CN106672904A - Method for comprehensively treating sulfur-containing flue gas and solid waste abraum salt - Google Patents
Method for comprehensively treating sulfur-containing flue gas and solid waste abraum salt Download PDFInfo
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- CN106672904A CN106672904A CN201710058371.9A CN201710058371A CN106672904A CN 106672904 A CN106672904 A CN 106672904A CN 201710058371 A CN201710058371 A CN 201710058371A CN 106672904 A CN106672904 A CN 106672904A
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- flue gas
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
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Abstract
The invention discloses a method for comprehensively treating sulfur-containing flue gas and solid waste abraum salt. According to the method, hydrogen chloride and sodium hydrogen sulfate crystals are produced through reaction of sulfuric acid prepared by virtue of flue gas desulfurization and solid waste abraum salt prepared from industrial wastewater by virtue of evaporative crystallization. The method comprises two stages, wherein the first stage is a flue gas desulfurization acid preparation stage, and the second stage is a reaction stage of solid waste abraum salt and solid waste abraum salt. The flue gas desulfurization acid preparation and the wastewater zero-discharging solid waste abraum salt are combined together in a resource manner, so that the linkage treatment of water-gas residue pollutants is realized, the spot utilization of acid prepared though flue gas desulfurization is realized, the transportation cost is saved, the added value of the solid waste abraum salt is increased, the resource utilization of waste is realized, the true zero-discharging closed loop is formed, and sustainable development requirements are met.
Description
Technical field
The invention belongs to resource reclaim processing technology field, and in particular to using sulphuric acid obtained in flue gas desulfurization and Industry Waste
The obtained solid waste carnallite of water evaporation crystallization carries out the method for reacting production hydrogen chloride and sodium bisulfate crystal.
Background technology
Existing environment-friendly treatment method can be directed to the boiler sulfur-containing smoke gas and highly concentrated salt waste water in chemical plant and be located respectively
Reason.Sulfur-containing smoke gas pollutant Jing after processing are transferred to desulfurization wastewater by flue gas or are formed in solid waste, with waste water or Gypsum Fibrosum
Form output；The pollutant that the high strong brine of chemical industry can be dissolved in waste water by techniques such as evaporative crystallizations are crystallized out,
Exported in the form of solid waste.It is another kind of form that above processing mode belongs to a pollutant from a kind of form transformation, and
It is non-to utterly destroy pollutant, it is impossible to fundamentally to realize " zero-emission " of environmental protection.The especially high strong brine Jing evaporations of biochemical waste water
The carnallite that crystallization is produced is clearly defined as hazardous waste by country, and disposal technology difficulty and cost input require higher.
The usual aqueous vapor slag pollution in chemical industrial park exists simultaneously, but the environment protection treating present situation of aqueous vapor slag is substantially belonged to " respectively
Political affairs ", pollutant from a kind of form transformation to another kind of form in when, not only increase the cost of pollutant control, and increase
Environmental protection treatment and the difficulty disposed.
With pollutant aqueous vapor slag with the linkage handling problems for considering the improvement of aqueous vapor slag are controlled as starting point, from the angle of overall planning
Spend to solve environmental issue, can preferably realize the minimizing of final pollutant.Resource is realized for different pollutant, especially
It is the recycling for realizing that final product danger is useless, then be the committed step for getting through waste water-waste gas-waste residue zero-emission closed loop,
It is to utterly destroy pollutant, really realize the key point of zero release of pollutant, is also the industry for meeting country and local government
With the inevitable requirement of the promotion hazardous waste comprehensive utilization of resources of technical policy.
The content of the invention
In order to overcome the shortcomings of current technology, the present invention provides the side of a kind of integrated treatment sulfur-containing smoke gas and solid waste carnallite
Method, realizes production hydrogen chloride and sodium bisulfate crystal, realizes aqueous vapor slag zero-emission, and the method is produced using the process of flue gas desulfurization
Concentrated sulphuric acid, then with the solid waste carnallite containing sodium sulfate and Sodium Chloride mixed salt of high strong brine evaporative crystallization generation as raw material, with cigarette
The sulfuric acid reaction production hydrogen chloride gas that desulfurization is produced, while co-producing sulfuric acid hydrogen sodium crystal, had both realized aqueous vapor slag zero-emission
Closed loop, the characteristics of desulfurization antacid and solid waste carnallite resource are combined again, makes full use of the natural resources, while processing pollutant again
Solid waste carnallite is changed into into the higher chemical products of added value, invests relatively low and easy to operate, meet the requirement of sustainable development.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of method of integrated treatment sulfur-containing smoke gas and solid waste carnallite, the system that described method is adopted is for by pipeline company
The flue gas desulfurization acid making system for connecing and solid waste carnallite processing system.Described flue gas desulfurization acid making system includes washing-absorption system
System, regeneration-cleaning system, catalysis-acid making system；Described washing-absorption system includes that pre-scrubber, granule and acid mist are filtered
Device and sulfur dioxide absorbing tower；Described regeneration-cleaning system include poor rich liquid heat exchanger, regenerator, amine purification device and
Cooler；Described catalysis-acid making system includes one stage catalyzing oxidation reactor, first grade absorption tower, two grades of catalytic oxidations
Device, two-level absorption tower, condenser and sulfuric acid storage tank；In described one stage catalyzing oxidation reactor and two grades of catalyst oxidation reactors
Multiple beds and heat exchanger are provided with, the heat transfer medium in heat exchanger is fuse salt, and then control heat exchanger import temperature
Degree, waste heat boiler feedwater and generation steam, the temperature of the salt that exchanges heat is needed higher than the sulphuric acid in two catalyst oxidation reactors
Dew point, therefore the temperature of fuse salt needs control at 240 DEG C.The sulphuric acid obtained in condenser, is entered into by down-comer
In the sulphuric acid of cooling, by constantly heat exchange, the hot sulphuric acid for obtaining constantly is condensed, so as to the sulphuric acid after most cooling down at last
Deliver to outside battery limit (BL).
Described solid waste carnallite processing system includes enamel glass reactor, the reactant liquor storage being sequentially connected by pipeline
Bucket, crystallizer, thickener, hanging bag centrifuge, pure material conveyer, air drier, siccative conveyer and automatic packaging machine；It is described
Enamel glass reactor top steam vent by pipeline connect hydrogen chloride absorption tower, hydrogen chloride absorption tower leakage fluid dram by pipe
Road connects hydrochloric acid tank；The exhaust outlet of described air drier connects cyclone dust extractor and air-introduced machine by pipeline.
Described method is comprised the following steps：
1) washing-absorption SO2：Sulfur dioxide flue gas is transported in pre-scrubber and spray chilling by cleaning mixture and satisfy
With, the little particle dust and most of acid mist in flue gas is removed, the flue gas after granule and acid mist filter are filtered enters two
Sulfur oxide absorption tower absorbs, and multi-stage countercurrent contact, SO are carried out with lean amine liquid in sulfur dioxide absorbing tower2By lean amine liquid selectivity
Ground absorbs, and obtains containing SO2Rich amine solution, the flue gas after purification meets the flue on discharge standard and Jing sulfur dioxide absorbing towers top
Discharge；
2) regeneration-purification SO2：Containing SO2Low temperature rich amine solution add through steam into regenerator through poor rich liquid heat exchanger
Heat, makes containing SO2Rich amine solution desorb pure high concentration SO2Gas and the lean amine liquid of high temperature regeneration, lean amine liquid Jing is lean for high temperature regeneration
Reach in sulfur dioxide absorbing tower after the heat exchange of rich solution heat exchanger and absorb SO2；Each absorbs the lean amine aqueous solution of partial regeneration in cycle
Into in amine purification device purify, remove solvent in gather thermal-stable salt (as sulfate, nitrate, thiosulfate,
Chloride etc.), enter back into afterwards in sulfur dioxide absorbing tower and absorb SO2；
3) catalysis-antacid：The SO parsed in Jing regenerators2Saturation high-purity is promoted to through condenser cooling
(99.99%) SO2Butt gas, is passed through one stage catalyzing oxidation reactor and two grades of catalyst oxidation reactors, in catalyst bed
In layer, the oxidation reaction for carrying out sulfur dioxide and oxygen generates SO3, overheated SO3Enter with sulphuric acid to inhale Jing after heat exchanger cooling
The first grade absorption tower and two-level absorption tower for receiving agent obtains high-purity concentrated sulphuric acid by absorption, and high-purity concentrated sulphuric acid is entered in sulfuric acid storage tank
As the raw material of postorder production technology；
4) hybrid reaction：High-purity concentrated sulphuric acid and consolidating containing sodium sulfate and Sodium Chloride are added in enamel glass reactor
Useless carnallite, controls temperature, pressure and the temperature retention time of reactor, is fully reacted under conditions of stirring, generates hydrogen sulfate
Sodium serosity and hydrogen chloride gas；
5) store：By step 4) generate sodium bisulfate serosity stored by reactant liquor storage tank；
6) absorbing hydrogen chloride：By step 4) in produce hydrogen chloride gas absorption process is carried out using hydrogen chloride absorption tower,
The hydrochloric acid of production is discharged into afterwards storing in hydrochloric acid tank；
7) crystallisation by cooling：Sodium bisulfate serosity is pumped to into crystallizer carries out crystallisation by cooling, forms low denseness sodium bisulfate
Semi-finished product crystallization solution；
8) solid-liquid separation：Low denseness sodium bisulfate semi-finished product crystallization solution is processed using thickener, a water is realized
Sodium bisulfate crystal is separated with water, be sink to bottom Bisulfate Monohydrate sodium crystal accumulate thick Sodium Bisulfate Monohydrate magma from
Bottom discharge mouth is discharged, and thickener supernatant mixes Posterior circle and uses with high-concentration sulfuric acid, and thickener supernatant is that chloride ion contains
The relatively low and higher solution of sulfuric acid concentration of amount, Jing mixes Posterior circle and uses with high-concentration sulfuric acid, without waste liquid discharge, meets sustainable
Demand for development；
9) centrifugal treating is washed：Sodium Bisulfate Monohydrate magma is carried out into centrifugal treating using hanging bag centrifuge, in centrifugation
During washing carried out using saturation sodium bisulfate obtain sodium bisulfate crystal, carried it to heat using pure material conveyer
Wind drying machine dried；
10) hot air drying：Sodium bisulfate crystal is put in air drier carries out hot air drying process, adopts after being dried
Dry conveyer is delivered to automatic packaging machine；
11) pack：Packing processes are carried out using automatic packaging machine through dried sodium bisulfate crystal, realizes that resource is returned
Receive and utilize.
Preferably, described pre-scrubber bottom connects water treatment system by pipeline.
Preferably, step 1) in, cleaning mixture pH is 1-2 in pre-scrubber, and cleaning mixture pH is very low in pre-scrubber, so
Under one strong acidic environment, SO can be prevented2With water reaction, it is ensured that SO2Sulfur dioxide absorbing tower is entered with gas phase traveling；Lean amine liquid
Weight/mass percentage composition >=20% of middle organic amine, organic amine is ethylenediamine, and non-volatile, heating is not decomposed, and is to absorb SO2Core
The heart.
Preferably, step 2) in, the vapor (steam) temperature that steam is passed through in regenerator is 110-120 DEG C, and pressure is in regenerator
0.15-0.2MPa, the lean amine liquid of high temperature regeneration temperature Jing after poor rich liquid heat exchanger heat exchange is 30-50 DEG C；Each absorbs cycle 3-
The purification in amine purification device of the 5% lean amine aqueous solution of regeneration, " thermal-stable salt " gathered in removing solvent (sulfate,
Nitrate, thiosulfate, chloride etc.).
Preferably, step 3) in, the catalyst in beds is V2O5, beds are by waste heat boiler generation
Steam heating, until beds temperature be 400-600 DEG C；Absorbent is 98% sulphuric acid, the sulfuric acid concentration of generation
For 92-98%.
Preferably, step 4) in, sodium sulfate is respectively 20-50% and 50- with the mass fraction of Sodium Chloride in solid waste carnallite
80%, the solid waste carnallite of addition is 1 with the amount ratio of sulphuric acid material:(1.7-3.5), wherein the purity of sulphuric acid is 90-96%；Enamel
It is 120-150 DEG C that vapor (steam) temperature is heated in glass reaction kettle, and steam pressure is 0.2-0.5MPa, and charging terminates rear temperature retention time and is
30-45min。
Preferably, step 7) in, the temperature cooled down in cooling concentration crystallization is 20-40 DEG C, and pressure is 0.1-0.2MPa.
Preferably, step 8) in, the operating pressure of thickener is 0-0.15MPa, and operating temperature is 20-40 DEG C.
Preferably, step 9) in, washed using saturation sodium bisulfate, obtain the hydrogen sulfate of moisture content 8-12%
Sodium crystal, operating pressure 0.08-0.12MPa of hanging bag centrifuge, operating temperature is 20-40 DEG C.
Preferably, step 10) in, hot-air drier hot air temperature is 100-110 DEG C, and discharged air temperature is 60-65
DEG C, sodium bisulfate crystal its moisture after air drier drying accounts for the 0.3-1.0% of gross mass.
It is an advantage of the invention that：
1) the method is with boiler flue gas desulfurization antacid, and makes it brilliant with solid waste carnallite reaction production hydrogen chloride and sodium bisulfate
Body, while realizing the closed loop of flue gas waste water and dregs zero-emission, realizes the resource of pollutant；
2) absorbent that the method is selected is to SO2Absorption selectivity is good, and flue gas desulphuization rate is up to more than 99%, and absorbent
Recycling rate is high, produces sour quality better；
3) the method is with solid waste carnallite as raw material production hydrochloric acid and sodium bisulfate product, it is to avoid Sodium Chloride and sulfur in carnallite
The sub-prime crystallization of sour sodium, has widened the range of application of solid waste carnallite, has both taken full advantage of chemical resource, and chemical plant wastewater is reached again
The zero-emission of processing system real meaning；
4) by carnallite resource technology, the expenditure of enterprise's solid waste carnallite disposal costs is saved, while obtaining related work
Industry side-product；
5) by carnallite resource technology, it is to avoid occupancy of the solid waste carnallite landfill to land resource, by environmental pollution journey
Degree is reduced to minimum；
6) sodium bisulfate thickener supernatant is the solution that chloride ion content is relatively low and sulfuric acid concentration is higher, Jing and high concentration
Sulphuric acid mixes Posterior circle and uses, and discharges without waste liquid, meets sustainable development requirement；
7) presence of sodium sulfate can suppress Sodium Chloride with the sulfuric acid system reaction acutely generation of slug phenomenon.
Description of the drawings
Fig. 1 is the structural representation of flue gas desulfurization acid making system in the present invention；
Fig. 2 is the structural representation of solid waste carnallite processing system in the present invention.
Specific embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated：
A kind of method of integrated treatment sulfur-containing smoke gas and solid waste carnallite, the system that described method is adopted is for by pipeline company
The flue gas desulfurization acid making system for connecing and solid waste carnallite processing system.
As shown in figure 1, described flue gas desulfurization acid making system include washing-absorption system, regeneration-cleaning system, catalysis-
Acid making system；Described washing-absorption system includes pre-scrubber 10, granule and acid mist filter 11 and sulfur dioxide absorbing tower
12；Described regeneration-cleaning system includes poor rich liquid heat exchanger 13, regenerator 14, amine purification device 15 and cooler 16；Institute
Catalysis-the acid making system stated include one stage catalyzing oxidation reactor 17,18, two grades of catalyst oxidation reactors 19 of first grade absorption tower,
Two-level absorption tower 20, condenser 21 and sulfuric acid storage tank 22；Described one stage catalyzing oxidation reactor 17 and two grades of catalysis oxidations is anti-
Answer and multiple beds 23 and heat exchanger 24 are provided with device 19, the heat transfer medium in heat exchanger 24 is fuse salt.
As shown in Fig. 2 described solid waste carnallite processing system includes the enamel glass reactor being sequentially connected by pipeline
25th, reactant liquor storage tank 26, crystallizer 27, thickener 28, hanging bag centrifuge 29, pure material conveyer 30, air drier 31, siccative
Conveyer 32 and automatic packaging machine 33；The steam vent on the described top of enamel glass reactor 25 connects hydrogen chloride and inhales by pipeline
Tower 34 is received, the leakage fluid dram of hydrogen chloride absorption tower 34 connects hydrochloric acid tank 35 by pipeline；The exhaust outlet of described air drier 31
Cyclone dust extractor 36 and air-introduced machine 37 are connected by pipeline.
Sulfur-containing smoke gas are processed with solid waste carnallite using above-mentioned flue gas desulfurization acid making system and solid waste carnallite processing system
Specific embodiment is as follows：
Embodiment 1：
Flue gas SO2Content is 1%, and using method of the present invention flue gas desulfurization is carried out, cleaning mixture pH in pre-scrubber
For 1, the weight/mass percentage composition of organic amine is 30% in lean amine liquid, and lean amine absorption temperature is 45 DEG C, and steam is passed through in regenerator
Vapor (steam) temperature be 110 DEG C, the pressure in regenerator is 0.16MPa, and each lean amine aqueous solution of regeneration for absorbing the cycle 4% is entered
Purify in amine purification device, SO2Removal efficiency 99%, remnants SO in tail gas2Content is 28.57mg/m3.Beds
Temperature is 400 DEG C, and absorbent is 94% sulphuric acid, and the sulfuric acid concentration of production is 96%.With agitator, thermal resistance, pressure
The glassed steel reaction vessels of table, liquidometer etc. are initially charged 2.18 tons of solid waste carnallites, and are slowly added to 3.11 ton 90% of sulphuric acid, solid waste
Sodium sulfate quality fraction is 35% in carnallite, and the mass fraction of Sodium Chloride is 62%.Hydrogen chloride absorption tower and hydrochloric acid tank are opened,
Carry out under constant agitation being heated to 135 DEG C by steam, be incubated 35min；Reactant liquor is introduced containing 0.48 ton of water
Mix homogeneously in reactant liquor storage tank, is introduced in crystallizer by pump, and it is 0.1MPa conditions to control mould temperature for 35 DEG C, pressure
Under carry out crystallisation by cooling, temperature be 30 DEG C, pressure be 0.1MPa under the conditions of thickener thickening, thickener hangs into high pure material
Band centrifuge, adds the washing of saturation sodium bisulfate while centrifuge dehydration, obtains 4.67 tons of sodium bisulfate crystal, Jing Guore
Wind exsiccator obtains 4.02 tons of sodium bisulfate products after being dried, it is first-class that gained sodium bisulfate product reaches (HG/T4516-2013) I type
Product requirement, sodium bisulfate weight/mass percentage composition >=93.00%, while Jing hydrogen chloride absorptions tower absorbs obtains 3.76 ton of 25% salt
Acid.
Embodiment 2：
Flue gas SO2Content is 3.5%, and using method of the present invention flue gas desulfurization is carried out, cleaning mixture in pre-scrubber
PH is 2, and the weight/mass percentage composition of organic amine is 25% in lean amine liquid, and lean amine absorption temperature is 40 DEG C, and steaming is passed through in regenerator
The vapor (steam) temperature of vapour is 120 DEG C, and the pressure in regenerator is 0.18MPa, and the lean amine aqueous solution of regeneration in each absorption cycle 5% enters
Enter in amine purification device and purify, SO2Removal efficiency 96%, remnants SO in tail gas2Content is 20.35mg/m3.Beds
Temperature be 500 DEG C, absorbent is 95% sulphuric acid, and the sulfuric acid concentration of production is 97%.With agitator, thermal resistance, pressure
The glassed steel reaction vessels of power table, liquidometer etc. are initially charged 2.18 tons of solid waste carnallites, and are slowly added to 3.11 ton 90% of sulphuric acid, Gu
Sodium sulfate quality fraction is 46% in useless carnallite, and the mass fraction of Sodium Chloride is 50%.Open hydrogen chloride absorption tower and hydrochloric acid storage
Tank, carries out being heated to 142 DEG C under constant agitation by steam, is incubated 45min；Reactant liquor is introduced and contains 0.48 ton of water
Reactant liquor storage tank in mix homogeneously, be introduced in crystallizer by pump, control mould temperature for 40 DEG C, pressure be 0.15MPa
Under the conditions of carry out crystallisation by cooling, temperature be 36 DEG C, pressure be 0.13MPa under the conditions of thickener thickening, thickener enters high
Pure material suspender belt centrifuge, adds the washing of saturation sodium bisulfate while centrifuge dehydration, obtains 4.32 tons of sodium bisulfate crystal,
3.85 tons of sodium bisulfate products are obtained after hot-air drier is dried, gained sodium bisulfate product reaches (HG/T4516-2013) I
The requirement of type Grade A, sodium bisulfate weight/mass percentage composition >=95.00%, while Jing hydrogen chloride absorptions tower absorbs obtains 3.45 tons
26% hydrochloric acid.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and and
The non-restriction to embodiment.For those of ordinary skill in the field, can also do on the basis of the above description
Go out the change or variation of other multi-forms.There is no need to be exhaustive to all of embodiment.And thus drawn
Obvious change that Shen goes out or among changing still in protection scope of the present invention.
Claims (10)
1. a kind of method of integrated treatment sulfur-containing smoke gas and solid waste carnallite, it is characterised in that the system that described method is adopted for
The flue gas desulfurization acid making system connected by pipeline and solid waste carnallite processing system；
Described flue gas desulfurization acid making system includes washing-absorption system, regeneration-cleaning system, catalysis-acid making system；It is described
Washing-absorption system include pre-scrubber, granule and acid mist filter and sulfur dioxide absorbing tower；Described regeneration-purification
System includes poor rich liquid heat exchanger, regenerator, amine purification device and cooler；Described catalysis-acid making system includes one-level
Catalyst oxidation reactor, first grade absorption tower, two grades of catalyst oxidation reactors, two-level absorption tower, condenser and sulfuric acid storage tanks；It is described
One stage catalyzing oxidation reactor and two grades of catalyst oxidation reactors in be provided with multiple beds and heat exchanger, heat exchanger
In heat transfer medium be fuse salt；
Described solid waste carnallite processing system includes enamel glass reactor, reactant liquor storage tank, the knot being sequentially connected by pipeline
Brilliant device, thickener, hanging bag centrifuge, pure material conveyer, air drier, siccative conveyer and automatic packaging machine；Described wards off
The steam vent on porcelain glass reaction kettle top connects hydrogen chloride absorption tower by pipeline, and hydrogen chloride absorption tower leakage fluid dram is connected by pipeline
Connect hydrochloric acid tank；The exhaust outlet of described air drier connects cyclone dust extractor and air-introduced machine by pipeline；
Described method is comprised the following steps：
1) washing-absorption SO2：Sulfur dioxide flue gas are transported in pre-scrubber chilling and saturation are sprayed by cleaning mixture, removed
Little particle dust and most of acid mist in flue gas, the flue gas after granule and acid mist filter are filtered is inhaled into sulfur dioxide
Receive tower to absorb, multi-stage countercurrent contact, SO are carried out with lean amine liquid in sulfur dioxide absorbing tower2Optionally absorbed by lean amine liquid,
Obtain containing SO2Rich amine solution, the flue gas after purification meets the flue on discharge standard and Jing sulfur dioxide absorbing towers top and discharges；
2) regeneration-purification SO2：Containing SO2Low temperature rich amine solution through poor rich liquid heat exchanger enter regenerator through steam heat, make
Containing SO2Rich amine solution desorb pure high concentration SO2Gas and the lean amine liquid of high temperature regeneration, the lean rich solutions of the lean amine liquid Jing of high temperature regeneration
Reach in sulfur dioxide absorbing tower after heat exchanger heat exchange and absorb SO2；Each lean amine aqueous solution of partial regeneration for absorbing the cycle is entered
Purify in amine purification device, remove the thermal-stable salt gathered in solvent, enter back into afterwards in sulfur dioxide absorbing tower and inhale
Receive SO2；
3) catalysis-antacid：The SO parsed in Jing regenerators2The highly purified SO of saturation is promoted to through condenser cooling2Butt
Gas, is passed through one stage catalyzing oxidation reactor and two grades of catalyst oxidation reactors, in beds, carry out sulfur dioxide and
The oxidation reaction of oxygen generates SO3, overheated SO3Enter Jing after heat exchanger cooling first grade absorption tower with sulphuric acid as absorbent and
Two-level absorption tower obtains high-purity concentrated sulphuric acid by absorption, and high-purity concentrated sulphuric acid is entered in sulfuric acid storage tank as postorder production technology
Raw material；
4) hybrid reaction：High-purity concentrated sulphuric acid and miscellaneous with the solid waste of Sodium Chloride containing sodium sulfate is added in enamel glass reactor
Salt, controls temperature, pressure and the temperature retention time of reactor, is fully reacted under conditions of stirring, generates sodium bisulfate slurry
Liquid and hydrogen chloride gas；
5) store：By step 4) generate sodium bisulfate serosity stored by reactant liquor storage tank；
6) absorbing hydrogen chloride：By step 4) in produce hydrogen chloride gas absorption process is carried out using hydrogen chloride absorption tower, afterwards
The hydrochloric acid of production is discharged into store in hydrochloric acid tank；
7) crystallisation by cooling：Sodium bisulfate serosity is pumped to into crystallizer carries out crystallisation by cooling, formed low denseness sodium bisulfate half into
Product crystallization solution；
8) solid-liquid separation：Low denseness sodium bisulfate semi-finished product crystallization solution is processed using thickener, sulfuric acid monohydrate is realized
Hydrogen sodium crystal is separated with water, and the Bisulfate Monohydrate sodium crystal for being sink to bottom accumulates thick Sodium Bisulfate Monohydrate magma from bottom
Discharging opening is discharged, and thickener supernatant mixes Posterior circle and uses with high-concentration sulfuric acid；
9) centrifugal treating is washed：Sodium Bisulfate Monohydrate magma is carried out into centrifugal treating using hanging bag centrifuge, in the process of centrifugation
Middle employing saturation sodium bisulfate carries out washing and obtains sodium bisulfate crystal, is carried it to hot air drying using pure material conveyer
Dry machine dried；
10) hot air drying：Sodium bisulfate crystal is put in air drier carries out hot air drying process, and drying is adopted after being dried
Conveyer is delivered to automatic packaging machine；
11) pack：Packing processes are carried out using automatic packaging machine through dried sodium bisulfate crystal, resource reclaim profit is realized
With.
2. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 1 and solid waste carnallite, it is characterised in that described
Pre-scrubber bottom connects water treatment system by pipeline.
3. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 2 and solid waste carnallite, it is characterised in that step 1)
In, cleaning mixture pH is 1-2 in pre-scrubber；Weight/mass percentage composition >=20% of organic amine in lean amine liquid, organic amine is ethylenediamine.
4. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 3 and solid waste carnallite, it is characterised in that step 2)
In, the vapor (steam) temperature that steam is passed through in regenerator is 110-120 DEG C, and pressure is 0.15-0.2MPa in regenerator, and high temperature regeneration is lean
Amine liquid temperature Jing after poor rich liquid heat exchanger heat exchange is 30-50 DEG C；Each lean amine aqueous solution of regeneration for absorbing cycle 3-5% enters amine
Purify in liquid purifier.
5. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 4 and solid waste carnallite, it is characterised in that step 3)
In, the catalyst in beds is V2O5, the temperature of beds is 400-600 DEG C；Absorbent is 98% sulphuric acid,
The sulfuric acid concentration of generation is 92-98%.
6. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 5 and solid waste carnallite, it is characterised in that step 4)
In, the mass fraction of sodium sulfate and Sodium Chloride is respectively 20-50% and 50-80% in solid waste carnallite, the solid waste carnallite of addition with
The amount ratio of sulphuric acid material is 1:(1.7-3.5), wherein the purity of sulphuric acid is 90-96%；Add vapourss in enamel glass reactor
Temperature is 120-150 DEG C, and steam pressure is 0.2-0.5MPa, and charging terminates rear temperature retention time for 30-45min.
7. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 6 and solid waste carnallite, it is characterised in that step 7)
In, the temperature cooled down in crystallisation by cooling is 20-40 DEG C, and pressure is 0.1-0.2MPa.
8. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 7 and solid waste carnallite, it is characterised in that step 8)
In, the operating pressure of thickener is 0-0.15MPa, and operating temperature is 20-40 DEG C.
9. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 8 and solid waste carnallite, it is characterised in that step 9)
In, washed using saturation sodium bisulfate, obtain the sodium bisulfate crystal of moisture content 8-12%, the work of hanging bag centrifuge
Make pressure 0.08-0.12MPa, operating temperature is 20-40 DEG C.
10. the method for a kind of integrated treatment sulfur-containing smoke gas as claimed in claim 9 and solid waste carnallite, it is characterised in that step
10) in, hot-air drier hot air temperature is 100-110 DEG C, and discharged air temperature is 60-65 DEG C, and sodium bisulfate crystal is passed through
Its moisture accounts for the 0.3-1.0% of gross mass after air drier drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710058371.9A CN106672904A (en) | 2017-01-23 | 2017-01-23 | Method for comprehensively treating sulfur-containing flue gas and solid waste abraum salt |
Applications Claiming Priority (1)
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