CN110421130A - The efficient separation method of sulphur in a kind of coal-fired flue-gas wet desulphurization gypsum - Google Patents
The efficient separation method of sulphur in a kind of coal-fired flue-gas wet desulphurization gypsum Download PDFInfo
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- CN110421130A CN110421130A CN201910746934.2A CN201910746934A CN110421130A CN 110421130 A CN110421130 A CN 110421130A CN 201910746934 A CN201910746934 A CN 201910746934A CN 110421130 A CN110421130 A CN 110421130A
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- coal
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- wet desulphurization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
- B22D11/111—Treating the molten metal by using protecting powders
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- 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
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/745—Preparation from sulfates
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Abstract
The present invention relates to a kind of efficient separation methods of sulphur in coal-fired flue-gas wet desulphurization gypsum.The invention belongs to Industrial Solid Waste innoxious process for treating fields, it is intended to solve the problems such as limitation existing for existing coal-fired flue-gas wet desulphurization gypsum innoxious process for treating is low with resource utilization utilization rate.It is mainly characterized by using coal-fired flue-gas wet desulphurization gypsum as raw material, using oxalic acid solution as release agent, realizes that sulphur efficiently separates in desulfurized gypsum by solid-liquid reaction.Separating technology according to the present invention is easy, and low in cost, sulphur content is up to 99.0% or more from efficiency.Meanwhile sulphur content can carry out Metallurgical resources utilization from solid matter remaining after the completion, liquid substance can be used as industrial sulphuric acid and be recycled, and accomplish the complete harmless treatment of coal-fired flue gas desulfurization solid waste.Market prospects of the present invention are good, and economic and practical type is strong, are worth carrying out marketing.
Description
Technical field
The invention belongs to Industrial Solid Waste innoxious process for treating fields, are related to a kind of desulfurized gypsum method for innocent treatment,
More particularly to a kind of efficient separation method of sulphur in coal-fired flue-gas wet desulphurization gypsum.
Background technique
The thermal power generation main generation mode current as China, can consume a large amount of coal in power generation process.It is fired in coal
During burning, the element sulphur in coal can be converted to SO at high temperature2It releases.China is as a coal-fired big country, annual SO2
Discharge amount is very high, shows according to the data that State Statistics Bureau issues, my SO in 20162Discharge amount is up to up to 19,630,000 tons, if contained
There is SO2Coal-fired flue-gas be directly discharged in air, will cause extremely serious environmental pollution.
Currently, Wet Flue Gas Desulfurization Technique is widely applied as a kind of effective flue gas desulfurization by coal-burning power plant, it is basic
Principle is using lime stone slurry as the SO in desulfurizing agent and flue gas2It is reacted, to realize flue gas desulfurization.Desulfurized gypsum
It is the by-product of smoke-gas wet desulfurization, every processing 1t SO22.7t desulfurized gypsum will be generated, according to statistics, ended for the end of the year 2017, it is wet
Method desulfurized gypsum yield is at 80,000,000 tons or more.
Desulfurized gypsum main component is CaSO4·2H2O, content account for 85.0% or more of desulfurized gypsum gross mass, wherein Ca
Element and S element mass percent are respectively 23.3wt% and 18.6wt%.In metallurgical process, Ca element is crystallizer protection
The important component of slag, and S element is all harmful for most steel grades in addition to automatic steel, therefore can not
Carry out Metallurgical resources utilization.
Currently, the most important Land use systems of desulfurized gypsum have it is following several: (1) making cement retarder；(2) paring stone is done
Cream；(3) Thistle board is made；(4) calcium sulfate crystal whiskers are prepared；(5) soil is improved.China can not provide remainder 20% at present
The desulfurized gypsum that source utilizes takes accumulation treatment measures, not only occupies large amount of land resources in this way, but also can cause to environment secondary
Pollution.Therefore, developing new desulfurized gypsum resource utilization approach seems particularly important to improve desulfurized gypsum utilization rate.
Summary of the invention
The object of the present invention is to provide a kind of efficient separation method of sulphur in coal-fired flue-gas wet desulphurization gypsum, feature exists
In, comprising the following steps:
(1) it will be crushed after the drying of coal-fired flue gas desulfurization gypsum raw material, obtain coal-fired flue gas desulfurization gypsum powder；
(2) it after oxalic acid crystal and water mix, is placed in water-bath and heats, stir to dissolve, obtain oxalic acid solution；
(3) the coal-fired flue gas desulfurization gypsum powder that step (1) obtains is weighed；
(4) step (3) are weighed into obtained coal-fired flue gas desulfurization gypsum powder and is added to the oxalic acid solution that step (2) obtains
In, stirring reacts it sufficiently, i.e., is efficiently separated by sulphur in solid-liquid reaction realization desulfurized gypsum；
(5) after the reaction was completed, the solution that step (4) obtains is separated by solid-liquid separation using filter device, is consolidated what is obtained
Body substance is collected after drying to constant weight, the closed preservation of liquid substance glass container.
Further, in step (1), the raw material main component is CaSO4·2H2O, content account for desulfurized gypsum gross mass
85.0%~95.0%.
Further, in step (1), raw material is crushed to 100~200 mesh after drying at 30~50 DEG C.
Further, step (2) institute's oxalic acid solution concentration obtained is 1.0wt%~20.0wt%.
Further, in step (3), before weighing coal-fired flue gas desulfurization gypsum powder, CaSO is measured4Content；So that step (4)
CaSO in the middle coal-fired flue gas desulfurization gypsum powder for participating in reaction4Molal weight ratio with oxalic acid is 0.8~1.0.
Further, the reaction temperature during described in step (4) efficiently separates is 25~50 DEG C.
Further, step (2) use electromagnetic agitation, stirring rate are as follows: 100~300 revs/min.Step (4) is using electricity
Magnetic stirring, stirring rate are as follows: 100~300 revs/min.
Further, the disengaging time of step (4) is 10~30 minutes, and sulphur separative efficiency is 99.0% or more.
Further, in step (5), drying to constant weight at 60~80 DEG C for solid matter.
Further, the solid matter that step (5) obtains carries out recycling benefit as metallurgical continuous casting crystallizer protecting residue slag former
With；Liquid substance is recycled as industrial sulphuric acid.
It is worth explanation, the desulfurized gypsum main component that the present invention is handled is CaSO4·2H2O, it is total that content accounts for desulfurized gypsum
85.0% or more of quality, wherein Ca element and S element mass percent are respectively 23.3wt% and 18.6wt%.In metallurgical mistake
Cheng Zhong, Ca element are the important components of crystallizer protecting residue, and S element is for most steel in addition to automatic steel
Kind is all harmful.In method disclosed by the invention, it is able to achieve efficiently separating for sulphur using oxalic acid solution processing desulfurized gypsum, point
It is up to 99.0% or more from rate, key reaction is as follows:
CaSO4·2H2O+H2C2O4·2H2O→CaC2O4·H2O↓+H2SO4+3H2O。
Sulphur content in coal-fired flue gas desulfurization gypsum can be left away and be removed by this method, and solid oxalic acid calcium obtained after separation can replace
Resource utilization is carried out as metallurgical continuous casting crystallizer protecting residue slag former for CaO, remaining sulfuric acid solution then can be used as work
Industry sulfuric acid is recycled.While realizing the harmless treatment of coal-fired flue gas desulfurization solid waste, desulfurization stone can be also greatlyd improve
Cream utilization rate.
In conclusion the present invention has the following advantages the solution have the advantages that unquestionable:
It 1) is release agent by raw material, oxalic acid of coal-fired flue-gas wet desulphurization gypsum, low in cost, simple process；
2) sulphur separation process can be completed at room temperature, and separative efficiency is high, react 10 under the conditions of temperature is 25~50 DEG C
It can be achieved within~30 minutes 99.0% sulphur separation rate；
3) sulphur content in desulfurized gypsum can carry out Metallurgical resources utilization, liquid from solid matter remaining after the completion
Body substance can be used as industrial sulphuric acid and be recycled, and accomplish the complete harmless treatment of coal-fired flue-gas wet desulphurization solid waste.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, various replacements and change are made, should all include within the scope of the present invention.
Embodiment 1:
Using Chongqing Hechuan power plant soot fume wet desulphurization gypsum as raw material, wherein CaSO4·2H2O content is
89.6wt%, sulfur content are as follows: 16.7wt%.
9.0g oxalic acid is weighed, the oxalic acid solution 900.0g for being 1.0wt% with deionized water compound concentration then will be all careless
Acid solution is placed in after water-bath is heated to 25 DEG C and keeps constant temperature.Weigh the drying desulfurized gypsum powder that granularity is 100~200 mesh
Weighed 12.0g desulfurized gypsum is added in the 900.0g oxalic acid solution of former configuration by 12.0g, improves electromagnetic agitation to 300
Rev/min, react desulfurized gypsum and oxalic acid solution sufficiently.After ten minutes, the solution after separation is consolidated with filter device
Liquid separation collects obtained solid matter after drying to constant weight at 60~80 DEG C, the closed guarantor of liquid substance glass container
It deposits.
Constituent analysis is carried out from solid matter after the completion to sulphur content in coal-fired flue-gas wet desulphurization gypsum, as the result is shown:
When desulfurized gypsum quality is 12.0g, release agent oxalic acid solution quality is 900.0g, concentration 1.0wt%, reaction temperature 25
DEG C, electromagnetic agitation revolving speed is 300 revs/min, and when the reaction time is 10 minutes, the separation rate of sulphur reaches in desulfurized gypsum
99.3% or more.
Embodiment 2:
Using Guizhou gold dollar power plant soot fume wet desulphurization gypsum as raw material, wherein CaSO4·2H2O content is
92.7wt%, sulfur content are as follows: 17.2wt%.
18.0g oxalic acid is weighed, the oxalic acid solution 360.0g for being 5.0wt% with deionized water compound concentration then will be whole
Oxalic acid solution is placed in after water-bath is heated to 30 DEG C and keeps constant temperature.Weigh the drying desulfurized gypsum powder that granularity is 100~200 mesh
Weighed 24.0g desulfurized gypsum is added in the 360.0g oxalic acid solution of former configuration by 24.0g, improves electromagnetic agitation to 200
Rev/min, react desulfurized gypsum and oxalic acid solution sufficiently.After 14 minutes, the solution after separation is consolidated with filter device
Liquid separation collects obtained solid matter after drying to constant weight at 60~80 DEG C, the closed guarantor of liquid substance glass container
It deposits.
Constituent analysis is carried out from solid matter after the completion to sulphur content in coal-fired flue-gas wet desulphurization gypsum, as the result is shown:
When desulfurized gypsum quality is 24.0g, release agent oxalic acid solution quality is 360.0g, concentration 5.0wt%, reaction temperature 30
DEG C, electromagnetic agitation revolving speed is 200 revs/min, and when the reaction time is 14 minutes, the separation rate of sulphur reaches in desulfurized gypsum
99.5% or more.
Embodiment 3:
Using two youth's power plant soot fume wet desulphurization gypsum of Xishui County as raw material, wherein CaSO4·2H2O content is
85.4wt%, sulfur content are as follows: 15.9wt%.
30.0g oxalic acid is weighed, the oxalic acid solution 200.0g for being 15.0wt% with deionized water compound concentration then will be whole
Oxalic acid solution is placed in after water-bath is heated to 40 DEG C and keeps constant temperature.Weigh the drying desulfurized gypsum powder that granularity is 100~200 mesh
Weighed 40.0g desulfurized gypsum is added in the 200.0g oxalic acid solution of former configuration by 40.0g, improves electromagnetic agitation to 250
Rev/min, react desulfurized gypsum and oxalic acid solution sufficiently.After 30 minutes, the solution after separation is consolidated with filter device
Liquid separation collects obtained solid matter after drying to constant weight at 60~80 DEG C, the closed guarantor of liquid substance glass container
It deposits.
Constituent analysis is carried out from solid matter after the completion to sulphur content in coal-fired flue-gas wet desulphurization gypsum, as the result is shown:
When desulfurized gypsum quality is 40.0g, release agent oxalic acid solution quality is 200.0g, concentration 15.0wt%, reaction temperature 40
DEG C, electromagnetic agitation revolving speed is 250 revs/min, and when the reaction time is 30 minutes, the separation rate of sulphur reaches in desulfurized gypsum
99.0% or more.
Claims (10)
1. the efficient separation method of sulphur in a kind of coal-fired flue-gas wet desulphurization gypsum, which comprises the following steps:
(1) it will be crushed after the drying of coal-fired flue gas desulfurization gypsum raw material, obtain the coal-fired flue gas desulfurization gypsum powder；
(2) it after the oxalic acid crystal and water mix, heats, stir to dissolve, obtain oxalic acid solution；
(3) the coal-fired flue gas desulfurization gypsum powder that step (1) obtains is weighed；
(4) step (3) obtained coal-fired flue gas desulfurization gypsum powder is weighed to be added in the oxalic acid solution that step (2) obtains,
Stirring reacts it sufficiently, i.e., is efficiently separated by sulphur in solid-liquid reaction realization desulfurized gypsum；
(5) after the reaction was completed, the solution that step (4) obtains is separated by solid-liquid separation using filter device, the solids that will be obtained
Matter recycles after drying to constant weight, and liquid substance container is saved and recycled.
2. the efficient separation method of sulphur in coal-fired flue-gas wet desulphurization gypsum according to claim 1, it is characterised in that: step
Suddenly in (1), the raw material main component is CaSO4·2H2O。
3. the efficient separation method of sulphur, feature exist in coal-fired flue-gas wet desulphurization gypsum according to claim 1 or 2
In: in step (1), raw material is crushed to 100~200 mesh after drying at 30~50 DEG C.
4. the efficient separation method of sulphur, feature exist in coal-fired flue-gas wet desulphurization gypsum according to claim 1 or 3
In: step (2) chooses suitable oxalic acid solution concentration.
5. the efficient separation method of sulphur, feature exist in coal-fired flue-gas wet desulphurization gypsum according to claim 1 or 3
In: in step (3), before weighing coal-fired flue gas desulfurization gypsum powder, measure CaSO4Content.
6. the efficient separation method of sulphur, feature exist in coal-fired flue-gas wet desulphurization gypsum according to claim 1 or 3
In: the reaction temperature during described in step (4) efficiently separates is 25~50 DEG C.
7. the efficient separation method of sulphur, feature exist in coal-fired flue-gas wet desulphurization gypsum according to claim 1 or 3
In:
Step (2) uses electromagnetic agitation, and step (4) uses electromagnetic agitation, and improves revolving speed.
8. the efficient separation method of sulphur, feature exist in coal-fired flue-gas wet desulphurization gypsum according to claim 1 or 3
In: the disengaging time of step (4) is 10~30 minutes.
9. the efficient separation method of sulphur, feature exist in coal-fired flue-gas wet desulphurization gypsum according to claim 1 or 3
In: in step (5), drying to constant weight at 60~80 DEG C for solid matter.
10. the efficient separation method of sulphur, feature exist in coal-fired flue-gas wet desulphurization gypsum according to claim 1 or 3
In: the solid matter that step (5) obtains is recycled as metallurgical continuous casting crystallizer protecting residue slag former；Liquid substance is made
It is recycled for industrial sulphuric acid.
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Citations (7)
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| KR20110008778A (en) * | 2009-07-21 | 2011-01-27 | 유 득 김 | Liquid catalyst compositions for desulfurization |
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| CN103551029A (en) * | 2013-10-22 | 2014-02-05 | 重庆大学 | Modification method for semi-dry sintering flue gas desulfurization ash |
| CN103910371A (en) * | 2014-04-17 | 2014-07-09 | 武汉钢铁(集团)公司 | Method for preparing calcium carbonate and coproducing ammonium sulfate by utilizing flue gas desulfurization gypsum or desulfurization ash residues |
-
2019
- 2019-08-14 CN CN201910746934.2A patent/CN110421130A/en active Pending
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|---|---|---|---|---|
| JPS54155173A (en) * | 1978-05-29 | 1979-12-06 | Hitachi Ltd | Exhaust gas desulfurizing method |
| JPH10137542A (en) * | 1996-11-18 | 1998-05-26 | Tohoku Electric Power Co Inc | Treatment of flue gas desulfurization waste water |
| CN1298754A (en) * | 2000-10-16 | 2001-06-13 | 中国石油化工集团公司 | Wet process for removing SO2 from fume |
| KR20110008778A (en) * | 2009-07-21 | 2011-01-27 | 유 득 김 | Liquid catalyst compositions for desulfurization |
| CN102825228A (en) * | 2012-07-31 | 2012-12-19 | 马鞍山科润冶金材料有限公司 | Continuous casting crystallizer covering slag for high-temperature alloy steel and method for preparing continuous casting crystallizer covering slag |
| CN103551029A (en) * | 2013-10-22 | 2014-02-05 | 重庆大学 | Modification method for semi-dry sintering flue gas desulfurization ash |
| CN103910371A (en) * | 2014-04-17 | 2014-07-09 | 武汉钢铁(集团)公司 | Method for preparing calcium carbonate and coproducing ammonium sulfate by utilizing flue gas desulfurization gypsum or desulfurization ash residues |
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