CN115178564A - Resource utilization method for harmless treatment of industrial waste salt - Google Patents
Resource utilization method for harmless treatment of industrial waste salt Download PDFInfo
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- CN115178564A CN115178564A CN202210697600.2A CN202210697600A CN115178564A CN 115178564 A CN115178564 A CN 115178564A CN 202210697600 A CN202210697600 A CN 202210697600A CN 115178564 A CN115178564 A CN 115178564A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 90
- 239000002440 industrial waste Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 60
- 238000001816 cooling Methods 0.000 claims abstract description 53
- 239000002893 slag Substances 0.000 claims abstract description 46
- 238000002425 crystallisation Methods 0.000 claims abstract description 37
- 230000008025 crystallization Effects 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000197 pyrolysis Methods 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 238000002076 thermal analysis method Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 24
- 238000003795 desorption Methods 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 42
- 239000010865 sewage Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 17
- 238000005192 partition Methods 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 15
- 230000003472 neutralizing effect Effects 0.000 claims description 14
- 239000000498 cooling water Substances 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 235000014443 Pyrus communis Nutrition 0.000 claims description 4
- 239000002737 fuel gas Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 3
- 239000008246 gaseous mixture Substances 0.000 abstract description 2
- 239000011343 solid material Substances 0.000 description 10
- 239000007921 spray Substances 0.000 description 10
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 chloride ions Chemical class 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/02—Settling tanks with single outlets for the separated liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a resource utilization method for harmless treatment of industrial waste salt, which comprises the steps of firstly feeding the industrial waste salt into a thermal analysis unit by adopting a dry-method feeding unit, heating the industrial waste salt to 300-600 ℃, evaporating moisture in the industrial waste salt, decomposing macromolecular organic matters by heating, spraying, cooling and purifying the produced high-temperature gaseous mixture to be used as boiler fuel, and using high-temperature steam produced by a boiler as a heat source of an evaporative crystallization unit; dissolving solid slag produced by pyrolysis, then performing filter pressing, removing impurities from obtained liquid, sending the obtained liquid into an evaporative crystallization unit to obtain industrial refined salt, and condensing evaporated water to return to a boiler or be used as circulating water. According to the invention, through the ordered combination of thermal desorption, dissolution and impurity removal, evaporative crystallization, cooling separation and the like, the industrial refined salt can be effectively extracted from the industrial waste salt, and the economic and environmental benefits are remarkable.
Description
Technical Field
The invention relates to the field of solid waste/hazardous waste treatment, in particular to a resource utilization method for harmless treatment of industrial waste salt.
Background
The industrial waste salt is mainly generated in the industrial production of pesticide production, drug synthesis, printing and dyeing and the like, and the process of high-salinity wastewater treatment and the like, and has the characteristics of various types, complex components, great environmental hazard and the like. In recent years, the yield of industrial waste salt in China is continuously increased, and no effective treatment method exists at present.
A lot of enterprises adopt a mode of self-building a warehouse and centrally temporarily storing industrial waste salt, but the industrial waste salt still needs to be treated subsequently. Some enterprises also adopt landfill, incineration and other modes to treat industrial waste salt. The landfill is that after the waste salt is solidified by concrete and the like, the waste salt is sent into a rigid landfill site for treatment according to the landfill standard requirement, the cost is high, the occupied area is large, and the method is not a final treatment method; the incineration is to heat the industrial waste salt to about 1000 ℃, the inorganic salt is melted at high temperature and flows into the furnace bottom to be discharged, and the organic matters are burnt and decomposed in the furnace, but the common problems of corrosion, secondary pollution of dioxin, slag formation and material blockage, high treatment cost and the like exist. Therefore, the development of the harmless treatment and resource utilization process technology of industrial waste salt is urgent.
Disclosure of Invention
Based on the technical problems, the invention provides a resource utilization method for harmless treatment of industrial waste salt.
The technical solution adopted by the invention is as follows:
a resource utilization method for harmless treatment of industrial waste salt comprises the following steps:
(1) Sending industrial waste salt into a dry-method feeding unit, and conveying the industrial waste salt to a thermal analysis unit through the dry-method feeding unit;
(2) The thermal analysis unit comprises a thermal analysis shell, and a conveying device and a heating device are arranged in the thermal analysis shell; the industrial waste salt entering the thermal desorption unit is flatly laid on the conveying device, the industrial waste salt moves along with the conveying device, and meanwhile, the industrial waste salt is heated to 300-600 ℃ through the heating device, so that moisture in the industrial waste salt is thermally desorbed, macromolecular organic matters are heated and decomposed, the produced high-temperature gas enters the cooling separation unit, and solid slag produced by pyrolysis enters the slag discharging cooling unit;
(3) A water cooling jacket is arranged on the slag cooling unit, cooling water is introduced into the water cooling jacket, solid slag produced by pyrolysis is cooled to 30-80 ℃ in an indirect water cooling mode, and then the solid slag is sent to a dissolving and impurity removing unit;
(4) The dissolving and impurity removing unit comprises a dissolving tank, solid slag from the slag cooling unit enters the dissolving tank to be dissolved, neutralizing liquid is added into the dissolving tank to precipitate soluble impurities in the dissolved solid slag, and mixed liquid after dissolving and precipitating is sent to the filtering unit;
(5) In the filtering unit, the mixed liquid is subjected to solid-liquid separation through a filtering device in the filtering unit, the separated solid slag is discharged, and the liquid is sent to an evaporation crystallization unit;
(6) The evaporative crystallization unit is provided with an evaporative crystallization device, and the liquid from the filtering unit is treated by the evaporative crystallization device to obtain the industrial refined salt.
Preferably, the method further comprises the steps of:
in the cooling separation unit, high-temperature gas generated by pyrolysis is directly cooled by spraying cooling water to 60-80 ℃, condensed sewage enters a sewage settling unit, and non-condensable gas enters a non-condensable gas treatment unit;
in the sewage settling unit, sewage is subjected to gravity settling separation, upper clear water is used as circulating water for spraying, and lower sewage is sent to the dissolving and impurity removing unit;
in the non-condensable gas treatment unit, the non-condensable gas is subjected to liquid separation, desulfurization and pressurization and then is used as boiler fuel gas.
Preferably, the dry-method feeding unit comprises an inclined conveying device, a feeding hole is formed in the bottom of the inclined conveying device, and a discharging hole is formed in the top of the inclined conveying device; a pretreatment unit is arranged above the feeding hole, the pretreatment unit comprises a stock bin, and a vibrating screen is arranged at the upper part of the stock bin; industrial waste salt is sent into the feed bin through the inclination belt, is provided with high low material level alarm device in the feed bin, and when high material level was reported to the police after, the material loading was stopped, when low material level was reported to the police, the start material loading was stopped after high material level reported to the police.
Preferably, be provided with dry-type distributing device in slope conveyor's discharge gate department, dry-type distributing device includes the cloth storehouse, is provided with the pan feeding mouth in the top center department of cloth storehouse, is provided with first pivot and second pivot in the inside in cloth storehouse, first pivot and second pivot parallel arrangement are provided with first blade in first pivot, and first blade is the symmetric distribution along the center of first pivot, is provided with the second blade in the second pivot, and the second blade is the symmetric distribution along the center of second pivot, and first blade and second blade are staggered arrangement.
Preferably, the conveying device is a crawler belt, a grate or a chain plate, and turning pear rakes are arranged above the conveying device at intervals; the heating device is a radiation plate or a radiation tube; the operating pressure inside the thermal desorption shell is micro-positive pressure, and the pressure range is gage pressure of 50-200 Pa.
Preferably, the neutralizing solution comprises BaCl 2 NaOH and Na 2 CO 3 Solution of said BaCl 2 NaOH and Na 2 CO 3 The solution is sequentially added into a dissolving tank, and Ca in the salt solution can be dissolved after the neutralization solution is added 2+ ，Mg 2+ ，SO 4 2- Soluble impurities are precipitated respectively.
Preferably, a first partition plate and a second partition plate are arranged inside the dissolving tank, and the dissolving tank is divided into a first compartment, a second compartment and a third compartment by the first partition plate and the second partition plate;
the upper part of the first bulkhead is provided with a material inlet, a dissolving liquid inlet and a first neutralizing liquid adding port, the first clapboard is positioned between the first bulkhead and the second bulkhead, the height of the first clapboard is higher than that of the second clapboard, and the upper part of the second bulkhead is provided with a second neutralizing liquid adding port; the bottoms of the first compartment and the second compartment are provided with conical sediment discharge ports; the bottom of the third compartment is provided with a mixed liquid outlet.
Preferably, the filtering device is a plate-and-frame filter press or a vacuum suction filter.
Preferably, the evaporative crystallization device is a multi-effect evaporative crystallization device, a multi-stage flash evaporation device or a mechanical evaporation device.
Preferably, the condensed water produced in the evaporative crystallization unit is used as boiler make-up water.
The beneficial technical effects of the invention are as follows:
the invention provides a brand new method for harmless treatment and resource utilization of industrial waste salt, and industrial refined salt can be effectively extracted from the industrial waste salt through the ordered matching of thermal desorption, dissolution impurity removal, evaporative crystallization, cooling separation and the like, and the economic and environmental benefits are obvious.
The invention also solves the problems of corrosion, secondary pollution of dioxin, slag formation and material blockage, high treatment cost and the like in the conventional incineration and other treatment methods, radiation heat transfer is adopted in the thermal desorption process, the high-temperature corrosion of halogen, particularly chloride ions, on refractory materials and steel is greatly avoided, and the industrial refined salt can be extracted by matching with the processes of dissolving, impurity removal and the like after thermal desorption, and meanwhile, the problem of coking and material blockage is effectively solved. In addition, high-temperature gas generated in the thermal desorption process passes through the cooling separation unit, condensed sewage enters the sewage settling unit for settling treatment, and non-condensable gas enters the non-condensable gas treatment unit for treatment and then is used as boiler fuel gas, so that the problem of secondary pollution caused by direct incineration of industrial waste salt can be solved, and comprehensive treatment and utilization can be realized.
Drawings
The invention is further described in the following detailed description with reference to the drawings in which:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic diagram of the overall architecture of a system embodying the present invention;
FIG. 3 is a schematic view of the structural principle of a dry distributor in the system employed in the present invention;
FIG. 4 is a schematic diagram of the structural principle of a thermal desorption device in the system adopted in the present invention;
FIG. 5 is a schematic view of the structure of a dissolving tank in the system of the present invention.
In the figure: i-a pretreatment unit, II-a feeding unit, III-a thermal desorption unit, IV-a cooling separation unit, V-a sewage settling unit, VI-a non-condensable gas treatment unit, VII-a slag cooling unit, VIII-a dissolving and impurity removing unit, IX-a filtering unit and X-an evaporative crystallization unit.
1-vibrating screen, 2-feeding port, 3-feeding port, 4-discharging port, 5-distributing device, 6-high temperature gas outlet, 7-slag outlet, 8-high temperature gas inlet, 9-spray water inlet, 10-noncondensable gas outlet, 11-sewage outlet, 12-noncondensable gas inlet, 13-noncondensable gas outlet, 14-filler, 15-sewage inlet, 16-dust-containing sewage outlet, 17-purified water outlet, 18-solid material inlet, 19-water cooling jacket, 20-solid material outlet, 21-material inlet, 22-mixed liquid outlet, 23-mixed liquid inlet, 24-solid slag outlet, 25-liquid outlet, 26-liquid inlet, 27-heating steam inlet, 28-industrial refined salt outlet, 29-steam condensate outlet, 30-evaporation steam outlet, 31-evaporation steam inlet, and 32-evaporation steam condensate outlet.
301-thermal desorption shell, 302-conveying device, 303-heating device, 304-stirring pear rake, 305-first pyrolysis section, 306-second pyrolysis section, 307-dry feed inlet, 308-feed outlet, 309-discharge shaft, 3010-upper sliding plate and 3011-lower sliding plate;
501-a distribution bin, 502-a first rotating shaft, 503-a second rotating shaft, 504-a first blade, 505-a second blade;
801-dissolving tank, 802-first partition plate, 803-second partition plate, 804-first compartment, 805-second compartment, 806-third compartment, 807-dissolving liquid inlet, 808-first neutralizing liquid adding port, 809-second neutralizing liquid adding port and 8010-precipitate discharging port.
Detailed Description
As shown in figure 1, the invention relates to a resource utilization method for harmless treatment of industrial waste salt, which comprises the steps of firstly sending the industrial waste salt into a thermal analysis unit by a dry-method feeding unit, heating the industrial waste salt to 300-600 ℃, evaporating moisture in the industrial waste salt, decomposing macromolecular organic matters by heating, spraying, cooling and purifying the produced high-temperature gaseous mixture to be used as boiler fuel, and using the high-temperature steam produced by a boiler as a heat source of an evaporative crystallization unit. Dissolving solid slag produced by pyrolysis, then performing filter pressing, removing impurities from obtained liquid, sending the obtained liquid into an evaporative crystallization unit to obtain industrial refined salt, and condensing evaporated water to return to a boiler or be used as circulating water.
A resource utilization method for harmless disposal of industrial waste salt specifically comprises the following steps:
(1) And (3) conveying the industrial waste salt into a dry-method feeding unit, and conveying the industrial waste salt to a thermal analysis unit III through the dry-method feeding unit.
As shown in fig. 2, the dry-method feeding unit comprises a pretreatment unit i and a feeding unit ii, the feeding unit ii comprises an inclined conveying device, a feeding port 3 is arranged at the bottom of the inclined conveying device, and a discharging port 4 is arranged at the top of the inclined conveying device. Pretreatment unit I sets up in the top of feed inlet 3, pretreatment unit I includes the feed bin, is provided with shale shaker 1 on the upper portion of feed bin, is provided with feed opening 2 in the bottom of feed bin. Industrial waste salt is sent into the feed bin through the belt of big inclination, is provided with height material level alarm device in the feed bin, and when high material level was reported to the police after, the material loading stopped, when low material level was reported to the police, the start-up material loading stopped after reporting to the police until high material level. The bottom of the storage bin is provided with an inclined conveying device, the materials are conveyed into a dry-type distributing device and then enter a thermal desorption furnace after being uniformly distributed
A dry distributor 5 is arranged at the discharge port of the inclined conveying device, as shown in fig. 3, the dry distributor 5 includes a distribution bin 501, a feed port is arranged at the top center of the distribution bin 501, a first rotating shaft 502 and a second rotating shaft 503 are arranged inside the distribution bin 501, and the first rotating shaft 502 and the second rotating shaft 503 are arranged in parallel. First blades 504 are disposed on first shaft 502, and first blades 504 are symmetrically distributed along the center of first shaft 502. The second rotating shaft 503 is provided with second blades 505, the second blades 505 are symmetrically distributed along the center of the second rotating shaft 503, and the first blades 504 and the second blades 505 are arranged in a staggered manner.
Industrial waste salt is fed into the dry-type distributing device 5 through the dry-type feeding unit, double-blade shafts which are meshed with each other are arranged in the dry-type distributing device 5, and blades on the shafts are in opposite pushing angles, so that after solid materials enter the dry-type distributing device, the solid materials can transversely move towards two sides, and uniform distribution of the solid materials is achieved.
(2) The thermal analysis unit iii includes a thermal analysis device, as shown in fig. 4, which includes a thermal analysis housing 301, and a transport device 302 and a heating device 303 are provided inside the thermal analysis housing 301; and material turning pear rakes 304 are arranged above the conveying device at intervals. The operating pressure inside the thermal desorption casing 301 is controlled to be micro-positive pressure, and the pressure range is gage pressure of 50-200 Pa.
The industrial waste salt that gets into thermal desorption unit tiles on conveyor 302, and industrial waste salt removes along with conveyor 302, heats industrial waste salt to 300 ~ 600 ℃ through heating device 303 simultaneously for the moisture thermal desorption in the industrial waste salt comes out, and the macromolecule organic matter is heated and is decomposed, and the high temperature gas of output gets into cooling separation unit IV through high temperature gas outlet 6, and the solid sediment of pyrolysis output gets into slag tap cooling unit VII through slag notch 7. When the industrial waste salt is treated in the thermal desorption unit, the industrial waste salt is not rolled or extruded, dust is hardly generated in the treatment process, a radiation plate or a radiation tube is adopted for radiation heat transfer, the high-temperature radiation tube is not contacted with the industrial waste salt, the halogen, especially the chloride ions are greatly prevented from corroding the refractory materials and the steel at high temperature, and the problem of blockage is effectively solved.
More specifically, the thermal resolution device includes a first pyrolysis section 305 and a second pyrolysis section 306, with the second pyrolysis section 306 being below a side of the first pyrolysis section 305. A dry feed port 307 is provided at an upper portion of one end of the first pyrolysis section 305, and a first conveyor and a first heating device are provided inside the first pyrolysis section 305. A high-temperature gas outlet 6 is arranged at the top of the middle of the first pyrolysis section, and a feed opening 308 is arranged at the lower part of the other end of the first pyrolysis section. First pyrolysis section passes through feed opening 308 and second pyrolysis section intercommunication, is provided with second conveyor and second heating device in the inside of second pyrolysis section, is provided with high-temperature gas export 6 at the middle top of thermal analysis section, is provided with ejection of compact axle 309 in the one end bottom of second pyrolysis section, is provided with slag notch 7 in the below of ejection of compact axle 309.
Further, the first conveying device and the second conveying device both adopt chain plates, and certainly, a fire grate or a crawler belt can also be adopted; the first heating device and the second heating device both adopt radiation plates or radiation tubes. Specifically, an upper-layer chain plate and an upper-layer radiation plate are arranged in the first pyrolysis section, industrial waste salt is conveyed along with the upper-layer chain plate, and the industrial waste salt is subjected to non-contact radiation heating through the upper-layer radiation plate in the conveying process. An upper sliding material plate 3010 is arranged at the tail end of the upper link plate, and materials processed by the first pyrolysis section enter the second pyrolysis section 306 through the upper sliding material plate 3010 and the feed opening 308. The inside of second pyrolysis section is provided with lower floor's link joint and lower floor's radiant panel, is provided with lower floor's smooth flitch 3011 and ejection of compact axle 309 at the tail end of lower floor's link joint, and the material after the pyrolysis in advance falls into lower floor's link joint to along with lower floor's link joint is carried, heats through lower floor's radiant panel in transportation process, and the material is discharged through lower floor's smooth flitch 3011, ejection of compact axle 309 and slag notch 7 after the pyrolysis. The material turning plow harrow 304 for turning materials is arranged above the inner parts of the first pyrolysis section and the second pyrolysis section, so that the materials can be heated uniformly.
(3) The slag cooling unit VII is provided with a water cooling jacket 19, cooling water is introduced into the water cooling jacket 19, and solid slag produced by pyrolysis is cooled to 30-80 ℃ in an indirect water cooling mode and then is sent into a dissolution impurity removal unit VIII. And a solid material inlet 18 is arranged at one end of the slag-tapping cooling unit VII, and a solid material outlet 20 is arranged at the other end of the slag-tapping cooling unit VII.
(4) The dissolving and impurity removing unit VIII comprises a dissolving tank 801, solid slag from the slag cooling unit VII enters the dissolving tank through a material inlet 21 to be dissolved, neutralizing liquid is added into the dissolving tank to precipitate soluble impurities in the dissolved solid slag, and mixed liquid after dissolving and precipitating is sent into the filtering unit IX through a mixed liquid outlet 22.
The neutralizing solution comprises BaCl 2 NaOH and Na 2 CO 3 In an equal solution of the BaCl 2 NaOH and Na 2 CO 3 The solution is added into a dissolving tank 801 in sequence, and Ca in the saline solution after solid residues are dissolved can be added into the solution after the neutralization solution is added 2+ ，Mg 2+ ，SO 4 2- And the soluble impurities are precipitated respectively.
The solid material from the slag cooling unit VII enters a dissolving tank to be dissolved, the dissolving tank is divided into a plurality of tanks, and BaCl is respectively added 2 NaOH and Na 2 CO 3 Waiting for the solution, and adding Ca in the salt solution 2+ ，Mg 2+ ，SO 4 2- And respectively generating precipitates after soluble impurities are dissolved, and sending the mixture into a filter pressing unit.
As shown in fig. 5, a first partition plate 802 and a second partition plate 803 are provided inside the dissolving tank 801, and the dissolving tank is divided into a first compartment 804, a second compartment 805, and a third compartment 806 by the first partition plate 802 and the second partition plate 803. A material inlet 21, a dissolving liquid inlet 807 and a first neutralizing liquid adding port 808 are arranged at the upper part of the first compartment 804, the first partition plate 802 is positioned between the first compartment 804 and the second compartment 805, and the height of the first partition plate 802 is higher than that of the second partition plate 803. A second neutralizing liquid addition port 809 is provided in the upper portion of the second compartment 805. A tapered sludge discharge port 8010 is provided at the bottom of both the first compartment 804 and the second compartment 805. A mixed liquor outlet 22 is provided at the bottom of the third compartment 806.
(5) In the filtering unit IX, the mixed liquid is subjected to solid-liquid separation by a filtering device in the filtering unit, the separated solid slag is discharged, and the liquid is sent to the evaporative crystallization unit X.
The filtering device is a plate-and-frame filter press or a vacuum pumping filter. A mixed liquid inlet 23 is arranged at one end of the filtering device, a liquid outlet 25 is arranged at the upper part of the other end of the filtering device, and a solid slag outlet 24 is arranged at the lower part of the other end of the filtering device.
(6) An evaporative crystallization device is arranged in the evaporative crystallization unit X, and the liquid from the filtering unit is treated by the evaporative crystallization device to obtain industrial refined salt.
The evaporative crystallization device is a multi-effect evaporative crystallization device, a multi-stage flash evaporation device or a mechanical evaporation device. The upper part of the evaporative crystallization device is provided with a liquid inlet 26, the top of the evaporative crystallization device is provided with an evaporative steam outlet 30, and the bottom of the evaporative crystallization device is provided with an industrial refined salt outlet 28. The evaporative crystallization device is also provided with a heating jacket, one end of the heating jacket is provided with a heating steam inlet 27, and the other end of the heating jacket is provided with a steam condensate outlet 29. The evaporative crystallization device is also connected with a condensation chamber, an evaporative steam inlet 31 is arranged on the condensation chamber, the evaporative steam inlet 31 is communicated with an evaporative steam outlet 30, and an evaporative steam condensate outlet 32 is also arranged on the condensation chamber.
The condensed water produced in the evaporative crystallization unit can be used as boiler water supplement.
(7) In the cooling separation unit IV, high-temperature gas generated by pyrolysis enters the spray cooling tower body through the high-temperature gas inlet 8, the spray cooling water entering the spray cooling tower body from the spray water inlet 9 at the top of the spray cooling tower body is directly sprayed and cooled to 60-80 ℃, the condensed sewage is discharged from the sewage outlet 11 at the bottom of the spray cooling tower body and enters the sewage settling unit V, and the non-condensable gas is discharged from the non-condensable gas outlet 10 at the upper part of the spray cooling tower body and enters the non-condensable gas treatment unit VI.
And a sewage settling shell is arranged in the sewage settling unit V, sewage enters the sewage settling shell through a sewage inlet 15, a dust-containing sewage outlet is arranged at the bottom of the sewage settling shell, and a purified water outlet 17 is arranged at the upper part of the sewage settling shell. After the sewage is subjected to gravity settling separation, the clear water at the upper part is discharged from a clean water outlet 17 and is used as circulating water for spraying of a condensation separation unit, and the sewage at the lower part is discharged from a dust-containing sewage outlet 16 and enters a dissolution impurity removal unit VIII through a dissolution liquid inlet 807. If the excess water exists, the water is sent to a sewage treatment plant or a sewage treatment device.
In the non-condensable gas processing unit VI, a filler 14 is arranged, and non-condensable gas enters through a non-condensable gas inlet 12, is subjected to liquid separation, desulfurization and pressurization sequentially and then is discharged through a non-condensable gas outlet 13 to be used as boiler fuel gas.
Generally, the process flow of the invention is as follows: sending industrial waste salt into a top bin through a large-inclination-angle belt, setting high and low level material level alarm in the bin, and stopping feeding after the high level material level alarm; and when the low material level alarms, starting feeding until the high material level alarms and then stopping feeding. The bottom of the storage bin is provided with an inclined conveying device, the materials are conveyed into the dry-type distributor and enter the thermal desorption furnace after being uniformly distributed. The processing flow of the industrial waste salt in the thermal analysis unit is shown in fig. 4, the thermal analysis device is divided into a first thermal analysis section and a second thermal analysis section, the industrial waste salt conveyed into the thermal analysis device through the dry-type distributing device is flatly laid on a grate, a track or a chain plate, the industrial waste salt moves along with the conveying device, the industrial waste salt does not roll or extrude, and almost no dust is generated in the processing process. Adopt radiant panel or radiant tube as the heat source in thermal desorption device, heat industry waste salt to 300 ~ 600 ℃, make the moisture in the industry waste salt evaporate by heating, macromolecule organic matter is heated and is decomposed, high-temperature gas gets into the cooling separation unit through top high-temperature gas export, directly spray the cooling through spraying cooling water, the cooling is to 60 ~ 80 ℃, the vapor condensation is liquid, get into sewage settlement unit, after gravity settling separation, the upper portion clear water is as spraying with recirculated cooling water, bottom sewage is sent into and is dissolved edulcoration unit, unnecessary bottom dusty waste water can be sent to the sewage treatment plant and handle. The non-condensable gas enters the non-condensable gas treatment unit from the top of the cooling separation unit, and can be used as supplementary fuel for boilers and the like after liquid separation, desulfurization and pressurization. Feeding solid materials produced by pyrolysis into a discharging device, cooling by adopting an indirect water-cooling jacket mode, cooling solid slag to 30-80 ℃, feeding the solid slag into a dissolving and impurity-removing unit, mixing sewage from a sewage settling unit for dissolving, dividing the dissolving and impurity-removing device into a plurality of compartments, enabling liquid to pass through the multistage compartments in an overflow mode, and adding the liquid such as BaCl into the liquid according to components 2 NaOH and Na 2 CO 3 Waiting for the solution, and adding Ca in the salt solution 2+ ，Mg 2+ ，SO 4 2- Respectively generating precipitates from soluble impurities, and feeding the mixed solutionSolid-liquid separation is realized in the filtering unit through a plate-and-frame filter press, solid slag is discharged and sent into a slag warehouse, liquid enters an evaporative crystallization unit, and industrial refined salt and condensed water are obtained through a multi-effect evaporative crystallization device.
The invention is further illustrated by the following specific application examples:
raw materials: industrial waste salt from a pharmaceutical factory;
comprises the following components: 5% of water, 20% of organic matters and 75% of solid.
The process flow of the invention is as follows: sending industrial waste salt into a top bin through a large-inclination-angle belt, setting high and low level material level alarm in the bin, and stopping feeding after the high level material level alarm; and when the low material level alarms, starting feeding until the high material level alarms and then stopping feeding. The bottom of the storage bin is provided with an inclined conveying device, the materials are conveyed into the distributing device and enter the thermal desorption device after being evenly distributed. The process of the industrial waste salt in the thermal analysis device is shown in fig. 4, the thermal analysis device is divided into a first thermal analysis section and a second thermal analysis section, the industrial waste salt conveyed into the thermal analysis device through the feeding unit is flatly laid on a fire grate, a track or a chain plate, the industrial waste salt moves along with the conveying device, the rolling and the extrusion are avoided, and no dust is generated in the treatment process. Adopt radiation plate or radiant tube as the heat source in thermal desorption device, heat industry waste salt to 550 ℃, make the moisture in the industry waste salt evaporate by heating, macromolecule organic matter is heated and decomposes, high-temperature gas gets into the cooling separation unit through top high-temperature gas export, directly spray the cooling through spraying cooling water, the cooling is to 60 ~ 80 ℃, the steam condensation is liquid, get into the sewage settlement unit, after gravity settling separation, the upper portion clear water is as spraying with recirculated cooling water, lower part sewage is sent into and is dissolved the edulcoration unit, unnecessary dirty waste water is sent to the sewage treatment plant and is dealt with. The non-condensable gas enters a non-condensable gas treatment unit from the top of the device, and can be used as supplementary fuel for boilers and the like after liquid separation, desulfurization and pressurization; feeding solid material produced by pyrolysis into a discharging device, cooling by adopting an indirect water-cooling jacket mode, cooling solid slag to 30-80 ℃, feeding the solid slag into a dissolving and impurity-removing unit, mixing sewage from a sewage settling unit for dissolving, dividing the dissolving and impurity-removing unit into a plurality of compartments, and discharging liquid in an overflow modeThe body is passed through multiple compartments, into which, depending on the composition, for example, baCl is added separately 2 NaOH and Na 2 CO 3 Waiting for the solution, and adding Ca in the salt solution 2+ ，Mg 2+ ，SO 4 2- And (3) respectively generating precipitates from soluble impurities, feeding the mixed solution into a filtering unit, realizing solid-liquid separation through a plate-and-frame filter press, discharging solid slag, feeding the solid slag into a slag warehouse, feeding the liquid into an evaporation crystallization unit, and obtaining industrial refined salt and condensed water through a multi-effect evaporation crystallization device. The operating pressure in the furnace is micro-positive pressure, and the pressure of a hearth is controlled to be about 100 Pa. The temperature of the hearth is 600 ℃, the temperature of the material outlet is 550 ℃, the residence time of the industrial waste salt in the furnace is 30min, and the temperature can be adjusted within the range of 20-120 min. The NaCl content in the industrial refined salt is higher than 99.5 percent.
Claims (10)
1. A resource utilization method for harmless treatment of industrial waste salt is characterized by comprising the following steps:
(1) Sending industrial waste salt into a dry-method feeding unit, and conveying the industrial waste salt to a thermal analysis unit through the dry-method feeding unit;
(2) The thermal analysis unit comprises a thermal analysis shell, and a conveying device and a heating device are arranged in the thermal analysis shell; the industrial waste salt entering the thermal desorption unit is flatly laid on the conveying device, moves along with the conveying device, and is heated to 300-600 ℃ through the heating device, so that moisture in the industrial waste salt is thermally desorbed, macromolecular organic matters are heated and decomposed, the produced high-temperature gas enters the cooling separation unit, and the solid slag produced by pyrolysis enters the slag cooling unit;
(3) A water cooling jacket is arranged on the slag cooling unit, cooling water is introduced into the water cooling jacket, solid slag produced by pyrolysis is cooled to 30-80 ℃ in an indirect water cooling mode, and then the solid slag is sent to a dissolving and impurity removing unit;
(4) The dissolving and impurity removing unit comprises a dissolving tank, solid slag from the slag cooling unit enters the dissolving tank to be dissolved, neutralizing liquid is added into the dissolving tank to precipitate soluble impurities in the dissolved solid slag, and mixed liquid after dissolving and precipitating is sent to the filtering unit;
(5) In the filtering unit, the mixed liquid is subjected to solid-liquid separation through a filtering device in the filtering unit, the separated solid slag is discharged, and the liquid is sent to an evaporative crystallization unit;
(6) The evaporative crystallization unit is provided with an evaporative crystallization device, and the liquid from the filtering unit is treated by the evaporative crystallization device to obtain the industrial refined salt.
2. The method for harmless disposal and resource utilization of industrial waste salt according to claim 1, characterized in that:
in the cooling separation unit, high-temperature gas generated by pyrolysis is directly cooled by spraying cooling water to 60-80 ℃, condensed sewage enters a sewage settling unit, and non-condensable gas enters a non-condensable gas treatment unit;
in the sewage settling unit, sewage is subjected to gravity settling separation, upper clear water is used as circulating water for spraying, and lower sewage is sent to the dissolving and impurity removing unit;
in the non-condensable gas treatment unit, the non-condensable gas is subjected to liquid separation, desulfurization and pressurization and then is used as boiler fuel gas.
3. The method for harmless treatment and resource utilization of industrial waste salt according to claim 1 or 2, characterized by comprising the following steps: the dry-method feeding unit comprises an inclined conveying device, a feeding hole is formed in the bottom of the inclined conveying device, and a discharging hole is formed in the top of the inclined conveying device; a pretreatment unit is arranged above the feeding hole, the pretreatment unit comprises a storage bin, and a vibrating screen is arranged at the upper part of the storage bin; industrial waste salt is sent into the feed bin through the inclination belt, is provided with high low material level alarm device in the feed bin, and when high material level was reported to the police after, the material loading was stopped, when low material level was reported to the police, the start material loading was stopped after high material level reported to the police.
4. The method for harmless disposal and resource utilization of industrial waste salt according to claim 3, characterized in that: the dry-type distributing device is arranged at the discharge port of the inclined conveying device and comprises a distributing bin, a feeding port is formed in the center of the top of the distributing bin, a first rotating shaft and a second rotating shaft are arranged inside the distributing bin, the first rotating shaft and the second rotating shaft are arranged in parallel, a first blade is arranged on the first rotating shaft, the first blade is symmetrically distributed along the center of the first rotating shaft, a second blade is arranged on the second rotating shaft, the second blade is symmetrically distributed along the center of the second rotating shaft, and the first blade and the second blade are arranged in a staggered mode.
5. The method for harmless disposal and resource utilization of industrial waste salt according to claim 1, characterized in that: the conveying device is a crawler belt, a grate or a chain plate, and turning pear rakes are arranged above the conveying device at intervals; the heating device is a radiation plate or a radiation tube; the operating pressure inside the thermal desorption shell is micro-positive pressure, and the pressure range is 50-200 Pa gauge pressure.
6. The method for harmless disposal and resource utilization of industrial waste salt according to claim 1, characterized in that: the neutralizing solution comprises BaCl 2 NaOH and Na 2 CO 3 Solution of said BaCl 2 NaOH and Na 2 CO 3 The solution is sequentially added into a dissolving tank, and Ca in the salt solution can be dissolved after the neutralization solution is added 2+ ，Mg 2+ ，SO 4 2- Soluble impurities are precipitated respectively.
7. The method for harmless disposal and resource utilization of industrial waste salt according to claim 1, characterized in that: a first partition plate and a second partition plate are arranged in the dissolving tank, and divide the dissolving tank into a first compartment, a second compartment and a third compartment;
the upper part of the first bulkhead is provided with a material inlet, a dissolving liquid inlet and a first neutralizing liquid adding port, the first clapboard is positioned between the first bulkhead and the second bulkhead, the height of the first clapboard is higher than that of the second clapboard, and the upper part of the second bulkhead is provided with a second neutralizing liquid adding port; the bottoms of the first compartment and the second compartment are provided with conical sediment discharge ports; the bottom of the third compartment is provided with a mixed liquid outlet.
8. The method for harmless treatment and resource utilization of industrial waste salt according to claim 1, which is characterized in that: the filtering device is a plate-and-frame filter press or a vacuum pumping filter.
9. The method for harmless disposal and resource utilization of industrial waste salt according to claim 1, characterized in that: the evaporative crystallization device is a multi-effect evaporative crystallization device, a multi-stage flash evaporation device or a mechanical evaporation device.
10. The method for harmless disposal and resource utilization of industrial waste salt according to claim 1, characterized in that: and the condensed water produced in the evaporative crystallization unit is used as boiler water supplement.
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