in atmosphere, gas can not react with sulphur, the 2nd, in atmosphere except the gas of sulphur can not and raw material reaction; In mixed gas, why limit volume parts >=15% of sulphur gaseous state sulphur, because gaseous state sulphur umber is too low, corresponding sulphur is also just few, and transformation efficiency is not high, and the gas needing also can be a lot.Preferred, the volume ratio of gaseous state sulphur and mixed gas is 15～85%.
The gas that described reductibility is less than gaseous state sulphur is at least one in nitrogen, gaseous sulfur, carbonic acid gas or sulfurous gas.
Below by embodiment, the present invention is specifically described; it is important to point out that embodiment is only for further illustrating of the present invention; can not be interpreted as limiting the scope of the invention, these those skilled in the art can make according to the present invention some nonessential improvement and adjustment.
The preparation method of embodiment 1 ferrous disulfide co-producing sulfuric acid
A, by 1g ferrous sulfate dry 120min at 50 ℃;
B, by dried ferrous sulfate raw material in nitrogen and gaseous sulfur atmosphere, in 400 ℃, (wherein, gaseous state sulphur accounts for 60% of mixed gas cumulative volume, i.e. S/ (S+N to pass into gaseous state sulphur
2) parts by volume rate be 60%, the total gas speed of gas is 100ml/min at mark under condition), reaction 45min, obtains ferrous disulfide and sulfurous gas; Gained sulfur dioxide concentration is 9.5vol%, can adopt double conversion and double absorption explained hereafter sulfuric acid.
After measured, the transformation efficiency of ferrous sulfate is 92%, and the purity of ferrous disulfide reaches 85wt%.
The preparation method of embodiment 2 ferrous disulfide co-producing sulfuric acids
A, by dry 80min at 100 ℃, 2g ferrous sulfate;
B, by dried ferrous sulfate raw material in nitrogen, gaseous sulfur and carbon dioxide atmosphere, at 500 ℃, (wherein, gaseous state sulphur accounts for 35% of mixed gas cumulative volume, i.e. S/ (S+N to pass into gaseous state sulphur
2+ CO
2) parts by volume rate be 35%, the total gas speed of gas is 100ml/min at mark under condition, reaction 35min, obtains ferrous disulfide and sulfurous gas; Gained sulfur dioxide concentration is 15vol%, can adopt double conversion and double absorption explained hereafter sulfuric acid.
After measured, the transformation efficiency of ferrous sulfate is 94%, and the purity of ferrous disulfide reaches 90wt%.
The preparation method of embodiment 3 ferrous disulfide co-producing sulfuric acids
A, by 2g ferric sulphate dry 60min at 200 ℃;
B, by dried ferric sulphate raw material in nitrogen, gaseous sulfur and sulfurous gas atmosphere, in 600 ℃, (wherein, gaseous state sulphur accounts for 35% of mixed gas cumulative volume, i.e. S/ (S+N to pass into gaseous state sulphur
2+ SO
2) parts by volume rate be 35%, the total gas speed of gas is 100ml/min at mark under condition, reaction 80min, obtains ferrous disulfide and sulfurous gas; Gained sulfur dioxide concentration is 12vol%, can adopt double conversion and double absorption explained hereafter sulfuric acid.
After measured, the transformation efficiency of ferric sulphate is 96%, and the purity of ferrous disulfide reaches 95wt%.
The preparation method of embodiment 4 ferrous disulfide co-producing sulfuric acids
A, by 4g ferric sulphate dry 10min at 300 ℃;
B, by dried ferric sulphate raw material in nitrogen, gaseous sulfur, sulfurous gas and carbon dioxide atmosphere, in 500 ℃, (wherein, gaseous state sulphur accounts for 20% of mixed gas cumulative volume, i.e. S/ (S+N to pass into gaseous state sulphur
2+ CO
2+ SO
2) parts by volume rate be 20%, the total gas speed of gas is 100ml/min at mark under condition, reaction 100min, obtains ferrous disulfide and sulfurous gas; Gained sulfur dioxide concentration is 10vol%, can adopt double conversion and double absorption explained hereafter sulfuric acid.
After measured, the transformation efficiency of ferric sulphate is 95%, and the purity of ferrous disulfide reaches 92wt%.
The preparation method of embodiment 5 ferrous disulfide co-producing sulfuric acids
A, by 4g ferric sulphate dry 120min at 200 ℃;
B, by dried ferric sulphate raw material in nitrogen, gaseous sulfur, sulfurous gas and carbon dioxide atmosphere, in 450 ℃, (wherein, gaseous state sulphur accounts for 15% of mixed gas cumulative volume, i.e. S/ (S+N to pass into gaseous state sulphur
2+ CO
2+ SO
2) parts by volume rate be 15%, the total gas speed of gas is 100ml/min at mark under condition, reaction 40min, obtains ferrous disulfide and sulfurous gas; Gained sulfur dioxide concentration is 18vol%, can adopt double conversion and double absorption explained hereafter sulfuric acid.
After measured, the transformation efficiency of ferric sulphate is 93%, and the purity of ferrous disulfide reaches 88wt%.
The preparation method of embodiment 6 ferrous disulfide co-producing sulfuric acids
A, by 4g ferric sulphate dry 100min at 300 ℃;
B, by dried ferric sulphate raw material in nitrogen and gaseous sulfur atmosphere, in 550 ℃, (wherein, gaseous state sulphur accounts for 85% of mixed gas cumulative volume, i.e. S/ (S+N to pass into gaseous state sulphur
2) parts by volume rate be 85%, the total gas speed of gas is 100ml/min at mark under condition, reaction 20min, obtains ferrous disulfide and sulfurous gas; Gained sulfur dioxide concentration is 20vol%, can adopt double conversion and double absorption explained hereafter sulfuric acid.
After measured, the transformation efficiency of ferric sulphate is 94%, and the purity of ferrous disulfide reaches 90wt%.
The preparation method of embodiment 7 ferrous disulfide co-producing sulfuric acids
A, by 2g ferric oxide dry 50min at 250 ℃;
B, by dried ferric oxide raw material in nitrogen, gaseous sulfur and carbon dioxide atmosphere, in 300 ℃, (wherein, gaseous state sulphur accounts for 30% of mixed gas cumulative volume, i.e. S/ (S+N to pass into gaseous state sulphur
2+ CO
2) parts by volume rate be 30%, the total gas speed of gas is 100ml/min at mark under condition, reaction 60min, obtains ferrous disulfide and sulfurous gas; Gained sulfur dioxide concentration is 10.5vol%, can adopt double conversion and double absorption explained hereafter sulfuric acid.
After measured, the transformation efficiency of ferric oxide is 90%, and the purity of ferrous disulfide reaches 80wt%.
The preparation method of embodiment 8 ferrous disulfide co-producing sulfuric acids
A, by 2g ferric oxide dry 90min at 150 ℃;
B, by dried ferric oxide raw material in nitrogen, gaseous sulfur and sulfurous gas atmosphere, in 700 ℃, (wherein, gaseous state sulphur accounts for 40% of mixed gas cumulative volume, i.e. S/ (S+N to pass into gaseous state sulphur
2+ SO
2) parts by volume rate be 40%, the total gas speed of gas is 100ml/min at mark under condition, reaction 120min, obtains ferrous disulfide and sulfurous gas; Gained sulfur dioxide concentration is 10vol%, can adopt double conversion and double absorption explained hereafter sulfuric acid.
After measured, the transformation efficiency of ferric oxide is 98%, and the purity of ferrous disulfide reaches 95wt%.
Claims (7)
1. a method of preparing ferrous disulfide co-producing sulfuric acid, is characterized in that, comprises the steps:
A in 300～700 ℃ of temperature, passes into gaseous state sulphur by the vitriol of iron or ferriferous oxide, reacts 20～120min, makes ferrous disulfide and sulfur dioxide gas;
The sulfur dioxide gas of b step a gained is for the preparation of sulfuric acid.
2. the method for preparing ferrous disulfide co-producing sulfuric acid according to claim 1, is characterized in that, the sulphate of iron of the iron in described step a is at least one in ferrous sulfate or ferric sulphate; Ferriferous oxide is at least one in ferric oxide, Z 250 or iron protoxide.
3. the method for preparing ferrous disulfide co-producing sulfuric acid according to claim 1 and 2, is characterized in that, the vitriol of iron or the water content≤15wt% of ferriferous oxide in described step a.
4. the method for preparing ferrous disulfide co-producing sulfuric acid according to claim 3, is characterized in that, in described step a, the vitriol of iron or ferriferous oxide are controlled the method for its water content≤15wt% and be: dry 10～120min at 50～300 ℃.
5. the method for preparing ferrous disulfide co-producing sulfuric acid according to claim 1 and 2, it is characterized in that, in described step a, also pass into the gas formation mixed gas that reductibility is less than gaseous state sulphur, wherein, volume ratio >=15% of gaseous state sulphur and mixed gas is 100ml/min under the gas speed mark condition of mixed gas.
6. the method for preparing ferrous disulfide co-producing sulfuric acid according to claim 5, is characterized in that, the volume ratio of described gaseous state sulphur and mixed gas is 15～85%.
7. according to the method for preparing ferrous disulfide co-producing sulfuric acid described in claim 5 or 6, it is characterized in that, the gas that described reductibility is less than gaseous state sulphur is at least one in nitrogen, gaseous sulfur, carbonic acid gas or sulfurous gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310554864.3A CN103539209B (en) | 2013-11-08 | 2013-11-08 | A kind of method preparing ferrous disulfide co-producing sulfuric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310554864.3A CN103539209B (en) | 2013-11-08 | 2013-11-08 | A kind of method preparing ferrous disulfide co-producing sulfuric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103539209A true CN103539209A (en) | 2014-01-29 |
| CN103539209B CN103539209B (en) | 2016-01-20 |
Family
ID=49963131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310554864.3A Active CN103539209B (en) | 2013-11-08 | 2013-11-08 | A kind of method preparing ferrous disulfide co-producing sulfuric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103539209B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108726577A (en) * | 2018-06-22 | 2018-11-02 | 济宁学院 | A kind of preparation method of ferrous sulfide nanometer sheet material |
| CN116102073A (en) * | 2023-01-09 | 2023-05-12 | 贵州雅友新材料有限公司 | Method for recycling pyrite cinder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303875A (en) * | 2013-07-10 | 2013-09-18 | 四川大学 | Method for recovering pyrite resources |
-
2013
- 2013-11-08 CN CN201310554864.3A patent/CN103539209B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303875A (en) * | 2013-07-10 | 2013-09-18 | 四川大学 | Method for recovering pyrite resources |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108726577A (en) * | 2018-06-22 | 2018-11-02 | 济宁学院 | A kind of preparation method of ferrous sulfide nanometer sheet material |
| CN108726577B (en) * | 2018-06-22 | 2020-07-24 | 济宁学院 | Preparation method of ferrous sulfide nanosheet material |
| CN116102073A (en) * | 2023-01-09 | 2023-05-12 | 贵州雅友新材料有限公司 | Method for recycling pyrite cinder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103539209B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102534187B (en) | Method for treating pyrite cinder by combining acidic leaching with alkaline dissolving | |
| CN104762466A (en) | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore | |
| CN103864024B (en) | A kind of method of catalytic decomposition phosphogypsum | |
| CN102838154A (en) | Process for producing sulfur and light calcium carbonate from phosphorus gypsum | |
| CN104313346B (en) | Process for recovering aluminum, potassium and gallium by quickly reducing and desulfurizing alunite at high temperature | |
| CN110562933B (en) | Method for quickly separating calcium and sulfur of industrial byproduct gypsum | |
| CN103539209B (en) | A kind of method preparing ferrous disulfide co-producing sulfuric acid | |
| CN102431976A (en) | Method for recovering sulfur and iron resources through reducing and decomposing titanium white waste slag green vitriol by sulfur | |
| CN101811737A (en) | Method for preparing manganese sulfate from sulfur-containing waste residue | |
| CN104528781A (en) | Method for removing sulfur dioxide in flue gas and preparing magnesium sulfate by utilizing phosphorus floatation tailings | |
| CN103303875A (en) | Method for recovering pyrite resources | |
| CN103553078B (en) | Technology for preparing ammonium sulfate by high-efficiency ammonia desulphurization and crystallization | |
| CN103318975B (en) | Recycling method of waste residue and waste sulfuric acid of titanium dioxide produced by sulfuric acid method | |
| CN105013317A (en) | Process flow for recovering high-purity magnesium sulfite by magnesium oxide flue gas desulphurization | |
| CN109734106B (en) | Method for preparing high-concentration sodium bisulfite solution by using industrial waste | |
| CN110844926A (en) | Production method of high-purity magnesium sulfite | |
| CN105925812B (en) | A kind of method that manganese is extracted from Mn-rich slag | |
| CN103539208B (en) | A kind of method preparing coproduction of iron oxide red sulfuric acid | |
| CN111453702B (en) | Method for recovering sulfur in industrial byproduct calcium sulfide slag by fixed bed | |
| CN101559960B (en) | Method for removing excessive hydrofluosilicic acid in process of producing potassium sulfate by low-temperature decomposing of potassium feldspar by hydrofluosilicic acid | |
| CN213865389U (en) | System for utilize cement kiln tail waste gas and ardealite preparation ammonium sulfate | |
| CN104495901B (en) | A kind of preparation method of needle-like calcium carbonate | |
| CN100497680C (en) | New method for extracting nickel from enriched ore of nickel sulfide | |
| CN103553143B (en) | The vitriol of sulphur reduction decomposition iron prepares the method for coproduction of iron oxide red sulfuric acid | |
| CN110980779A (en) | Recovery method of magnesium oxide desulfurizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |