CN114906822A - Harmless treatment method and application of coke oven gas waste desulfurizer - Google Patents
Harmless treatment method and application of coke oven gas waste desulfurizer Download PDFInfo
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- CN114906822A CN114906822A CN202210449471.5A CN202210449471A CN114906822A CN 114906822 A CN114906822 A CN 114906822A CN 202210449471 A CN202210449471 A CN 202210449471A CN 114906822 A CN114906822 A CN 114906822A
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- 239000002699 waste material Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000000571 coke Substances 0.000 title claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 77
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 43
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000292 calcium oxide Substances 0.000 claims abstract description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 230000003009 desulfurizing effect Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- 229910052602 gypsum Inorganic materials 0.000 abstract description 4
- 239000010440 gypsum Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012485 toluene extract Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
- C01B17/02—Preparation of sulfur; Purification
- C01B17/027—Recovery of sulfur from material containing elemental sulfur, e.g. luxmasses or sulfur containing ores; Purification of the recovered sulfur
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention provides a harmless treatment method and application of a coke oven gas waste desulfurizer, which are characterized in that elemental sulfur in the waste desulfurizer is removed at high temperature and collected, ferric oxide, calcium carbonate and other impurities in the waste desulfurizer are dissolved by hydrochloric acid, calcium sulfate is separated and used in the gypsum industry, the solution is roasted at high temperature to form a mixture of ferric oxide and calcium oxide and used as a sintering raw material, and gas is absorbed to form hydrochloric acid, so that the harmless treatment of the waste desulfurizer is realized. Compared with the prior art, the method provided by the invention has the advantages that different components contained in the coke oven gas waste desulfurizer are extracted and recovered by different processes and methods, so that all valuable components in the waste desulfurizer are utilized, and the waste desulfurizer is effectively treated and recycled.
Description
Technical Field
The invention belongs to the field of steel smelting, and particularly relates to a harmless treatment method and application of a coke oven gas waste desulfurizer.
Background
In the coking industry, the coke oven gas is generally subjected to secondary purification desulfurization, and commonly used desulfurizing agents include an iron-based desulfurizing agent, an active carbon desulfurizing agent, a zinc-based desulfurizing agent and the like, wherein an iron oxide desulfurizing agent in the iron-based desulfurizing agent loses efficacy due to the reduction of sulfur capacity after long-term use to become a waste desulfurizing agent, and the waste desulfurizing agent contains partial benzene, naphthalene, sulfur and the like, so that the accumulation causes pollution of soil, water quality and the like,
at present, except for part of steel mills which utilize sintering technology for treatment, the main treatment mode is mixed with other industrial wastes for landfill, which can pollute the environment, has high disposal cost, and effectively utilizes valuable elements such as sulfur, iron and the like in the waste desulfurizer, thereby causing resource waste.
Patent publication No. CN 105727746A, published in 7/6/2017, discloses a waste desulfurizer treatment device and a waste desulfurizer treatment method thereof, and the device comprises a tank body, a grid plate, a wire mesh and an air supply power device, and solves the problems of environmental pollution and the like caused by the conventional waste desulfurizer treatment method, but the process and the method do not effectively recover valuable elements such as sulfur, iron and the like in the waste desulfurizer, and cause resource waste.
Patent CN 103771346A published 5/7/2014 discloses a method for recovering sulfur in waste desulfurizer, namely, the waste desulfurizer is mixed with catalytic cracking diesel oil at 40-250 ℃ and then subjected to solid-liquid separation to obtain desulfurizer material and desulfurization liquid, the elemental sulfur is recovered after cooling, and the desulfurization liquid can be recycled, but the problem of overlong time for heating and cooling in the process causes energy waste.
Patent No. CN101985069A published 3/16.2011 discloses a harmless treatment process for waste desulfurizer, namely, the waste desulfurizer is placed in a regeneration furnace for 8-12 hours, and then toluene extract is added and mixed with the waste desulfurizer to separate elemental sulfur, the treatment efficiency reaches 80-85%, but the toluene recycling process is too long, and the solvent consumption is too large.
Disclosure of Invention
The invention aims to provide a harmless treatment method of a coke oven gas waste desulfurizer, which removes and collects elemental sulfur in the waste desulfurizer at high temperature, dissolves ferric oxide, calcium carbonate and other impurities in the waste desulfurizer by hydrochloric acid, separates calcium sulfate for the gypsum industry, forms a mixture of ferric oxide and calcium oxide by high-temperature roasting of the solution, uses the mixture as a sintering raw material, and absorbs gas to form hydrochloric acid, thereby realizing the harmless treatment of the waste desulfurizer.
The invention also provides an application of the harmless treatment method of the coke oven gas waste desulfurizer, which is used for the harmless treatment of the coke oven gas waste desulfurizer.
The specific technical scheme of the invention is as follows:
a harmless treatment method of a waste desulfurizer of coke oven gas comprises the following steps:
1) crushing the ferric oxide waste desulfurizer generated by the desulfurization of the coke oven gas;
2) heating the crushed waste desulfurizer powder for pretreatment, and condensing the sulfur elementary substance generated by heating to obtain liquid sulfur elementary substance;
3) mixing the pretreated waste desulfurizer powder and a hydrochloric acid solution, heating and reacting, and carrying out solid-liquid separation to obtain solid calcium sulfate;
4) roasting the liquid obtained by solid-liquid separation in the step 3), and recovering gas generated by roasting to form hydrochloric acid; the solid is a mixture of calcium oxide and iron oxide.
The waste desulfurizer in the step 1) mainly comprises the following components in percentage by mass: CaSO 4 50-80% of S, 0-20% of Fe 2 O 3 10-20% of CaCO 3 0-15% of other inevitable impurities0-5%, and 100% in total;
the process of the crushing treatment in the step 1) is not limited, and the crushed waste desulfurizer powder is required to have a particle size of less than 250 micrometers, wherein the mass proportion of the particle size of less than 75 micrometers is not less than 50%, and the mass proportion of the particle size of less than 150 micrometers is not less than 80%.
And 3) heating in the step 2), introducing inert gas components into a heating furnace or keeping a vacuum state, keeping the vacuum state, controlling the vacuum degree to be not lower than 0.08MPa, and controlling the heating temperature to be 350-500 ℃.
In the step 2), one end of a heating furnace for heating is connected with a condensing device, the sulfur simple substance enters the condensing device after being volatilized, the liquid sulfur simple substance is formed through condensation, the mass percentage content of the sulfur is more than or equal to 90%, and the condensing device adopts circulating water condensation or other condensing modes.
In the step 2), the reaction of heating for pretreatment is as follows:
S(s)→S(g)；
in the step 3), the pretreated waste desulfurizer powder reacts with the hydrochloric acid solution as follows:
Fe 2 O 3 +6HCl＝2FeCl 3 +3H 2 O；
CaCO 3 +2HCl＝CaCl 2 +CO 2 +H 2 O；
step 3), feeding the waste desulfurizer powder into a stirring tank, and adding a hydrochloric acid solution, wherein the mass fraction of the hydrochloric acid solution is 5-25%; the mass ratio of HCl in the hydrochloric acid solution to the pretreated waste desulfurizer powder is 1 (2.2-7.3).
The mixing and heating reaction in the step 3) is heating to a reaction temperature of 50-80 ℃; preferably, the reaction is carried out at a stirring speed of 0-300 r/min;
the solid-liquid separation in the step 3) is not limited in the manner, and can be performed by filtration, filter pressing or centrifugation. Calcium sulfate in the desulfurizer does not react with hydrochloric acid and becomes precipitate in the solution.
The reactions occurring during the calcination in step 4) are as follows:
2FeCl 2 +2H 2 O+1/2O 2 ＝Fe 2 O 3 +4HCl；
2FeCl 3 +3H 2 O＝Fe 2 O 3 +6HCl；
CaCl 2 +H 2 O＝CaO+2HCl；
and 4) roasting, wherein the roasting temperature is controlled within 550-850 ℃, and the liquid supply pressure is 350-550 KPa. And (3) introducing gas generated by roasting into a spray absorption device to form a total acid value of salt of 150-250 g/L.
In the acid mist absorption device in the step 4), in order to absorb hydrogen chloride gas generated by roasting, desalted water or rinsing water is adopted as absorption water, and the hydrogen chloride gas is absorbed to form regenerated acid.
The invention utilizes CaSO 4 The characteristic of difficult acid-base is that CaSO can be obtained by solid-waste separation after other oxides are dissolved by hydrochloric acid solution or waste hydrochloric acid 4 I.e. gypsum. The chloride dissolved in the waste hydrochloric acid is oxidized and roasted to form metal oxide for reuse, and the waste acid is regenerated to be used. Elemental sulfur and CaSO in waste desulfurizer 4 And metal elements are respectively utilized, so that the resource utilization effect is good.
The inventor finds that the waste desulfurizer contains more calcium sulfate besides valuable elemental sulfur, and also contains a certain amount of iron oxide and calcium oxide, and most of the remaining components except the elemental sulfur are not recycled in the prior art, and the two main reasons are as follows: firstly, the current lack of deep research on other components except elemental sulfur in the waste desulfurizer, the elemental sulfur is analyzed only from the theoretical reaction, and the main component is not found to be calcium sulfate actually. Secondly, the separation technology of the mixture of calcium sulfate, ferric oxide and calcium oxide is almost not available, the technology of the invention utilizes hydrochloric acid to separate the calcium sulfate from the ferric oxide and the calcium oxide, and the separated ferric chloride and calcium chloride solution can not be treated or utilized at present, but the invention utilizes a roasting technology which is difficult to think to convert the ferric chloride and the calcium chloride into the ferric oxide and the calcium oxide again for metal oxidation recycling, and simultaneously forms regenerated acid for continuous utilization. The total amount of acid does not vary from front to back, depending on the conservation of mass.
The design of the inventionThe harmless treatment method of the waste desulfurizer has simple process and good treatment effect. Respectively extracting and recovering the main components of the waste desulfurizer by different processes and methods, and respectively separating CaSO 4 Can be used in gypsum industry, the separated S is used in sulfuric acid industry and the like, and Fe 2 O 3 And CaO can be used for sintering in steel mills or other uses of Fe 2 O 3 And CaO. Compared with the prior art, the method provided by the invention has the advantages that different components contained in the coke oven gas waste desulfurizer are extracted and recovered by different processes and methods, so that all valuable components in the waste desulfurizer are utilized, and the waste desulfurizer is effectively treated and recycled.
Drawings
FIG. 1 is a schematic flow chart of the method of the present invention.
Detailed Description
Example 1
A harmless treatment method of a coke oven gas waste desulfurizer comprises the following steps:
the iron oxide waste desulfurizer produced by refining and desulfurizing certain coke oven gas comprises the following components in percentage by mass: CaSO 4 78.8% of S, 9.8% of Fe 2 O 3 The content is 10.3 percent, and other inevitable impurity components are 1.1 percent. 1 ton of waste desulfurizer is crushed, and the crushed waste desulfurizer powder requires that the particle size is less than 250 microns, wherein the mass fraction of the particle size less than 75 microns is not less than 50%, and the particle size less than 150 microns is not less than 80%; the crushed waste desulfurizer powder is pretreated by a heating device, the heating temperature is 450 ℃, the heating atmosphere is argon protection, the elemental sulfur generated by heating volatilizes into a condensing device, and the elemental sulfur is collected into liquid elemental sulfur, the purity of the elemental sulfur is 98.2 percent, and the mass of the elemental sulfur is 99 kg. 901kg of pretreated waste desulfurizer powder enters a stirring tank, is mixed with 10% by mass of hydrochloric acid solution and is stirred, the reaction temperature is 50 ℃, the stirring speed is 100r/min, the addition amount of the hydrochloric acid solution is 1.37 tons, and finally, solid-liquid separation is carried out, wherein the solid part is calcium sulfate, the dry basis weight is 791kg, and the purity of the calcium sulfate is 98.9%; the liquid part enters a roasting furnace, the roasting temperature ranges from 650 ℃ to 700 ℃, and the liquid supply pressure ranges from 450 ℃ to 500KPa, introducing gas generated by roasting into a spray absorption device to form hydrochloric acid, wherein the total acid value of the hydrochloric acid is 250g/L (the mass of HCl contained in 1 liter of hydrochloric acid solution), and the solid part is mainly ferric oxide and 98kg of ferric oxide.
Example 2
A harmless treatment method of a coke oven gas waste desulfurizer comprises the following steps:
iron oxide based waste desulfurizer, CaSO, produced by certain coke oven gas desulfurization process 4 51.2% of S, 14.6% of Fe 2 O 3 19.5% of CaCO 3 Content of 14.4% and other components 0.3%. 1 ton of waste desulfurizer is crushed, and the crushed waste desulfurizer powder requires that the particle size is less than 250 microns, wherein the mass fraction of the particle size less than 75 microns is not less than 50%, and the mass fraction of the particle size less than 150 microns is not less than 80%; the crushed waste desulfurizer powder is pretreated by a heating device, the heating temperature is 480 ℃, the heating atmosphere is argon protection, elemental sulfur generated by heating is volatilized into a condensing device, and the elemental sulfur is collected to be liquid elemental sulfur, the purity of the elemental sulfur is 94.6 percent, and the mass of the elemental sulfur is 145 kg. 855kg of pretreated waste desulfurizer powder enters a stirring tank, is mixed with hydrochloric acid solution with the mass concentration of 15% and is stirred, the reaction temperature is 80 ℃, the stirring speed is 300r/min, the adding amount of the hydrochloric acid solution is 2.55 tons, and finally, solid-liquid separation is carried out, wherein the solid part is calcium sulfate, the dry basis weight is 525kg, and the purity of the calcium sulfate is 97.1%; and (3) feeding the liquid part into a roasting furnace, wherein the roasting temperature is 700-750 ℃, the liquid supply pressure is 500-550 KPa, gas generated by roasting enters a spray absorption device to form hydrochloric acid, the total acid value of the hydrochloric acid is 150g/L, and the solid part becomes a mixture of calcium oxide and ferric oxide, and the total amount is 262 kg.
Example 3
A harmless treatment method of a coke oven gas waste desulfurizer comprises the following steps:
iron oxide based waste desulfurizer, CaSO, produced by certain coke oven gas desulfurization process 4 67.7% of S, 13.8% of Fe 2 O 3 14.7% of CaCO 3 The content is 1.6 percent, and the other components are 2.2 percent. 1 ton of waste desulfurizer is crushed, and the crushed waste desulfurizer powder needs to be crushedSolving the particle size of less than 250 microns, wherein the mass fraction of the particle size of less than 75 microns is not less than 50%, and the mass fraction of the particle size of less than 150 microns is not less than 80%; the crushed waste desulfurizer powder is pretreated by a heating device, the heating temperature is 460 ℃, the heating atmosphere is under the protection of argon, elemental sulfur generated by heating volatilizes into a condensing device, and the elemental sulfur is collected into liquid elemental sulfur, the purity of the elemental sulfur is 95.2%, and the mass of the elemental sulfur is 130 kg. 870kg of pretreated waste desulfurizer powder enters a stirring tank, is mixed with hydrochloric acid solution and is stirred, the reaction temperature is 60 ℃, the stirring speed is 200r/min, the adding amount of hydrochloric acid with the mass concentration of 20 percent is 1.1 ton, and finally, solid-liquid separation is carried out, wherein the solid part is calcium sulfate, the dry basis weight is 706kg, and the purity of the calcium sulfate is 95.4 percent; and (3) feeding the liquid part into a roasting furnace, wherein the roasting temperature ranges from 680 ℃ to 720 ℃, the liquid supply pressure is 480 KPa to 520KPa, feeding gas generated by roasting into a spray absorption device, forming hydrochloric acid, the total acid value of the hydrochloric acid is 190g/L, and the solid part becomes a mixture of calcium oxide and ferric oxide, and the total amount is 141 kg.
Comparative example 1
Iron oxide based waste desulfurizer, CaSO, produced by certain coke oven gas desulfurization process 4 78.8% of S, 9.8% of Fe 2 O 3 The content is 10.3 percent, and the other components are 1.1 percent. 1 ton of waste desulfurizer is crushed, and the particle size of the crushed waste desulfurizer powder is required to be less than 250 microns, wherein the particle size is not less than 50% of 75 microns, and the particle size is not less than 80% of 150 microns; the crushed waste desulfurizer powder is pretreated by a heating device, the heating temperature is 340 ℃, the heating atmosphere is argon protection, elemental sulfur generated by heating volatilizes into a condensing device, and is collected to form liquid elemental sulfur, the elemental sulfur purity is 98.1%, the elemental sulfur has the mass of 52kg (the temperature does not meet the requirement, and the obtained elemental sulfur is less). 948kg of pretreated waste desulfurizer powder enters a stirring tank, is mixed with a hydrochloric acid solution and is stirred, the reaction temperature is 40 ℃, the stirring speed is 100r/min, the mass concentration of the hydrochloric acid solution is 10 percent, the adding amount is 1.37 tons, and finally, solid-liquid separation is carried out, wherein the solid part is calcium sulfate, the dry basis weight is 836kg, and the purity of the calcium sulfate is 95.3 percent; the liquid part enters a roasting furnace, the roasting temperature is 540 ℃, the liquid supply pressure is 450-500 KPa, and the gas generated by roasting enters spray absorptionIn the device, hydrochloric acid is formed, the total acid value of the hydrochloric acid is 100g/L, and the solid part is mainly ferric oxide, namely 95kg of ferric oxide. Improper control of the calcination temperature causes a decrease in the yield of the collected hydrochloric acid.
Claims (10)
1. A harmless treatment method of a waste desulfurizer of coke oven gas is characterized by comprising the following steps:
1) crushing the ferric oxide waste desulfurizer generated by the desulfurization of the coke oven gas;
2) heating the crushed waste desulfurizer powder for pretreatment, and condensing the sulfur elementary substance generated by heating to obtain liquid sulfur elementary substance;
3) mixing the pretreated waste desulfurizer powder and a hydrochloric acid solution, heating and reacting, and carrying out solid-liquid separation to obtain solid calcium sulfate;
4) roasting the liquid obtained by solid-liquid separation in the step 3), and recovering gas generated by roasting to form hydrochloric acid; the solid is a mixture of calcium oxide and iron oxide.
2. The harmless treatment method of the waste desulfurizer for coke oven gas as claimed in claim 1, wherein the main component of the waste desulfurizer in step 1) is CaSO 4 50-80% of S, 0-20% of Fe 2 O 3 10-20% of CaCO 3 0 to 15 percent of the total content, and 0 to 5 percent of other inevitable impurities, accounting for 100 percent.
3. The method for harmless treatment of the coke oven gas waste desulfurizer as claimed in claim 1, wherein the crushed waste desulfurizer powder in the step 1) is required to have a particle size of less than 250 microns, wherein the mass proportion of the particle size of less than 75 microns is not less than 50%, and the mass proportion of the particle size of less than 150 microns is not less than 80%.
4. The harmless treatment method of the waste desulfurizer of the coke oven gas as recited in claim 1, wherein in the step 2), the heating furnace is used for introducing inert gas components or keeping a vacuum state, and the vacuum degree is not lower than 0.08 MPa.
5. The harmless treatment method of the coke oven gas waste desulfurizer as claimed in claim 1 or 4, wherein the heating temperature in the step 2) is controlled to be 350-500 ℃.
6. The harmless treatment method of the coke oven gas waste desulfurizer as claimed in claim 1 or 4, characterized in that in the step 2), one end of a heating furnace used for heating is connected with a condensing device, elemental sulfur enters the condensing device after being volatilized, and is condensed to form liquid elemental sulfur, wherein the mass content of sulfur is more than or equal to 90%.
7. The harmless treatment method of the coke oven gas waste desulfurizer as claimed in claim 1 or 4, wherein in the step 3), the mass ratio of HCl in the hydrochloric acid solution to the waste desulfurizer powder is within 1 (2.6-7.3).
8. The harmless treatment method of the waste desulfurizing agent of the coke oven gas as claimed in claim 1 or 4, characterized in that in the step 4), the roasting temperature is controlled within 550-850 ℃.
9. The harmless treatment method for the waste desulfurizer of coke oven gas as claimed in claim 1 or 8, wherein the liquid supply pressure is 350-550 KPa.
10. The application of the method of any one of claims 1 to 9, which is used for harmless treatment of the waste desulfurizer of the coke oven gas.
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| KR20030035016A (en) * | 2001-10-29 | 2003-05-09 | 한국전력공사 | The Manufacturing Method of α-Calcium Sulfate Hemihydrate from FGD Gypsum by Heating under Reduced Pressure |
| CN102010014A (en) * | 2010-12-30 | 2011-04-13 | 北京三聚环保新材料股份有限公司 | Method for preparing iron oxide red from waste desulfurizer |
| CN104211104A (en) * | 2014-08-23 | 2014-12-17 | 耿兆翔 | Separation and recovery method of thermal coal power plant flue gas desulfurization gypsum waste residues |
| CN109607491A (en) * | 2018-12-18 | 2019-04-12 | 武汉科技大学 | A kind of method that Desulphurization prepares sulfuric acid |
| CN110817804A (en) * | 2019-12-11 | 2020-02-21 | 中冶南方工程技术有限公司 | Spray roasting hydrochloric acid regeneration method and system for high-specific-surface-area iron oxide powder |
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| KR20030035016A (en) * | 2001-10-29 | 2003-05-09 | 한국전력공사 | The Manufacturing Method of α-Calcium Sulfate Hemihydrate from FGD Gypsum by Heating under Reduced Pressure |
| CN102010014A (en) * | 2010-12-30 | 2011-04-13 | 北京三聚环保新材料股份有限公司 | Method for preparing iron oxide red from waste desulfurizer |
| CN104211104A (en) * | 2014-08-23 | 2014-12-17 | 耿兆翔 | Separation and recovery method of thermal coal power plant flue gas desulfurization gypsum waste residues |
| CN109607491A (en) * | 2018-12-18 | 2019-04-12 | 武汉科技大学 | A kind of method that Desulphurization prepares sulfuric acid |
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