CN113460970A - Device and method for green separation and purification of sulfur in desulfurization waste liquid - Google Patents
Device and method for green separation and purification of sulfur in desulfurization waste liquid Download PDFInfo
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- 239000011593 sulfur Substances 0.000 title claims abstract description 223
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 223
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 239000007788 liquid Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000000926 separation method Methods 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- 238000000746 purification Methods 0.000 title claims abstract description 51
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 48
- 230000023556 desulfurization Effects 0.000 title claims abstract description 48
- 238000002844 melting Methods 0.000 claims abstract description 63
- 230000008018 melting Effects 0.000 claims abstract description 63
- 238000005188 flotation Methods 0.000 claims abstract description 44
- 230000008929 regeneration Effects 0.000 claims abstract description 14
- 238000011069 regeneration method Methods 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 33
- 238000010521 absorption reaction Methods 0.000 claims description 32
- 239000012065 filter cake Substances 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- 239000002893 slag Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 14
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 14
- 239000002912 waste gas Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 4
- 238000007323 disproportionation reaction Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002076 thermal analysis method Methods 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000011269 tar Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- -1 sulfur ions Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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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
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0232—Purification, e.g. degassing
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
本发明公开了一种脱硫废液中硫的绿色分离提纯的装置和方法，该装置包括固液分离器、气浮熔硫釜、精细分离器和解析分离器；气浮熔硫釜的硫滤饼加料口和硫液出口分别与固液分离器的固相出口和精细分离器的进料口相连；精细分离器的溶硫液出口与解析分离器的进料口相连。本发明可快速将脱硫废液中的粗硫磺、焦油和杂质在气浮熔硫釜中分开，节省能耗；利用系统循环的再生回收液进行提纯分离，在解析分离硫磺的同时回收有效成分，得到再生回收液返回精细分离器，避免对环境造成危害，减少运行成本；所提供的硫的绿色分离提纯的装置，尤其是气浮熔硫釜，设计巧妙科学，所提纯生产的工业硫磺纯度在99.5％以上，易于大规模推广使用。
The invention discloses a green separation and purification device and method for sulfur in desulfurization waste liquid. The cake feeding port and the sulfur liquid outlet are respectively connected with the solid phase outlet of the solid-liquid separator and the feed port of the fine separator; the dissolved sulfur liquid outlet of the fine separator is connected with the feed port of the analytical separator. The method can quickly separate the crude sulfur, tar and impurities in the desulfurization waste liquid in the air flotation sulfur melting kettle to save energy consumption; the regeneration recovery liquid circulating in the system is used for purification and separation, and the effective components are recovered while analyzing and separating the sulfur. The regenerated recovered liquid is returned to the fine separator to avoid harm to the environment and reduce operating costs; the provided device for green separation and purification of sulfur, especially the air flotation sulfur melting kettle, has an ingenious and scientific design, and the purity of the purified industrial sulfur is in More than 99.5%, easy to promote and use on a large scale.
Description
Technical Field
The invention relates to the technical field of recycling of coking product desulfurization waste liquid, in particular to a device and a method for green separation and purification of sulfur in desulfurization waste liquid.
Background
The coke oven gas byproduct crude sulfur of the coke-oven plant is obtained in a desulfurization working section for purifying coke oven gas, HPF wet liquid phase catalysis method which takes ammonia as alkali source is mainly adopted for desulfurization, most of sulfur foam obtained at the top of a regeneration tower recovers wet sulfur by a filter pressing method, or a sulfur melting kettle recovers solid sulfur.
In the desulfurization working section, impurities such as tar, naphthalene and the like in the coal gas not only have great influence on the desulfurization efficiency, but also seriously influence the purity of sulfur, so that the ammonia method HPF desulfurization process is the same as other desulfurization processes, and the content of the tar and the content of the naphthalene in the coal gas entering a desulfurization tower are required to be respectively less than 50mg/m3And 0.5g/m3. In the actual production, the impurities of tar, naphthalene and the like in the purified gas still cause the sulfur content of the sulfur product to be low, generally 60-75%, and the color of the sulfur product is earthy yellow or black yellow, thereby influencing the sulfur contentThe usage of the sulfur can only be sold at a very low price, even the sulfur cannot be used due to poor color or low purity sometimes, and can only be stacked in the form of solid waste, and at the present stage, if the crude sulfur cannot be timely recovered by adopting an effective technical means, a large amount of sulfur resources are wasted, the environment is seriously polluted, and potential safety hazards are brought.
The Chinese patent application with publication number CN111232934A discloses a device for utilizing desulfurization waste liquid and an operation method thereof, which adopts the procedures of sulfur incineration and two-conversion and two-absorption to prepare crude sulfur into sulfuric acid so as to achieve the purpose of recycling the crude sulfur; although the method can prepare the crude sulfur and the desulfurized liquid into the sulfuric acid by the acid preparation equipment, the waste is changed into valuable, but the method has the problems of large investment, high energy consumption, low benefit and the like.
The Chinese patent application with the publication number of CN101397127A discloses a method for purifying crude sulfur, which adopts a vacuum distillation method, controls the system pressure and the distillation temperature in an external heating type vacuum furnace to carry out vacuum distillation, and purifies the crude sulfur; the method adopts an external heating type vacuum furnace, carries out vacuum distillation under the conditions that the system pressure is 5-400Pa, the distillation temperature is 50-100 ℃ and the distillation time is 15-120min, and finally obtains purer sulfur, but has the problems of high requirements on equipment materials and performance, high energy consumption in the production process and the like.
The Chinese patent application with the publication number of CN101397127A discloses a decoloring and purifying process of coke oven gas desulfurization byproduct crude sulfur, which adopts a nonpolar organic solvent with good sulfur solubility to extract sulfur in the crude sulfur; the method adopts CS2、C2HCl3And CCl4The extraction method of organic solvent can also obtain relatively pure sulfur, but the used organic solvent has relatively high toxicity and relatively high volatility, belongs to inflammable and explosive substances, and has the problems of relatively complicated process, relatively high requirement on production safety, relatively high environmental pollution and the like.
Disclosure of Invention
In view of the above, the invention provides a device and a method for green separation and purification of sulfur in desulfurization waste liquid.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a device for green separation and purification of sulfur in desulfurization waste liquid comprises a solid-liquid separator, an air floatation sulfur melting kettle, a fine separator and an analytical separator.
Specifically, a sulfur filter cake feeding port and a sulfur liquid outlet of the air-flotation sulfur melting kettle are respectively connected with a solid phase outlet of the solid-liquid separator and a feeding port of the fine separator.
Specifically, a sulfur solution outlet of the fine separator is connected with a feed inlet of the desorption separator.
In the technical scheme, the air-flotation sulfur melting kettle comprises a kettle body and a jacket layer arranged outside the kettle body.
The sulfur filter cake feeding port is arranged between the baffle plate and the inner wall of the kettle body close to one side of the baffle plate, the inner wall of the kettle body far away from one side of the baffle plate is sequentially provided with a water-scum outlet and a sulfur liquid outlet from top to bottom, the top of the kettle body far away from one side of the baffle plate is provided with a tail gas suction port, and the bottom of the kettle body is provided with a heavy slag outlet.
Specifically, the bottom and the top of the jacket layer are respectively provided with a heat source inlet and a heat source outlet.
Further, in the above technical solution, the air-flotation sulfur melting kettle further comprises a thermometer port disposed at the top of the kettle body and/or a plurality of gas pipe inlets uniformly disposed at the bottom of the side surface of the kettle body.
Still further, in the above technical solution, the apparatus for green separation and purification of sulfur in desulfurized waste liquid further comprises a tail gas absorption tower and/or a hot-pressing separator.
Specifically, the tail gas absorption tower is connected with a tail gas absorption port of the air floatation sulfur melting kettle;
specifically, the hot-pressing separator is connected with a water-scum outlet and a heavy-scum outlet of the air-flotation sulfur melting kettle.
Still further, in the above technical solution, the apparatus for green separation and purification of sulfur in the desulfurization waste liquid further comprises a waste gas absorption tower; and a waste gas inlet and a regenerated liquid outlet of the waste gas absorption tower are respectively connected with a desorption gas outlet of the desorption separator and a recovery agent inlet of the fine separator.
The invention also provides a method for green separation and purification of sulfur in the desulfurization waste liquid, which comprises the following steps:
s1, treating the desulfurization waste liquid by using a solid-liquid separator to obtain a sulfur-containing filter cake with the water content of 20-50%;
s2, introducing the sulfur-containing filter cake obtained in the step S1 into an air-flotation sulfur melting kettle, firstly heating to control the temperature of the air-flotation sulfur melting kettle to be 75-90 ℃, separating water in the sulfur-containing filter cake, then discharging the sulfur-containing filter cake from a water-scum outlet of the air-flotation sulfur melting kettle, then heating to control the temperature of the air-flotation sulfur melting kettle to be 125-cake 165 ℃, separating scum, crude sulfur liquid and heavy slag in the sulfur-containing filter cake, and then respectively discharging the sulfur-containing filter cake from a water-scum outlet, a sulfur liquid outlet and a heavy slag outlet of the air-flotation sulfur melting kettle;
s3, introducing the crude sulfur liquid in the step S2 into a fine separator, and adding S2-Ions and/or HS-Recovering agent of ion (main component (NH)4)2S、NH4HS, etc.), sulfur ions are utilized to react with sulfur under alkaline conditions, and solid-liquid separation is carried out after the reaction to obtain sulfur-dissolved solution and tar;
s4, introducing the sulfur-dissolved solution obtained in the step S3 into an analytical separator, performing disproportionation reaction through thermal analysis, controlling the temperature in the analytical separator in the reaction process to be 80-100 ℃, reacting for 30-120min, and performing gas-solid-liquid separation to obtain hydrogen sulfide + ammonia gas, high-purity sulfur and analyzed solution.
In the above technical scheme, the method for green separation and purification of sulfur in the desulfurization waste liquid further comprises,
s5, the hydrogen sulfide + ammonia gas in step S4 is introduced into an exhaust gas absorption tower, and the regenerated liquid obtained after absorption is introduced into a fine separator in step S3 and recovered for reuse.
Preferably, in the above technical solution, the method for green separation and purification of sulfur in desulfurization waste liquid further includes returning the analyzed liquid in step S4 to a regeneration tower in the coking HPF wet desulfurization process.
In the above technical solution, in step S1, the sulfur content of the desulfurized waste liquid is 40 to 90 wt%.
Further, in the above technical solution, in the step S2, the method further includes blowing nitrogen gas from an air pipe inlet of the air-flotation sulfur melting kettle while heating and controlling the temperature of the air-flotation sulfur melting kettle to 125-.
Further, in the above technical solution, in step S2, the method further includes introducing the exhaust gas generated in the air-flotation sulfur melting kettle into an off-gas absorption tower for absorption treatment.
Further, in the above technical solution, in step S2, the method further includes introducing scum and heavy slag generated in the air floatation sulfur melting kettle into a hot-pressing separator, and separating to obtain impurities and recyclable tar.
Further, in the above technical solution, in step S2, the temperature of the air-float sulfur melting kettle is controlled to 125-.
In the method for green separation and purification of sulfur in the desulfurization waste liquid, the following formula is mainly involved:
(NH4)2S+nS＝(NH4)2S(1+n)
NH4HS+nS＝NH4HS(1+n)
(NH4)2S(1+n)＝(n-1)S↓+2NH3↑+2H2s ↓ (heating)
NH4HS(1+n)＝nS↓+NH3↑+H2S ↓ (heating)
2NH3+H2S＝(NH4)2S。
Compared with the prior art, the invention has the following advantages:
(1) the method for green separation and purification of sulfur skillfully utilizes the difference of physical properties of all components in the desulfurization waste liquid, quickly separates tar, impurities, crude sulfur and other components in the desulfurization waste liquid in the self-designed air-flotation sulfur melting kettle with a specific structure, has good separation effect and saves energy consumption;
(2) the method for green separation and purification of sulfur skillfully utilizes the recycled regeneration liquid, obtains high-purity sulfur through analytic separation, simultaneously utilizes the waste gas absorption tower to absorb the obtained hydrogen sulfide and ammonia gas to obtain the regeneration liquid, reuses the obtained regeneration liquid, returns the obtained regeneration liquid to the front fine separator, takes both the front and the back into consideration, and forms a complete internal circulation system, thereby not only avoiding the harm to the environment, but also reducing the operation cost;
(3) the method for green separation and purification of sulfur provided by the invention purifies and recovers the crude sulfur in the desulfurization waste liquid to obtain products such as tar, sulfur and the like, and separates to obtain miscellaneous salts, thereby thoroughly solving the problem that the foam desulfurization waste liquid is difficult to be effectively recycled, realizing the purification and recovery of the sulfur with low cost and creating economic benefits;
(4) the device for green separation and purification of sulfur, particularly the self-designed air-flotation sulfur melting kettle with a specific structure, provided by the invention, has the advantages that the design is ingenious and scientific, the industrial sulfur purified and produced by the method for green separation and purification of sulfur can meet the national standard requirements, the purity of the sulfur product is over 99.5 percent, and the device is easy to popularize and use on a large scale.
Drawings
FIG. 1 is a process flow diagram of a method for green separation and purification of sulfur in desulfurized waste liquid provided in the embodiment of the present invention;
FIG. 2 is a schematic structural diagram of an air-flotation sulfur melting kettle of the device for green separation and purification of sulfur in desulfurized waste liquid provided in the embodiment of the present invention;
in the figure:
the device comprises a kettle body 1, a sulfur filter cake feeding port 2, a tail gas absorption port 3, a water-scum outlet 4, a sulfur liquid outlet 5, a heavy slag outlet 6, a heat source inlet 7, a heat source outlet 8, a jacket layer 9, a thermometer port 10, a baffle plate 11 and a gas pipe inlet 12.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the means used are conventional in the art unless otherwise specified.
The terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The embodiment of the invention provides a device for green separation and purification of sulfur in desulfurization waste liquid, which specifically comprises a solid-liquid separator, an air-flotation sulfur melting kettle, a fine separator and an analytical separator.
Wherein:
the solid-liquid separator is a solid-liquid separating device commonly used in the field, such as a centrifugal separator, a filter, a suction filter and the like.
The air-flotation sulfur melting kettle comprises a kettle body 1 and a jacket layer 9 arranged outside the kettle body 1, as shown in figure 2. Specifically, a baffle plate 11 is fixedly arranged on the inner wall of the kettle body 1, a sulfur filter cake feeding port 2 is arranged at the top of the kettle body between the baffle plate 11 and the inner wall of the kettle body close to one side of the baffle plate 11, a water-scum outlet 4 and a sulfur liquid outlet 5 are sequentially arranged on the inner wall of the kettle body far away from one side of the baffle plate 11 from top to bottom, a tail gas suction port 3 is arranged at the top of the kettle body far away from one side of the baffle plate 11, and a heavy slag outlet 6 is arranged at the bottom of the kettle body 1; the bottom and the top of the jacket layer 9 are respectively provided with a heat source inlet 7 and a heat source outlet 8.
The fine separator and the analytical separator are those commonly used in the art and will not be described herein.
In detail, a sulfur filter cake feeding port and a sulfur liquid outlet of the air-flotation sulfur melting kettle are respectively connected with a solid phase outlet of a solid-liquid separator and a feeding port of a fine separator; the sulfur solution outlet of the fine separator is connected with the feed inlet of the desorption separator.
In an embodiment of the present invention, the air-flotation sulfur melting kettle in the apparatus for green separation and purification of sulfur from desulfurized waste liquid further includes a thermometer port 10 and/or a plurality of gas pipe inlets 12.
Specifically, the temperature measuring port 10 is arranged at the top of the kettle body 1 of the air-flotation sulfur melting kettle, and the plurality of gas pipe inlets 12 are uniformly arranged at the bottom of the side surface of the kettle body 1.
In a preferred embodiment of the present invention, the apparatus for green separation and purification of sulfur from desulfurized waste liquid further includes a tail gas absorption tower and/or a hot-pressing separator.
Specifically, the tail gas absorption tower is connected with a tail gas absorption port 3 of the air floatation sulfur melting kettle; the hot-pressing separator is connected with a water-scum outlet 4 and a heavy-scum outlet 6 of the air-flotation sulfur melting kettle.
In another preferred embodiment of the present invention, the apparatus for green separation and purification of sulfur from desulfurized waste liquid further comprises a waste gas absorption tower.
Specifically, the waste gas inlet and the regenerated liquid outlet of the waste gas absorption tower are respectively connected with the desorption gas outlet of the desorption separator and the recycling agent inlet of the fine separator.
The embodiment of the invention also provides a method for green separation and purification of sulfur in desulfurization waste liquid by using the device, which specifically comprises the following steps as shown in figure 1:
s1, treating the desulfurization waste liquid by using a solid-liquid separator to obtain a sulfur-containing filter cake with the water content of 20-50%, and returning the obtained separated filtrate to a desulfurization working section through a centrifugal pump;
s2, introducing the sulfur-containing filter cake obtained in the step S1 into an air-flotation sulfur melting kettle, controlling the temperature of the air-flotation sulfur melting kettle to be 75-90 ℃ through steam or electric heating, separating water in the sulfur-containing filter cake, then discharging the water-scum from a water-scum outlet of the air-flotation sulfur melting kettle, controlling the temperature of the air-flotation sulfur melting kettle to be 125-165 ℃ through steam or electric heating, and separating the scum, crude sulfur liquid and heavy slag in the sulfur-containing filter cake, then respectively discharging the scum, the crude sulfur liquid and the heavy slag from the water-scum outlet, the sulfur liquid outlet and the heavy slag outlet of the air-flotation sulfur melting kettle;
s3, introducing the crude sulfur liquid obtained in the step S2 into a fine separator, and adding S2-Ion ((NH)4)2S) and/or HS-Ion (NH)4HS), separating sulfur from tar by utilizing the principle that sulfide ions react with sulfur and sulfur under alkaline conditions to generate polysulfide, and performing solid-liquid separation after reaction to obtain sulfur-dissolved solution and tar;
s4, introducing the sulfur-dissolved solution obtained in the step S3 into an analytical separator, performing disproportionation reaction through thermal analysis, controlling the temperature in the analytical separator in the reaction process to be 80-100 ℃, reacting for 30-120min, and performing gas-solid-liquid separation to obtain hydrogen sulfide + ammonia gas, high-purity sulfur and analyzed solution.
In the method for green separation and purification of sulfur in the desulfurization waste liquid, the following formula is mainly involved:
(NH4)2S+nS＝(NH4)2S(1+n)
NH4HS+nS＝NH4HS(1+n)
(NH4)2S(1+n)＝(n-1)S↓+2NH32H2S pieces (heating)
NH4HS(1+n)＝nS↓+NH3A + H2S pieces (heating)
2NH3+H2S＝(NH4)2S。
In an embodiment of the present invention, the method for green separation and purification of sulfur in desulfurized waste liquid further includes:
s5, the hydrogen sulfide + ammonia gas obtained in step S4 is introduced into an exhaust gas absorption tower, and after absorption, the regenerated liquid obtained is introduced into a fine separator in step S3 and recovered for reuse.
Step S5 further includes returning the analyzed solution in step S4 to a regenerator in the coking HPF wet desulfurization process.
Specifically, in the method for separating and purifying sulfur in the desulfurization waste liquid in the green color, in step S1, the sulfur content of the desulfurization waste liquid is 40-90 wt%.
In a preferred embodiment of the present invention, in the method for separating and purifying sulfur from sulfur-containing waste liquid, step S2 further includes blowing nitrogen gas from the gas inlet of the air-flotation sulfur melting kettle while heating and controlling the temperature of the air-flotation sulfur melting kettle to 125-165 ℃, so as to accelerate the separation of dross, crude sulfur liquid and heavy slag.
In another preferred embodiment of the present invention, in the method for green separation and purification of sulfur in desulfurized waste liquid, step S2 further includes introducing the waste gas generated in the air-float sulfur melting kettle into a tail gas absorption tower for absorption treatment.
In another preferred embodiment of the present invention, in the method for green separation and purification of sulfur from desulfurized waste liquid, step S2 further includes introducing scum and heavy slag generated in the air floatation sulfur melting kettle into a hot pressing separator, and separating to obtain impurities and recyclable tar.
In an embodiment of the invention, in the method for separating and purifying sulfur from the desulfurization waste liquid, in step S2, the temperature of the air-float sulfur melting kettle is controlled to 125-.
Example 1
The device for green separation and purification of the sulfur and the method for green separation and purification of the sulfur are utilized to treat the foamy desulfurization waste liquid obtained from the coke oven gas purification and desulfurization section of the coke-oven plant, and the specific process is as follows:
carrying out suction filtration treatment on the foam desulfurization waste liquid with the water content of more than 75 wt% and the sulfur content of 74.3 wt% in the solid waste to obtain a sulfur-containing filter cake with the water content of 20.2 wt%; then introducing the sulfur-containing filter cake into an air-flotation sulfur melting kettle, firstly heating to control the temperature of the air-flotation sulfur melting kettle to be 80 ℃, keeping the temperature for about 1h, separating water in the sulfur-containing filter cake, then discharging the water-scum from a water-scum outlet of the air-flotation sulfur melting kettle, subsequently heating to control the temperature of the air-flotation sulfur melting kettle to be 145 ℃, keeping the temperature for 3h, continuously blowing a small amount of nitrogen with the pressure of 0.35Mpa during the period, stopping blowing the nitrogen after the reaction is finished, discharging crude sulfur liquid from a sulfur liquid outlet in the middle of the air-flotation sulfur melting kettle, cooling to normal temperature, and then putting into a fine separator; adding the recycled regeneration liquid into a fine separator, controlling the dissolving temperature to be 40-60 ℃, stirring and reacting for 1-2h to obtain a dark red sulfur-dissolved liquid, filtering and separating to return the obtained slag to an air-flotation sulfur melting kettle, introducing the sulfur-dissolved liquid into an analytical separator, controlling the temperature in the analytical separator to be 90-100 ℃, reacting for 1.5h, and carrying out gas-solid-liquid separation to obtain hydrogen sulfide + ammonia gas, the analyzed liquid and golden yellow sulfur solid.
According to the analysis of GB/T2449-2006 standard, the purity of the prepared golden yellow sulfur solid reaches 99.6 wt%, the first-grade product requirement is met, and meanwhile, the recovery rate of sulfur in the separation and purification process is 95.68%.
In addition, hydrogen sulfide and ammonia gas are introduced into a waste gas absorption tower, absorbed by water, and the obtained regeneration liquid is returned to the fine reactor for recycling.
The method for green separation and purification of sulfur skillfully utilizes the difference of physical properties of all components in the desulfurization waste liquid, quickly separates tar, impurities, crude sulfur and other components in the desulfurization waste liquid in the self-designed air-flotation sulfur melting kettle with a specific structure, has good separation effect and saves energy consumption; the method for green separation and purification of sulfur skillfully utilizes the recycled regeneration liquid, obtains high-purity sulfur through analytic separation, simultaneously utilizes the waste gas absorption tower to absorb the obtained hydrogen sulfide and ammonia gas to obtain the regeneration liquid, reuses the obtained regeneration liquid, returns the obtained regeneration liquid to the front fine separator, takes both the front and the back into consideration, and forms a complete internal circulation system, thereby not only avoiding the harm to the environment, but also reducing the operation cost; the method for green separation and purification of sulfur provided by the embodiment of the invention purifies and recovers the crude sulfur in the desulfurization waste liquid to obtain products such as tar, sulfur and the like, and separates to obtain miscellaneous salts, thereby thoroughly solving the problem that the foam desulfurization waste liquid is difficult to be effectively recycled, realizing the purification and recovery of sulfur with low cost and creating economic benefits; the device for green separation and purification of sulfur provided by the embodiment of the invention, in particular to the self-designed air-flotation sulfur melting kettle with a specific structure, is ingenious and scientific in design, industrial sulfur purified and produced by the method for green separation and purification of sulfur can meet the national standard requirements, the purity of a sulfur product is over 99.5%, and the device is easy to popularize and use on a large scale.
It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A device for green separation and purification of sulfur in desulfurization waste liquid, which is characterized in that,
comprises a solid-liquid separator, an air-flotation sulfur melting kettle, a fine separator and an analytical separator;
a sulfur filter cake feeding port and a sulfur liquid outlet of the air floatation sulfur melting kettle are respectively connected with a solid phase outlet of the solid-liquid separator and a feeding port of the fine separator;
and a sulfur solution outlet of the fine separator is connected with a feed inlet of the desorption separator.
2. The apparatus for green separation and purification of sulfur in desulfurized waste liquid according to claim 1, wherein,
the air-floatation sulfur melting kettle comprises a kettle body and a jacket layer arranged outside the kettle body;
a baffle plate is fixedly arranged on the inner wall of the kettle body, the sulfur filter cake feeding port is arranged between the baffle plate and the inner wall of the kettle body close to one side of the baffle plate, the inner wall of the kettle body far away from one side of the baffle plate is sequentially provided with a water-scum outlet and a sulfur liquid outlet from top to bottom, the top of the kettle body far away from one side of the baffle plate is provided with a tail gas suction port, and the bottom of the kettle body is provided with a heavy slag outlet;
and the bottom and the top of the jacket layer are respectively provided with a heat source inlet and a heat source outlet.
3. The apparatus for green separation and purification of sulfur in desulfurized waste liquid according to claim 2, wherein,
the air-floatation sulfur melting kettle further comprises a thermometer port arranged at the top of the kettle body and/or a plurality of air pipe inlets uniformly arranged at the bottom of the side surface of the kettle body.
4. The apparatus for green separation and purification of sulfur in desulfurized waste liquid according to claim 2 or 3, wherein,
the system also comprises a tail gas absorption tower and/or a hot-pressing separator;
the tail gas absorption tower is connected with a tail gas absorption port of the air floatation sulfur melting kettle;
the hot-pressing separator is connected with a water-scum outlet and a heavy-scum outlet of the air-floatation sulfur melting kettle.
5. The apparatus for green separation and purification of sulfur in desulfurized waste liquid according to any of claims 1 to 4, wherein,
also comprises a waste gas absorption tower;
and a waste gas inlet and a regenerated liquid outlet of the waste gas absorption tower are respectively connected with a desorption gas outlet of the desorption separator and a recovery agent inlet of the fine separator.
6. A method for green separation and purification of sulfur in desulfurization waste liquid, which is characterized in that,
the method comprises the following steps:
s1, treating the desulfurization waste liquid by using a solid-liquid separator to obtain a sulfur-containing filter cake with the water content of 20-50%;
s2, introducing the sulfur-containing filter cake obtained in the step S1 into an air-flotation sulfur melting kettle, firstly heating to control the temperature of the air-flotation sulfur melting kettle to be 75-90 ℃, separating water in the sulfur-containing filter cake, then discharging the sulfur-containing filter cake from a water-scum outlet of the air-flotation sulfur melting kettle, then heating to control the temperature of the air-flotation sulfur melting kettle to be 125-cake 165 ℃, separating scum, crude sulfur liquid and heavy slag in the sulfur-containing filter cake, and then respectively discharging the sulfur-containing filter cake from a water-scum outlet, a sulfur liquid outlet and a heavy slag outlet of the air-flotation sulfur melting kettle;
s3, introducing the crude sulfur liquid in the step S2 into a fine separator, and adding S2-ion and/or HS-ion recovery agent, solid-liquid separation after reaction to obtain sulfur-dissolved solution and tar;
s4, introducing the sulfur-dissolved solution obtained in the step S3 into an analytical separator, performing disproportionation reaction through thermal analysis, controlling the temperature in the analytical separator in the reaction process to be 80-100 ℃, reacting for 30-120min, and performing gas-solid-liquid separation to obtain hydrogen sulfide + ammonia gas, high-purity sulfur and analyzed solution.
7. The method for green separation and purification of sulfur in desulfurized waste liquid according to claim 6, characterized in that,
also comprises the following steps of (1) preparing,
s5, introducing the hydrogen sulfide and ammonia gas in the step S4 into an exhaust gas absorption tower, and introducing the regenerated liquid obtained after absorption into a fine separator in the step S3 for recycling;
preferably, the method further comprises the step of returning the analyzed liquid in the step S4 to a regeneration tower in the coking HPF wet desulphurization process.
8. The method for green separation and purification of sulfur in desulfurized waste liquid according to claim 6 or 7, characterized in that,
in step S1, the sulfur content of the desulfurization waste liquid is 40 to 90 wt%.
9. The method for green separation and purification of sulfur in desulfurized waste liquid according to any of claims 6 to 8, characterized in that,
in step S2, the method further comprises,
blowing nitrogen from an air pipe inlet of the air floatation sulfur melting kettle while heating and controlling the temperature of the air floatation sulfur melting kettle to be 125-165 ℃ to accelerate the separation of scum, crude sulfur liquid and heavy slag;
and/or introducing waste gas generated in the air floatation sulfur melting kettle into a tail gas absorption tower for absorption treatment;
and/or guiding scum and heavy slag generated in the air floatation sulfur melting kettle into a hot-pressing separator, and separating to obtain impurities and recyclable tar.
10. The method for green separation and purification of sulfur in desulfurized waste liquid according to any one of claims 6 to 9, characterized in that,
in step S2, the temperature of the air-float sulfur melting kettle is controlled at 125-165 ℃ to separate the scum, the crude sulfur liquid and the heavy slag for 1-6 h.
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