CN113621392A - Method for improving sulfur fixation rate in coal pyrolysis by using ash heat carrier - Google Patents
Method for improving sulfur fixation rate in coal pyrolysis by using ash heat carrier Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 88
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000011593 sulfur Substances 0.000 title claims abstract description 57
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 57
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000010883 coal ash Substances 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 239000002956 ash Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 9
- 239000000571 coke Substances 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 description 15
- 230000023556 desulfurization Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004774 atomic orbital Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The application discloses a method for improving sulfur fixation rate in coal pyrolysis by using an ash heat carrier, which comprises the following specific processes: the first step is as follows: dissolving water-soluble calcium salt and/or water-soluble zinc salt in water to prepare a treatment solution, soaking coal ash burnt by a power plant in the treatment solution for 20-30 min, and drying for later use; the second step is that: mixing a certain amount of raw material coal with the treated coal ash, and pyrolyzing the raw material coal and the treated coal ash under the condition of isolating air to inhibit the separation of sulfur-containing compound gas in the pyrolysis of the coal and obtain clean pyrolysis gas; the third step: and completely soaking the pyrolyzed semicoke or coke in an acid solution for 1-3 h, dissolving sulfur in coal in the acid solution, washing to remove coal ash mixed in the coal after soaking, removing most of sulfur in the coal, and obtaining clean semicoke or coke. The method can reduce the discharge amount of sulfur oxides in the pyrolysis gas generated in the coal pyrolysis, is simple, has easily controlled process conditions, and has multiple benefits of environmental protection, economy and the like.
Description
Technical Field
The invention belongs to the field of coal pyrolysis product desulfurization utilization, and particularly relates to a method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier.
Background
Sulfur is one of the harmful elements of coal and can cause different degrees of harm in the utilization processes of combustion, gasification, coke making and the like of coal. Wherein about 50% to 70% of the sulfur in the pyrolysis process is transferred to the coke, which has a large impact on the subsequent utilization of the coke. The current research on the desulfurization technology before coal utilization mainly focuses on three types of physical washing, chemical desulfurization and microbial desulfurization. The chemical desulfurization method is commonly used, and mainly refers to that sulfur existing in coal is converted into other forms which are easy to remove by using a certain chemical reaction, so that the aim of desulfurization is fulfilled. Currently, the chemical desulfurization methods under development include alkaline desulfurization, acid-washing desulfurization, solvent extraction desulfurization, microwave method, radiation method, electrochemical method, and the like, as well as multi-method combined desulfurization processes. The pickling desulfurization is mainly characterized in that: through acid-base reaction, sulfur of sulfide species is released in the form of hydrogen sulfide, so that the aim of desulfurization is fulfilled.
The metal oxide desulfurizing agent has been studied for decades, but the requirement for high temperature desulfurizing agent is high, which seriously affects the progress of industrialization. Many research institutes in the world have been subjected to extensive research work to reach substantial conclusions. The metal-based desulfurizer can promote the removal of sulfur, the cation outer electron layer is easy to gain and lose electrons and has stronger oxidability, and when meeting with an external orbit, a crystal field is formed due to the atomic orbital characteristic of the inner layer, so that the chemical adsorption is influenced, and the catalytic reaction is further influenced. The metal-based desulfurizing agent reduces the activation energy of pyrolysis on one hand in the coal pyrolysis process, so that metal ions generate a complex compound at an unsaturated functional group, and more micromolecular free radicals are formed; on the other hand, the oxidation of the metal-based desulfurizer can oxidize and decompose the sulfur in a low valence state, thereby improving the desulfurization rate.
Disclosure of Invention
The technical problem to be solved is as follows:
aiming at the defects of the prior art, the application provides a method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier, and solves the difficult problems of high requirement and the like of the existing high-temperature desulfurizer.
The technical scheme is as follows:
in order to achieve the purpose, the application is realized by the following technical scheme:
a method for improving sulfur fixation rate in coal pyrolysis by using an ash heat carrier comprises the following steps:
the first step is as follows: dissolving water-soluble calcium salt and/or water-soluble zinc salt in water to prepare a treatment solution, soaking coal ash burnt by a power plant in the treatment solution for 20-30 min, and drying for later use to obtain treated coal ash;
the second step is that: mixing the raw material coal with the treated coal ash, and pyrolyzing the raw material coal and the treated coal ash under the condition of isolating air to inhibit the separation of sulfur-containing compound gas in the pyrolysis of the coal so as to obtain clean pyrolysis gas;
the third step: and completely soaking the pyrolyzed semicoke or coke in an acid solution for 1-3 h, dissolving the sulfur in the coal in the acid solution, washing to remove the coal ash mixed in the solution after soaking, removing the sulfur in the coal, and obtaining clean semicoke or coke.
Further, in the first step, the water-soluble calcium salt is calcium nitrate and/or calcium chloride, and the water-soluble zinc salt is zinc nitrate and/or zinc chloride.
Further, the mass ratio of the water-soluble calcium salt and/or the water-soluble zinc salt in the treating fluid in the first step to the coal ash after combustion in a power plant is 0.01-0.05.
Further, the mass ratio of the water used in the first step to the treated coal ash is 1: 1.2 to 1.5.
Further, the coal pyrolysis temperature in the second step is 600-.
Further, the mass ratio of the treated coal ash to the raw material coal in the second step is 1: 2 to 5.
Further, the acid solution is one or a mixture of several of hydrochloric acid, sulfuric acid, acetic acid and oxalic acid, and the concentration of the acid solution is 0.1-0.2 mol/L.
Further, the mass ratio of the acid solution to the raw material coal in the third step is 1: 5.
has the advantages that:
the application provides a method for improving sulfur fixation rate in coal pyrolysis by using an ash heat carrier, which has the following beneficial effects:
1. the removal efficiency of sulfur in coal is high: the coal ash treated by the treatment fluid is mixed with the pyrolysis coal, so that the emission of sulfur-containing gas in the pyrolysis gas can be effectively reduced.
2. The influence on the utilization process of the pyrolysis gas after coal pyrolysis is small: the coal ash mixing after the treatment by the treatment liquid can reduce the emission of harmful sulfur-containing gas in coal pyrolysis, and the pressure of a subsequent device for treating the coal pyrolysis gas is reduced.
3. The technical method has wide applicability: when the treated coal ash is mixed, the coal ash can be used together with the corresponding sulfur-fixing desulfurization type addition auxiliary agent, thereby achieving multiple purposes, reducing the production procedures and having strong universality.
4. The required ingredients are readily available: the coal ash used in the invention is the waste coal ash after the combustion in the power plant, which contains a large amount of minerals and natural metal oxides, and provides a new idea for recycling the solid waste coal ash. Meanwhile, in the actual operation, the wet coal preparation method is introduced in the existing process of preparing the semicoke by pyrolysis, only the acid washing process needs to be added into the coal preparation, the coal ash after the sulfur treatment is fixed can be removed from the coal along with the acid washing solution, and the method can be realized without more additional processes, is simple, mature and effective.
Detailed Description
The following will further explain the embodiments and working procedures of the present invention by referring to examples.
Dissolving water-soluble calcium salt and/or water-soluble zinc salt (the mass ratio of an additive to coal ash is 0.01-0.05) in water (the mass ratio of the amount of water to the coal ash to be treated is 1: 1.2-1.5) to prepare a treatment solution, soaking the coal ash burnt by a power plant in the treatment solution for 20-30 min, drying the coal ash for later use to obtain treated coal ash, wherein the additive contained in the treatment solution is the water-soluble calcium salt and/or the water-soluble zinc salt, and mixing the coal ash treated by the treatment solution and raw coal in a ratio of 1: 2-5, putting the mixed coal sample into a high-temperature tubular furnace, and pyrolyzing under the condition of isolating air, wherein the coal pyrolysis temperature is 600-900 ℃.
The semicoke after the coal pyrolysis is subjected to acid pickling by an acid solution to remove the mixed coal ash and the sulfides fixed by the coal ash, so that the sulfur removal efficiency is improved. The acid comprises any one or a mixture of hydrochloric acid, sulfuric acid, acetic acid and oxalic acid. The concentration of the acid solution is 0.1-0.2 mol/L. The mass ratio of the acid solution to the raw material coal is 1: 5. the acid solution immersion cleaning time is 1-3 h. And washing the acid-washed coal sample with a large amount of water to remove impurity ions introduced into the coal.
The coal coke obtained by the invention can be used as a civil fuel or a coal gasification and liquefaction raw material.
The principle of the invention is as follows:
the coal ash contains oxides such as ferric oxide and calcium oxide, and after the coal ash is soaked in the treating liquid, more effective components such as calcium and the like are added in the coal ash. The coal ash treated by the treatment liquid is mixed in raw coal, rich substances in the coal ash contain a large amount of cations, and the cation outer electron layer is easy to lose the characteristics of electrons and stronger oxidizability, and meanwhile, due to the complex synergistic effect of various metals, the treated coal ash can play a role in fixing sulfur and fixing sulfur in the coal pyrolysis processBy inhibiting the formation of sulfur oxides by gases, such as H, evolved from the coal during pyrolysis2S, COS and other sulfur-containing gases react with the metal additive to generate sulfide, and H is inhibited due to the synergistic effect of the minerals and effective components in the coal ash2S, COS, etc., to achieve the effect of fixing sulfur. And (4) eluting the pyrolyzed coal, and removing the mixed coal ash and the generated sulfide.
The present invention will be further described with reference to the following specific examples.
Example 1:
weighing zinc chloride according to the mass ratio of the zinc chloride to the coal ash of 0.05 in coal ash combusted in an electric power plant, dissolving the zinc chloride in water and the coal ash in a mass ratio of 1: 1.5 in tap water to prepare a treatment liquid. Soaking coal ash in the treating solution for 30min, and drying. The pyrolysis raw material coal has 3.15 percent of total sulfur content and less than 0.15mm of granularity. Mixing the raw material coal and the treated coal ash according to the proportion of 2: 1, and uniformly mixing. 2g of the treated coal sample was loaded on a porcelain boat, which was placed in a high temperature tube furnace and pyrolyzed in the absence of air, at a final pyrolysis temperature of 800 ℃ and held at the final temperature for 30 min. Preparing 0.2mol/L oxalic acid solution, wherein the mass ratio of the oxalic acid solution to raw material coal is 1: and 5, soaking the pyrolyzed coal sample in the water for 3 hours. And (4) carrying out three-wheel water washing on the soaked coal sample, wherein each time of water washing is 10 min. The pyrolysis result shows that the mass ratio of the sulfur in the flue gas to the total sulfur of the raw coal is reduced from 18.7% to 3.1%, the mass ratio of the sulfur in the tar to the total sulfur of the raw coal is reduced from 36.9% to 16.3%, and the sulfur fixing rate is 80.6%.
Example 2:
weighing calcium chloride according to the mass ratio of the calcium chloride to the coal ash of 0.04 in coal ash combusted in an electric power plant, dissolving the calcium chloride in water and the coal ash in a mass ratio of 1: 1.5 of tap water. And (3) soaking the coal ash in the treatment solution for 30min, and drying to obtain the pyrolyzed raw material coal with the total sulfur content of 3.15%. Mixing the raw material coal and the treated coal ash according to the ratio of 3: 1, and uniformly mixing. A porcelain boat was used to carry 3g of the treated coal sample, and the porcelain boat was placed in a high temperature tube furnace and pyrolyzed in the absence of air, with a final pyrolysis temperature of 900 ℃ and held at the final temperature for 30 min. Preparing 0.1mol/L hydrochloric acid solution, wherein the mass ratio of the hydrochloric acid solution to the raw material coal is 1: and 5, soaking the pyrolyzed coal sample in the water for 1 h. And (4) carrying out three-wheel water washing on the soaked coal sample, wherein each time of water washing is 10 min. The pyrolysis result shows that the mass ratio of the sulfur in the flue gas to the total sulfur of the raw coal is reduced from 18.7% to 5.8%, the mass ratio of the sulfur in the tar to the total sulfur of the raw coal is reduced from 36.9% to 16.6%, and the sulfur fixing rate is 77.6%.
Example 3:
weighing zinc chloride and calcium chloride according to the mass ratio of the zinc chloride to the coal ash of 0.03 to 0.02, dissolving the zinc chloride to the calcium chloride in a solution of water to the coal ash in a mass ratio of 1: 1.5 of tap water. And (3) soaking the coal ash in the treatment solution for 30min, and drying to obtain the pyrolyzed raw material coal with the total sulfur content of 3.15%. Mixing the raw material coal and the treated coal ash according to the proportion of 2: 1, and uniformly mixing. 2g of the treated coal sample was loaded on a porcelain boat, which was placed in a high temperature tube furnace and pyrolyzed in the absence of air, with a final pyrolysis temperature of 800 ℃ and left at the final temperature for 30 min. Preparing 0.1mol/L hydrochloric acid solution, wherein the mass ratio of the hydrochloric acid solution to the raw material coal is 1: and 5, soaking the pyrolyzed coal sample in the water for 1 h. And (4) carrying out three-wheel water washing on the soaked coal sample, wherein each time of water washing is 10 min. The mass ratio of the sulfur in the flue gas to the total sulfur in the raw coal is reduced from 18.7% to 2.8%, the mass ratio of the sulfur in the tar to the total sulfur in the raw coal is reduced from 36.9% to 12.1%, and the sulfur fixing rate is 85.1%.
Finally, it should be understood that the above-described preferred embodiments are merely illustrative of the technical solutions of the present application and are not intended to limit the present application, and although the present application has been described in detail through the above-described preferred embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the present application, and any changes, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. A method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier is characterized by comprising the following steps:
the first step is as follows: dissolving water-soluble calcium salt and/or water-soluble zinc salt in water to prepare a treatment solution, soaking coal ash burnt by a power plant in the treatment solution for 20-30 min, and drying for later use to obtain treated coal ash;
the second step is that: mixing the raw material coal with the treated coal ash, and pyrolyzing the raw material coal and the treated coal ash under the condition of isolating air to inhibit the separation of sulfur-containing compound gas in the pyrolysis of the coal so as to obtain clean pyrolysis gas;
the third step: and completely soaking the pyrolyzed semicoke or coke in an acid solution for 1-3 h, dissolving the sulfur in the coal in the acid solution, washing to remove the coal ash mixed in the solution after soaking, removing the sulfur in the coal, and obtaining clean semicoke or coke.
2. The method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier according to claim 1, wherein the method comprises the following steps: in the first step, the water-soluble calcium salt is calcium nitrate and/or calcium chloride, and the water-soluble zinc salt is zinc nitrate and/or zinc chloride.
3. The method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier according to claim 1, wherein the method comprises the following steps: and in the first step, the mass ratio of the water-soluble calcium salt and/or water-soluble zinc salt in the treatment liquid to the coal ash burnt by the power plant is 0.01-0.05.
4. The method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier according to claim 1, wherein the method comprises the following steps: the mass ratio of the water consumption in the first step to the treated coal ash is 1: 1.2 to 1.5.
5. The method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier according to claim 1, wherein the method comprises the following steps: the coal pyrolysis temperature in the second step is 600-900 ℃.
6. The method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier according to claim 1, wherein the method comprises the following steps: the mass ratio of the treated coal ash to the raw material coal in the second step is 1: 2 to 5.
7. The method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier according to claim 1, wherein the method comprises the following steps: the acid solution is one or a mixture of several of hydrochloric acid, sulfuric acid, acetic acid and oxalic acid, and the concentration of the acid solution is 0.1-0.2 mol/L.
8. The method for improving the sulfur fixation rate in coal pyrolysis by using an ash heat carrier according to claim 1, wherein the method comprises the following steps: in the third step, the mass ratio of the acid solution to the raw material coal is 1: 5.
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| CN202110865046.XA CN113621392A (en) | 2021-07-29 | 2021-07-29 | Method for improving sulfur fixation rate in coal pyrolysis by using ash heat carrier |
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| CN202110865046.XA CN113621392A (en) | 2021-07-29 | 2021-07-29 | Method for improving sulfur fixation rate in coal pyrolysis by using ash heat carrier |
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