CN106698481A - Device and method for environmental-protection recycling of solid wastes in production process of sodium sulfide - Google Patents
Device and method for environmental-protection recycling of solid wastes in production process of sodium sulfide Download PDFInfo
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- CN106698481A CN106698481A CN201611156805.0A CN201611156805A CN106698481A CN 106698481 A CN106698481 A CN 106698481A CN 201611156805 A CN201611156805 A CN 201611156805A CN 106698481 A CN106698481 A CN 106698481A
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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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- 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
- C01B17/22—Alkali metal sulfides or polysulfides
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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
- C01D5/18—Dehydration
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Abstract
The invention discloses a device and method for environmental-protection recycling of solid wastes in a production process of sodium sulfide; waste residues and waste mud in the production line of sodium sulfide are added into a slurry mixing pool and are subjected to slurry mixed, and steam is introduced to make the temperature of a slurry rise to 40-50 DEG C; then the mixed slurry is pumped into a reaction kettle, a sulfuric acid solution is added for adjusting the pH of the material to 6.0-7.0 under stirring, and hydrogen sulfide gas generated in the reaction process is introduced into a hydrogen sulfide recovery device for generating a sodium sulfide solution to return to a main production line for recycling; after a material after the reaction is filtered, a filter residue is detected to be qualified and then can be land-filled or sold to the outside, and a filtrate is collected, then enters a sodium sulfate crystallizer and is concentrated and crystallized to generate anhydrous sodium sulfate crystals to return to the main production line for being used as a raw material. The method has the advantages of simple process and simple device, can solve the problem that solid wastes in the production process of sodium sulfide are not up to standard on the spot, extracts and recycles effective components in the solid wastes, reduces the environmental-protection pressure of enterprises, and also has certain economic benefits.
Description
Technical field
The present invention relates to solid waste environmental protection treatment technical field, the environmental protection of solid waste is returned in specifically a kind of vulcanized sodium production process
Receiving method and device.
Background technology
Current akali sulphide industry faces very big pressure in terms of environmental protection, and what three-protection design was most difficult to is salkali waste mud, Solid state fermentation.
Akali sulphide is most basic chemical products, is mostly using extensive style processing method to alkali mud alkaline residue：One is piled up in plant area, product
Tire out a certain amount of rear outward transport landfill；Two is to return kiln calcining；Three is to send cement plant to make raw material；Four is to send brick field to make raw material；Five is to send
Make raw material to coal yard.
Above-mentioned five kinds of processing modes all existing defects：Solid waste is directly filled using first method, because containing in solid waste
There is 0.5~5% Na2S and 5~15% Na2SO4, both materials are all solubility salts, big for environment pollution, directly fill meeting
Underground water and farmland are impacted, good farmland is changed into alkali salt lick, underground water is changed into poisonous water, bright by national environmental protection department
Order is forbidden；Second method by solid waste return kiln calcining, but this kind of method can only process part solid waste, most of alkali mud still without
Method treatment, while yield is too low, does not calculate on cost；The third method, factory pays out of one's own pocket and gives cement plant and make raw material, although 0.3
~2% Na2SO4There is early stage curing to cement, but it is aqueous higher in alkali mud（Aqueous about 15~20%）, early stage high temperature
Under the conditions of the Na that contains in alkali mud2S can cause corrosion to cement equipment, while Na in solid waste2SO4Content is unstable, it is difficult to control
Its consumption, Na in cement2SO4Content causes dispute once more than 2%, will make the phenomenon that becomes mildewed occur on cement works thing；4th
Kind of method, factory pays out of one's own pocket and gives brick field and do brick, due to Na2SO4Content is high, and bad may result in after brick dispatches from the factory of batch mixing is become mildewed
Phenomenon, causes dispute；Fifth method, takes out coal works and makees raw material, and coal works is added 10% coal in solid waste, is made with 2500
The fuel of kilocalorie, toxic gas can be produced during due to coal combustion containing solid waste, and this method is also unworkable.
In harmful influence ranks are listed akali sulphide solid waste by country at present, it is desirable to which solid waste is up to standard just to dispatch from the factory, and conventional vulcanized sodium is consolidated
Useless treatment does not meet national policy obviously, therefore, it is industry interior urgently to find a kind of environment-friendly treatment method of vulcanized sodium solid waste
Problem to be solved.
The content of the invention
The purpose of the present invention cannot be processed aiming at the solid waste that current vulcanized sodium industry is produced in process of production, to enterprise
Industry brings the problem of very big environmental protection pressure, there is provided the environmental protection recycling method and device of solid waste in a kind of vulcanized sodium production process.
The environmental protection recycling method of solid waste, comprises the steps in a kind of vulcanized sodium production process of the invention：
（1）In waste residue, useless size-mixing tank of the mud addition with agitating device that will be produced on vulcanized sodium production line, add water and sized mixing,
The water content of slurry is set to reach 40~60%, and being passed through steam makes slurry temperature rise to 40~50 DEG C；
（2）Slurries sludge pump in size-mixing tank is squeezed into the reactor with stirring and sealing device, matter is added under agitation
Amount fraction is 40~98% sulfuric acid solution, adds sulfuric acid while stirring until the pH of material in reactor is 6.0~7.0；Reacted
The hydrogen sulfide gas produced in journey introduce vulcanization hydrogen recovery unit generation sodium sulfide solution, and sodium sulfide solution is recycled into main production
Line is further purified；
（3）The material that pH in reactor reaches 6.0~7.0 is squeezed into flame filter press with sludge pump to be filtered, gained filter residue
Detection wherein sodium sulfide content is zero, and during sodium sulphate content ＜ 0.3%, i.e. meet the requirement of environmental protection can be used for cement plant, brick field former
Material, also can directly fill（If harmful substance contents are somewhat exceeded in filter residue, filter residue is rinsed using clear water, filtering is harmful to it
Processed again after content of material is up to standard）；Gained filtrate is collected into sodium sulphate mother liquor holding tank, detection wherein sodium sulfate quality point
During number >=35%, into next step operation, during sodium sulfate quality fraction ＜ 35%, return to step（1）Size-mixing tank is added as tune
Slurry water；
（4）By step（3）During the metabisulfite solution of mass fraction >=35% pumps into sulfate crystal device in mother liquor holding tank, in pressure
Be -0.07~-0.09MPa, temperature is evaporative crystallization under conditions of 60~70 DEG C, when in sulfate crystal device solid-to-liquid ratio up to 30%
When~70%, anhydrous sodium sulfate solid and sulfuric acid mother liquid of sodium, anhydrous slufuric acid is centrifuged to obtain during the material in crystallizer is pumped into centrifuge
Sodium solid is used into main line as raw material, and sulfuric acid mother liquid of sodium is recycled in returning to crystallizer or mother liquor holding tank.
Heretofore described waste residue, the water content of useless mud are 18~25%, and sodium sulfide content is 0.5~5%, sodium sulphate content
It is 5~15%.
Heretofore described reactor is enamel reaction still, its proof pressure≤0.6MPa.
Heretofore described vulcanization hydrogen recovery unit includes one-level alkali neutralizing tank, two grades of alkali neutralizing tanks and alkali liquor storage tank, one
Wireway and feed tube are respectively arranged with the top of level alkali neutralizing tank, two grades of alkali neutralizing tanks and alkali liquor storage tank, bottom is respectively arranged with drain pipe,
Wireway stretch into blast pipe at the top of the reacted kettle of hydrogen sulfide gas produced in 5~10cm of tank bottom, reactor in tank according to
Secondary entrance one-level alkali neutralizing tank, two grades of alkali neutralizing tanks and alkali liquor storage tank are completely absorbed；Alkali lye in alkali liquor storage tank passes through its bottom
The drain pipe in portion to supplementing alkali lye step by step in two grades of alkali neutralizing tanks, one-level alkali neutralizing tank, while the sodium sulfide solution of generation is to one
It is enriched with level alkali neutralizing tank, the sodium sulfide solution in one-level alkali neutralizing tank is enriched to mass fraction for 20~25% return to master afterwards
Production line purification is evolved；The alkali lye be use mass fraction for 16~20% sodium hydroxide solution.（In NaOH excess
In the case of, vulcanized sodium is generated, in the case of the non-excess of NaOH, NaHS is first generated, then vulcanized with generation with NaOH
Sodium）.
Heretofore described sodium sulphate condensing crystallizing device is produced using Hebei Shijiazhuang Bo Te Environmental Protection Technology Co., Ltd
Model BT~FSZF sulfate crystal device.
The condensed device of steam produced in heretofore described sodium sulphate condensing crystallizing device is condensed as production cycle water,
Or be introduced into tank of sizing mixing and used as heating steam.
Device in a kind of vulcanized sodium production process of the invention used by the environmental protection recycling method of solid waste, with tank of sizing mixing,
Particularly：Sizing mixing reactor, flame filter press, sodium sulphate mother liquor holding tank, sulfate crystal device, the centrifugation of be sequentially connected in series after tank
Machine, described to size mixing tank and reactor is respectively arranged with agitating device, reactor top is also equipped with mechanically-sealing apparatus and has blast pipe, arranges
The external vulcanization hydrogen recovery unit of tracheae, the vulcanization hydrogen recovery unit includes one-level alkali neutralizing tank, two grades of alkali neutralizing tanks and alkali lye
Storage tank, wireway and feed tube are respectively arranged with the top of one-level alkali neutralizing tank, two grades of alkali neutralizing tanks and alkali liquor storage tank, and bottom is respectively arranged with
Drain pipe, wireway is stretched into tank apart from 5~10cm of tank bottom；Branch is also equipped with drain pipe below the sodium sulphate mother liquor holding tank
Pipe is returned and is connected to tank of sizing mixing, and the drain pipe of the centrifuge is returned and is connected to sodium sulphate condensing crystallizing device.
A mother liquor holding tank, the drain pipe and sulphur of mother liquor holding tank are also added on the drain pipe of heretofore described centrifuge
The feed tube of sour sodium crystallizer is connected.
Orifice plate is also equipped with inside heretofore described one-level alkali neutralizing tank and two grades of alkali neutralizing tanks, for increasing stink damp
The contact area of body and alkali lye.
The inventive method is that first the solid waste produced on vulcanized sodium production line is sized mixing, and is passed through steam and makes slurry temperature
40~50 DEG C are warming up to, at this temperature, the solubility of sodium sulphate can reach maximum, slurry is then pumped into enamel reaction
Add sulfuric acid in kettle, make vulcanized sodium and sulfuric acid reaction generation sodium sulphate and hydrogen sulfide gas in slurry, the hydrogen sulfide gas of generation
It is introduced into two grades of vulcanization hydrogen recovery units equipped with sodium hydroxide solution, the sodium sulfide solution of generation can return to main line to be made
With；Reaction equation is as follows：
Na2S+H2SO4=Na2SO4+H2S↑；
H2S+NaOH=Na2S+H2O；
Slurry after reaction kettle for reaction is squeezed into flame filter press and is filtered, and the content of harmful substance reaches state in gained filter residue
Family's environmental protection standard, can directly fill or take out brick field, cement plant, coal yard etc., and filtrate detection sodium sulfate quality fraction reaches
Condensing crystallizing generation anhydrous sodium sulfate in sodium sulphate crystallizing evaporator can be entered when more than 35% and return to main line as raw material
Use, return to size mixing circulate in tank when sodium sulfate quality fraction is less than 35% and size mixing.The steam produced in sulfate crystal device is through cold
Condenser is condensed as production cycle water, or is introduced into tank of sizing mixing and use as heating steam.
The inventive method in the akali sulphide factory for Xinjiang or Sichuan, because the akali sulphide factory in Xinjiang and Sichuan is to adopt
Sodium sulphate is extracted with subsurface brine and salt alkali lake, bittern is refined, during vacuum evaporation, the concentration of bittern is not higher than 20%, therefore, can
To save the sulfate crystal device after flame filter press, and sodium sulfate quality fraction after filtering is directly reached more than 20%
Filtrate is evaporated together with bittern, only increases tank of sizing mixing, reactor and vulcanization hydrogen recovery unit.Xinjiang and the akali sulphide in Sichuan
Yield accounts for the 70% of national total output, if the enterprise in above-mentioned two places uses the inventive method, it will produce economic benefit very high
And environmental benefit.
The inventive method technological process is succinct, and device is simple, and solid waste does not reach in can on the spot solving vulcanized sodium production process
Target problem, and the extracts active ingredients in solid waste are recycled, the environmental protection pressure of enterprise is not only reduced, also with certain
Economic benefit, should vigorously promote the use.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Fig. 2 is schematic device of the invention.
In figure, 1-size-mixing tank, 2-sludge pump, 3-reactor, 4-flame filter press, 5-sodium sulphate mother liquor holding tank,
6-sulfate crystal device, 7-one-level alkali neutralizing tank, 8-two grades of alkali neutralizing tanks, 9-alkali liquor storage tank, 10-wireway, 11-enter
Liquid pipe, 12-drain pipe, 13-blast pipe, 14-condenser, 15-centrifuge, 16-agitating device, 17-mechanical seal dress
Put, 18-branch pipe, 19-orifice plate.
Specific embodiment
Embodiment 1
Referring to Fig. 1, Fig. 2, the environmental protection recycling method of solid waste, comprises the steps in a kind of vulcanized sodium production process：
（1）In waste residue, useless size-mixing tank 1 of the mud addition with agitating device 16 that will be produced on vulcanized sodium production line, add water and adjusted
Slurry, makes the water content of slurry reach 40%, and being passed through steam makes slurry temperature rise to 45 DEG C；
（2）Slurries sludge pump 2 in size-mixing tank 1 is squeezed into the reactor 3 with stirring and sealing device, is added under agitation
Mass fraction is 60% sulfuric acid solution, adds sulfuric acid while stirring until the pH of material in reactor is 6.5；Produced in course of reaction
Raw hydrogen sulfide gas introduce vulcanization hydrogen recovery unit generation sodium sulfide solution, and sodium sulfide solution is recycled into main line and enters one
Step purification；
（3）The material that pH in reactor 3 reaches 6.5 is squeezed into flame filter press 4 with sludge pump 2 to be filtered, the inspection of gained filter residue
It is zero to survey wherein sodium sulfide content, and sodium sulphate content is 0.25%, i.e. meet the requirement of environmental protection, can be used for cement plant, brick field raw material,
Also can directly fill；Gained filtrate is collected into sodium sulphate mother liquor holding tank 5, return to step（1）Size-mixing tank 1 is added as use of sizing mixing
Water；Repeat step（1）~（3）, until the mass fraction of sodium sulphate is 35% in sodium sulphate mother liquor holding tank 5, into next step；
（4）By step（3）Mass fraction is that 35% metabisulfite solution pumps into sulfate crystal device 6 in sodium sulphate mother liquor holding tank 5
In, be -0.08MPa in pressure, temperature is evaporative crystallization under conditions of 65 DEG C, when in sulfate crystal device 6 solid-to-liquid ratio up to 45%
When, anhydrous sodium sulfate solid and sulfuric acid mother liquid of sodium is centrifuged to obtain during the material in crystallizer is pumped into centrifuge, anhydrous sodium sulfate is solid
Body is used into main line as raw material, and sulfuric acid mother liquid of sodium is recycled in returning to crystallizer or mother liquor holding tank 5.
Waste residue described in the present embodiment, the water content of useless mud are 22%, and sodium sulfide content is 3%, and sodium sulphate content is 10%.
Reactor 3 described in the present embodiment is enamel reaction still, its proof pressure≤0.6MPa.
Vulcanizing hydrogen recovery unit described in the present embodiment includes one-level alkali neutralizing tank 7, two grades of alkali neutralizing tanks 8 and alkali liquor storage tanks
9, the top of 7, two grades of alkali neutralizing tanks 8 of one-level alkali neutralizing tank and alkali liquor storage tank 9 is respectively arranged with wireway 10 and feed tube 11, and bottom is equal
Equipped with drain pipe 12, wireway 10 stretches into the reacted kettle top of hydrogen sulfide gas produced in tank bottom 10cm, reactor 3 in tank
The blast pipe 13 in portion sequentially enters 7, two grades of alkali neutralizing tanks 8 of one-level alkali neutralizing tank and alkali liquor storage tank 9 is completely absorbed；Alkali liquor storage tank
Alkali lye in 9 by the drain pipe 12 of its bottom to supplementing alkali lye step by step in two grades of alkali neutralizing tanks 8, one-level alkali neutralizing tank 7, while
The sodium sulfide solution of generation is enriched with one-level alkali neutralizing tank 7, and the sodium sulfide solution in one-level alkali neutralizing tank 7 is enriched to quality point
Number is evolved for 20% or so return main line purification afterwards；The alkali lye is to use mass fraction molten for 20% NaOH
Liquid.Note：In the case of NaOH excess, generation vulcanized sodium is neutralized, in the case of the non-excess of NaOH, generates NaHS,
Again with NaOH and generation vulcanized sodium.
The device of sodium sulphate condensing crystallizing described in the present embodiment is given birth to using Hebei Shijiazhuang Bo Te Environmental Protection Technology Co., Ltd
The sulfate crystal device of the model BT~FSZF of product.
The condensed device 14 of steam produced in sulfate crystal device described in the present embodiment 6 is condensed to be used as production cycle
Water, or be introduced into tank 1 of sizing mixing and used as heating steam.
Embodiment 2
The environmental protection recycling method of solid waste, comprises the steps in a kind of vulcanized sodium production process：
（1）In waste residue, useless size-mixing tank 1 of the mud addition with agitating device 16 that will be produced on vulcanized sodium production line, add water and adjusted
Slurry, makes the water content of slurry reach 50%, and being passed through steam makes slurry temperature rise to 40 DEG C；
（2）Slurries sludge pump 2 in size-mixing tank 1 is squeezed into the reactor 3 with stirring and sealing device, is added under agitation
Mass fraction is 40% sulfuric acid solution, adds sulfuric acid while stirring until the pH of material in reactor is 6.0；Produced in course of reaction
Raw hydrogen sulfide gas introduce vulcanization hydrogen recovery unit generation sodium sulfide solution, and sodium sulfide solution is recycled into main line and enters one
Step purification；
（3）The material that pH in reactor 3 reaches 6.0 is squeezed into flame filter press 4 with sludge pump 2 to be filtered, the inspection of gained filter residue
It is zero to survey wherein sodium sulfide content, and sodium sulphate content is 0.3%, i.e. meet the requirement of environmental protection, can be used for cement plant, brick field raw material,
Can directly fill；Gained filtrate is collected into sodium sulphate mother liquor holding tank 5, and detection wherein sodium sulfate quality fraction is 8%, returns to step
Suddenly（1）Size-mixing tank 1 is added to use water as sizing mixing；Repeat step（1）~（3）, until in sodium sulphate mother liquor holding tank 5 sodium sulphate matter
Amount fraction is 35%, into next step；
（4）By step（3）Mass fraction is that 35% metabisulfite solution pumps into sulfate crystal device 6 in sodium sulphate mother liquor holding tank 5
In, be -0.09MPa in pressure, temperature is evaporative crystallization under conditions of 70 DEG C, when in sulfate crystal device 6 solid-to-liquid ratio up to 30%
When, anhydrous sodium sulfate solid and sulfuric acid mother liquid of sodium is centrifuged to obtain during the material in crystallizer is pumped into centrifuge, anhydrous sodium sulfate is solid
Body is used into main line as raw material, and sulfuric acid mother liquid of sodium is recycled in returning to crystallizer or mother liquor holding tank 5.
Waste residue described in the present embodiment, the water content of useless mud are 25%, and sodium sulfide content is 0.5%, and sodium sulphate content is 5%.
Reactor 3 described in the present embodiment is enamel reaction still, its proof pressure≤0.6MPa.
Vulcanizing hydrogen recovery unit described in the present embodiment includes one-level alkali neutralizing tank 7, two grades of alkali neutralizing tanks 8 and alkali liquor storage tanks
9, the top of 7, two grades of alkali neutralizing tanks 8 of one-level alkali neutralizing tank and alkali liquor storage tank 9 is respectively arranged with wireway 10 and feed tube 11, and bottom is equal
Equipped with drain pipe 12, wireway 10 stretches into the reacted kettle top of hydrogen sulfide gas produced in tank bottom 7cm, reactor 3 in tank
The blast pipe 13 in portion sequentially enters 7, two grades of alkali neutralizing tanks 8 of one-level alkali neutralizing tank and alkali liquor storage tank 9 is completely absorbed；Alkali liquor storage tank
Alkali lye in 9 by the drain pipe 12 of its bottom to supplementing alkali lye step by step in two grades of alkali neutralizing tanks 8, one-level alkali neutralizing tank 7, while
The sodium sulfide solution of generation is enriched with one-level alkali neutralizing tank 7, and the sodium sulfide solution in one-level alkali neutralizing tank 7 is enriched to quality point
Number is evolved for 20% return main line purification afterwards；The alkali lye be use mass fraction for 16% sodium hydroxide solution.
The device of sodium sulphate condensing crystallizing described in the present embodiment is given birth to using Hebei Shijiazhuang Bo Te Environmental Protection Technology Co., Ltd
The sulfate crystal device of the model BT~FSZF of product.
The condensed device 14 of steam produced in sulfate crystal device described in the present embodiment 6 is condensed to be used as production cycle
Water, or be introduced into tank 1 of sizing mixing and used as heating steam.
Embodiment 3
The environmental protection recycling method of solid waste, comprises the steps in a kind of vulcanized sodium production process：
（1）In waste residue, useless size-mixing tank 1 of the mud addition with agitating device 16 that will be produced on vulcanized sodium production line, add water and adjusted
Slurry, makes the water content of slurry reach 60%, and being passed through steam makes slurry temperature rise to 50 DEG C；
（2）Slurries sludge pump 2 in size-mixing tank 1 is squeezed into the reactor 3 with stirring and sealing device, is added under agitation
Mass fraction is 98% sulfuric acid solution, adds sulfuric acid while stirring until the pH of material in reactor is 7.0；Produced in course of reaction
Raw hydrogen sulfide gas introduce vulcanization hydrogen recovery unit generation sodium sulfide solution, and sodium sulfide solution is recycled into main line and enters one
Step purification；
（3）The material that pH in reactor 3 reaches 7.0 is squeezed into flame filter press 4 with sludge pump 2 to be filtered, the inspection of gained filter residue
It is 0 to survey wherein sodium sulfide content, and sodium sulphate content is 0.25%, i.e. meet the requirement of environmental protection, can be used for cement plant, brick field raw material,
Can directly fill；Gained filtrate is collected into sodium sulphate mother liquor holding tank 5, and detection wherein sodium sulfate quality fraction is 13%, returns to step
Suddenly（1）Size-mixing tank 1 is added to use water as sizing mixing；Repeat step（1）~（3）, until in sodium sulphate mother liquor holding tank 5 sodium sulphate matter
Amount fraction is 35%, into next step；
（4）By step（3）Mass fraction is that 40% metabisulfite solution pumps into sulfate crystal device 6 in sodium sulphate mother liquor holding tank 5
In, be -0.07MPa in pressure, temperature is evaporative crystallization under conditions of 60 DEG C, when in sulfate crystal device 6 solid-to-liquid ratio up to 70%
When, anhydrous sodium sulfate solid and sulfuric acid mother liquid of sodium is centrifuged to obtain during the material in crystallizer is pumped into centrifuge, anhydrous sodium sulfate is solid
Body is used into main line as raw material, and sulfuric acid mother liquid of sodium is recycled in returning to crystallizer or mother liquor holding tank 5.
Waste residue described in the present embodiment, the water content of useless mud are 18%, and sodium sulfide content is 5%, and sodium sulphate content is 15%.
Reactor 3 described in the present embodiment is enamel reaction still, its proof pressure≤0.6MPa.
Vulcanizing hydrogen recovery unit described in the present embodiment includes one-level alkali neutralizing tank 7, two grades of alkali neutralizing tanks 8 and alkali liquor storage tanks
9, the top of 7, two grades of alkali neutralizing tanks 8 of one-level alkali neutralizing tank and alkali liquor storage tank 9 is respectively arranged with wireway 10 and feed tube 11, and bottom is equal
Equipped with drain pipe 12, wireway 10 stretches into the reacted kettle top of hydrogen sulfide gas produced in tank bottom 5cm, reactor 3 in tank
The blast pipe 13 in portion sequentially enters 7, two grades of alkali neutralizing tanks 8 of one-level alkali neutralizing tank and alkali liquor storage tank 9 is completely absorbed；Alkali liquor storage tank
Alkali lye in 9 by the drain pipe 12 of its bottom to supplementing alkali lye step by step in two grades of alkali neutralizing tanks 8, one-level alkali neutralizing tank 7, while
The sodium sulfide solution of generation is enriched with one-level alkali neutralizing tank 7, and the sodium sulfide solution in one-level alkali neutralizing tank 7 is enriched to quality point
Number is evolved for 25% return main line purification afterwards；The alkali lye be use mass fraction for 20% sodium hydroxide solution.
The device of sodium sulphate condensing crystallizing described in the present embodiment is given birth to using Hebei Shijiazhuang Bo Te Environmental Protection Technology Co., Ltd
The sulfate crystal device of the model BT~FSZF of product.
The condensed device 14 of steam produced in sulfate crystal device described in the present embodiment 6 is condensed to be used as production cycle
Water, or be introduced into tank 1 of sizing mixing and used as heating steam.
Embodiment 4
A kind of device in vulcanized sodium production process used by the environmental protection recycling method of solid waste, with tank 1 of sizing mixing, particularly：Size mixing
Reactor 3, flame filter press 4, sodium sulphate mother liquor holding tank 5, sulfate crystal device 6, centrifuge 15, institute have been sequentially connected in series after tank 1
State and size mixing tank 1 and reactor 3 is respectively arranged with agitating device 16, the top of reactor 3 is also equipped with mechanically-sealing apparatus 17 and has blast pipe
13, the external vulcanization hydrogen recovery unit of blast pipe 13, the vulcanization hydrogen recovery unit includes that 7, two grades of alkali of one-level alkali neutralizing tank are neutralized
The top of tank 8 and alkali liquor storage tank 9,7, two grades of alkali neutralizing tanks 8 of one-level alkali neutralizing tank and alkali liquor storage tank 9 is respectively arranged with wireway 10 and enters
Liquid pipe 11, bottom is respectively arranged with drain pipe 12, and wireway 10 is stretched into tank apart from 5~10cm of tank bottom（It is specially in the present embodiment
10cm）；Branch pipe 18 is also equipped with the drain pipe 12 of the lower section of the sodium sulphate mother liquor holding tank 5 and returns to be connected to tank 1 of sizing mixing, the centrifuge
15 drain pipe 12 is returned and is connected to sulfate crystal device 6.
Also add a mother liquor holding tank 5 on the drain pipe 12 of centrifuge 15 described in the present embodiment, mother liquor holding tank 5 goes out
Liquid pipe 12 is connected with the feed tube 11 of sulfate crystal device 6.
Orifice plate 19 is also equipped with inside the neutralizing tank of one-level alkali described in the present embodiment 7 and two grades of alkali neutralizing tanks 8, for increasing sulphur
Change the contact area of hydrogen and alkali lye.
Claims (9)
1. in a kind of vulcanized sodium production process solid waste environmental protection recycling method, it is characterised in that comprise the steps：
（1）In waste residue, useless size-mixing tank of the mud addition with agitating device that will be produced on vulcanized sodium production line, add water and sized mixing,
The water content of slurry is set to reach 40~60%, and being passed through steam makes slurry temperature rise to 40~50 DEG C；
（2）Slurries sludge pump in size-mixing tank is squeezed into the reactor with stirring and sealing device, matter is added under agitation
Amount fraction is 40~98% sulfuric acid solution, adds sulfuric acid while stirring until the pH of material in reactor is 6.0~7.0；Reacted
The hydrogen sulfide gas produced in journey introduce vulcanization hydrogen recovery unit generation sodium sulfide solution, and sodium sulfide solution is recycled into main production
Line is further purified；
（3）The material that pH in reactor reaches 6.0~7.0 is squeezed into flame filter press with sludge pump to be filtered, gained filter residue
Detection wherein sodium sulfide content is zero, and during sodium sulphate content ＜ 0.3%, i.e. meet the requirement of environmental protection can be used for cement plant, brick field former
Material, also can directly fill；Gained filtrate is collected into sodium sulphate mother liquor holding tank, when detecting wherein sodium sulfate quality fraction >=35%,
Into next step operation, during sodium sulfate quality fraction ＜ 35%, return to step（1）Size-mixing tank is added to use water as sizing mixing；
（4）By step（3）During the metabisulfite solution of mass fraction >=35% pumps into sodium sulphate condensing crystallizing device in mother liquor holding tank,
Vacuum pressure is -0.07~-0.09MPa, and temperature is evaporative crystallization under conditions of 60~70 DEG C, when in sodium sulphate condensing crystallizing device
When solid-to-liquid ratio is up to 30%~70%, anhydrous sodium sulfate solid and sodium sulphate mother is centrifuged to obtain during the material in crystallizer is pumped into centrifuge
Liquid, anhydrous sodium sulfate solid is used into main line as raw material, and sulfuric acid mother liquid of sodium is followed in returning to crystallizer or mother liquor holding tank
Ring is used.
2. in a kind of vulcanized sodium production process according to claim 1 solid waste environmental protection recycling method, it is characterised in that：Institute
It is 18~25% to state waste residue, the water content of useless mud, and sodium sulfide content is 0.5~5%, and sodium sulphate content is 5~15%.
3. in a kind of vulcanized sodium production process according to claim 1 solid waste environmental protection recycling method, it is characterised in that：Institute
Reactor is stated for enamel reaction still, its proof pressure≤0.6MPa.
4. in a kind of vulcanized sodium production process according to claim 1 solid waste environmental protection recycling method, it is characterised in that：Institute
Stating vulcanization hydrogen recovery unit includes one-level alkali neutralizing tank, two grades of alkali neutralizing tanks and alkali liquor storage tank, in one-level alkali neutralizing tank, two grades of alkali
With wireway and feed tube are respectively arranged with the top of tank and alkali liquor storage tank, bottom is respectively arranged with drain pipe, and wireway stretches into distance in tank
5~10cm of tank bottom, the blast pipe at the top of the reacted kettle of hydrogen sulfide gas produced in reactor sequentially enter one-level alkali neutralizing tank,
Two grades of alkali neutralizing tanks and alkali liquor storage tank are completely absorbed；Alkali lye in alkali liquor storage tank is by the drain pipe of its bottom in two grades of alkali
Alkali lye is supplemented step by step with tank, one-level alkali neutralizing tank, while the sodium sulfide solution of generation is enriched with one-level alkali neutralizing tank, one-level
Sodium sulfide solution in alkali neutralizing tank is enriched to mass fraction for 20~25% return to main line purification evolution afterwards；The alkali
Liquid be use mass fraction for 16~20% sodium hydroxide solution.
5. in a kind of vulcanized sodium production process according to claim 1 solid waste environmental protection recycling method, it is characterised in that：Institute
It is the model BT~FSZF using the production of Hebei Shijiazhuang Bo Te Environmental Protection Technology Co., Ltd to state sodium sulphate condensing crystallizing device
Sulfate crystal device.
6. in a kind of vulcanized sodium production process according to claim 1 solid waste environmental protection recycling method, it is characterised in that：Institute
State the condensed device of steam produced in sulfate crystal device to condense as production cycle water, or be introduced into conduct heating in tank of sizing mixing
Steam is used.
7. the device in a kind of vulcanized sodium production process as claimed in claim 1 used by the environmental protection recycling method of solid waste, has
Size mixing tank, it is characterised in that：Size mixing and be sequentially connected in series reactor, flame filter press, sodium sulphate mother liquor holding tank, sodium sulphate knot after tank
Brilliant device, centrifuge, described to size mixing tank and reactor is respectively arranged with agitating device, reactor top is also equipped with mechanically-sealing apparatus and has
Blast pipe, the external vulcanization hydrogen recovery unit of blast pipe, the vulcanization hydrogen recovery unit includes that one-level alkali neutralizing tank, two grades of alkali are neutralized
Tank and alkali liquor storage tank, wireway and feed tube, bottom are respectively arranged with the top of one-level alkali neutralizing tank, two grades of alkali neutralizing tanks and alkali liquor storage tank
Portion is respectively arranged with drain pipe, and wireway is stretched into tank apart from 5~10cm of tank bottom；On drain pipe below the sodium sulphate mother liquor holding tank
It is also equipped with branch pipe and returns to be connected to tank of sizing mixing, the drain pipe of the centrifuge is returned and is connected to sulfate crystal device.
8. the device in a kind of vulcanized sodium production process according to claim 7 used by the environmental protection recycling method of solid waste, its
It is characterised by：A mother liquor holding tank is also added on the drain pipe of the centrifuge, the drain pipe of mother liquor holding tank is dense with sodium sulphate
The feed tube of contracting crystallizer is connected.
9. the device in a kind of vulcanized sodium production process according to claim 7 used by the environmental protection recycling method of solid waste, its
It is characterised by：Orifice plate is also equipped with inside the one-level alkali neutralizing tank and two grades of alkali neutralizing tanks, for increasing hydrogen sulfide gas and alkali
The contact area of liquid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107867709A (en) * | 2017-12-11 | 2018-04-03 | 广州叶林环保科技有限公司 | A kind of processing technology for being concentrated by evaporation aqueous sodium persulfate solution crystallization |
| CN109650727A (en) * | 2018-09-13 | 2019-04-19 | 西南科技大学 | A kind of method that vulcanized sodium slag prepares cellular glass |
| CN109650847A (en) * | 2018-09-13 | 2019-04-19 | 西南科技大学 | A kind of vulcanized sodium slag prepares insulating wall material method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107867709A (en) * | 2017-12-11 | 2018-04-03 | 广州叶林环保科技有限公司 | A kind of processing technology for being concentrated by evaporation aqueous sodium persulfate solution crystallization |
| CN109650727A (en) * | 2018-09-13 | 2019-04-19 | 西南科技大学 | A kind of method that vulcanized sodium slag prepares cellular glass |
| CN109650847A (en) * | 2018-09-13 | 2019-04-19 | 西南科技大学 | A kind of vulcanized sodium slag prepares insulating wall material method |
| CN109650847B (en) * | 2018-09-13 | 2021-07-20 | 西南科技大学 | Method for preparing heat-insulating wall material from sodium sulfide slag |
| CN109650727B (en) * | 2018-09-13 | 2021-09-17 | 西南科技大学 | Method for preparing porous glass from sodium sulfide slag |
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| CN106698481B (en) | 2017-11-17 |
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