CN109354252A - A kind of processing method of Sewage from Sulphuric Acid Plants - Google Patents
A kind of processing method of Sewage from Sulphuric Acid Plants Download PDFInfo
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- CN109354252A CN109354252A CN201811427663.6A CN201811427663A CN109354252A CN 109354252 A CN109354252 A CN 109354252A CN 201811427663 A CN201811427663 A CN 201811427663A CN 109354252 A CN109354252 A CN 109354252A
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- sewage
- sulphuric acid
- acid plants
- neutralization reaction
- processing method
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
Abstract
The invention discloses a kind of processing methods of Sewage from Sulphuric Acid Plants, belong to technical field of sewage.The processing method of the Sewage from Sulphuric Acid Plants, includes the following steps: step 1: continuous neutralization reaction；Step 2: being separated by solid-liquid separation.The present invention is with H2SO4The Sewage from Sulphuric Acid Plants that concentration is 10g/L~300g/L is process object, using agstone as neutralizer, is continuously neutralized, and for obtained neutralized reaction product after filter is separated by solid-liquid separation, obtained solid is industrial gypsum, for sale；After obtained filtered fluid otherwise processed recycles valuable metal therein, then externally discharges or return other production stations and recycle.The processing method of Sewage from Sulphuric Acid Plants of the invention, can output qualification gypsum product, be finally reached the purpose of Sewage from Sulphuric Acid Plants progress resource utilization, have many advantages, such as that process flow is short, production cost is low, the stacking and problem of management of not no melting waste slag.
Description
Technical field
The present invention relates to a kind of processing methods of Sewage from Sulphuric Acid Plants, belong to technical field of sewage.
Background technique
In the production process of the nonferrous metal products such as copper, lead, zinc, the sulfur dioxide flue gas of high concentration before Sulphuric acid,
It requires to carry out washing, purifying to flue gas, to remove the dust in flue gas.A small amount of sulfur dioxide in washing, purifying, in flue gas
It is dissolved in cleaning dust water, forms sulfurous acid, sulfurous acid is dissolved in the dioxygen oxidation in cleaning dust water simultaneously, is changed into
Dilute sulfuric acid.This cleaning dust aqueous solution containing dilute sulfuric acid, is referred to as Sewage from Sulphuric Acid Plants.In Sewage from Sulphuric Acid Plants, H2SO4Concentration is
10g/L~300g/L, and contain a small amount of copper, lead, zinc metal ion, also contain a small amount of fluorine ion, chloride ion, sulfurous acid
Root, arsenic ion, cadmium ion etc..
Currently, for H2SO4Concentration is that the main method of Sewage from Sulphuric Acid Plants of 10g/L~300g/L is: using lime (including
Quick lime, white lime, digestion lime) it is neutralized.In N-process, control neutralize terminal pH value > 10.5, lime with
Sulfuric acid is reacted, and generates that solubility is smaller and the good calcium sulfate of stability.Meanwhile copper in Sewage from Sulphuric Acid Plants, lead, zinc from
Son, cadmium ion and part arsenic ion are respectively formed corresponding hydroxide precipitating, into calcium sulfate slag.In addition, a small amount of Asia
Sulfate radical and calcium binding, which are formed after calcium sulfite, to be further oxided as calcium sulfate, and part arsenic ion forms arsenic acid calcium salt,
Also enter in calcium sulfate slag.The above method has the advantages that technology maturation, adaptable, easy to operate, processing cost is low etc., but
It, can not since a large amount of calcium sulfate slags that N-process is formed do not meet the gypsum product standard requirements of cement industry or building material industry
It realizes resource utilization, ultimately forms the dangerous waste residue of smelting, the dangerous waste residue of this smelting is deposited in subsequent storage, management process
In biggish environment hidden danger, the development of enterprise is constrained.
To overcome the above disadvantages, some enterprises handle sulfuric acid dirt using two sections of neutralization methods or three sections of neutralization methods
Water.When using two sections of neutralization methods, first segment agstone makees neutralizer, and control neutralizes endpoint pH < 1.5；Second segment is used
Lime makees neutralizer, and control neutralizes endpoint pH > 10.5.When using two sections of neutralization methods, in the first paragraph and in the process, copper,
The heavy metals such as lead, zinc, arsenic, cadmium are still dissolved in the water in the form of an ion, do not form hydroxide precipitating, first segment output
Calcium sulfate slag is theoretically containing less heavy metal；And in second segment N-process, the huge sum of money such as copper, lead, zinc, arsenic, cadmium forms hydrogen
The calcium sulfate slag of oxide precipitation, second segment output is enriched with heavy metal, keeps this part of sulfuric acid calcium slag economically first
Step has the value of development and utilization.Compared to one section neutralization method, two sections of neutralization methods are due to using cost more in first segment
Low agstone makees neutralizer, therefore reagent cost consumption is lower, simultaneously as the calcium sulfate slag that second segment obtains tentatively has
For the value of development and utilization, can develop and utilize, in this way, the dangerous waste residue of output has measured reduction.But in two sections
And method, bigger investment, broader land occupation, more complicated operation, higher wage cost are needed, and in the first paragraph and mistake
Cheng Zhong forms the gypsum product standard requirements that a large amount of calcium sulfate slags still do not meet cement industry or building material industry, cannot achieve
Resource utilization.Therefore, it says on the whole, two sections of neutralization methods have obvious advantage there is no than one section neutralization method, practical
The enterprise of application is simultaneously few.
When using three sections of neutralization methods, implement generally directed to ferric ion and the higher solution of aluminium ion.First segment
Make neutralizer with agstone, control neutralizes endpoint pH < 1.5；Second segment lime makees neutralizer, and control neutralizes terminal pH
Value < 4.5；Second segment lime makees neutralizer, and control neutralizes endpoint pH > 10.5.When using three sections of neutralization methods, first
In section N-process, the heavy metals such as copper, lead, zinc, arsenic, cadmium, iron, aluminium are still dissolved in the water in the form of an ion, do not form hydrogen
Oxide precipitation, the calcium sulfate slag of first segment output is theoretically containing less heavy metal；And in second segment N-process, trivalent
Iron ion or aluminium ion form sediment, and into slag, and the huge sum of money such as copper, lead, zinc, arsenic, cadmium does not form hydroxide precipitating,
The calcium sulfate slag of second segment output is enriched iron or aluminium can further development and production iron oxide red or aluminum sulfate product.In third section
And when, the huge sum of money such as copper, lead, zinc, arsenic, cadmium forms hydroxide precipitating, and the calcium sulfate slag of third section output obtains heavy metal
Higher enrichment makes this part of sulfuric acid calcium slag have value of exploiting and utilizing.Three sections of neutralization methods, due to first segment use at
This lower agstone makees neutralizer, therefore than one section neutralization technology of reagent cost consumption is lower；Simultaneously as in second segment
And have a stronger specific aim, the calcium sulfate slag of second segment output also has the value of development and utilization；It is obtained due to third section
Calcium sulfate slag metal enrichment ratio is higher, has the value of development and utilization, can develop and utilize, in this way, the danger of output
Waste residue amount, which has been got back, to be further reduced.But three sections of neutralization methods need bigger investment, broader land occupation, more complicated behaviour
Make, higher wage cost, and in second segment N-process, forms iron content or the calcium sulfate slag development and utilization containing aluminium, only stop
The experimental study stage is stayed in, industrial application can not be formed, and the calcium sulfate slag of first segment output does not still meet cement industry
Or the gypsum product standard requirements of building material industry, it cannot achieve resource utilization.Therefore, three sections of neutralization methods, currently without reality
The enterprise of border application.
In addition, the resource utilization in order to realize Sewage from Sulphuric Acid Plants, some enterprises attempt to have carried out ion exchange technique, solvent
Abstraction technique, sulfide precipitation removing heavy-metal technology, macromolecule organic complex-precipitation defluorinate chlorine technology, the purpose is to sulfuric acid is dirty
After various impurity or the removing of main objectionable impurities in water, the dry post that absorbs that dilute sulfuric acid is used for flue gas acid preparing is matched
Acid, but these methods are due at high cost, and can not obtain satisfied technical indicator.Currently, still without success and the industry of maturation
Using.
In consideration of it, it is necessary to develop a kind of processing method of new Sewage from Sulphuric Acid Plants, to make up the deficiencies in the prior art.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of processing method of Sewage from Sulphuric Acid Plants.The present invention with
The Sewage from Sulphuric Acid Plants that concentration is 10g/L~300g/L is process object, using agstone as neutralizer, is continuously neutralized, is obtained
Neutralized reaction product after filter is separated by solid-liquid separation, obtained solid is industrial gypsum, for sale；Obtained filtered fluid
After otherwise processed recycles valuable metal therein, then externally discharges or return other production stations and recycle.Sulphur of the invention
The processing method of sour sewage, the gypsum product of energy output qualification are finally reached the purpose that Sewage from Sulphuric Acid Plants is carried out to resource utilization,
Have many advantages, such as that process flow is short, production cost is low, the stacking and problem of management of not no melting waste slag.
The technical scheme to solve the above technical problems is that a kind of processing method of Sewage from Sulphuric Acid Plants, including it is as follows
Step:
Step 1: continuous neutralization reaction
Sewage from Sulphuric Acid Plants and agstone are continuously put into neutralization reaction equipment, continuous neutralization reaction is carried out, is controlled
The temperature of reaction is 20 DEG C~80 DEG C, pH value is 3.0~5.0, and the reaction mass residence time is 5h~100h, obtains neutralization reaction
Product slurry；
Step 2: being separated by solid-liquid separation
The neutralization reaction product slurry that step 1 is obtained, is separated by solid-liquid separation, respectively obtains industrial gypsum and filtered fluid,
Industrial gypsum is for sale, it discharges or recycles again after filtered fluid is recycled valuable metal.
The principle of the present invention is:
(1) Sewage from Sulphuric Acid Plants gets utilization
Cement industry and building material industry have two basic technical indicator requirements to industrial gypsum product, first is that SO in gypsum3
Effective content is not less than 40%, second is that the moisture content of gypsum is not higher than 12%.The present invention is made using cheap agstone
Neutralizer, the reaction mainly occurred in N-process are as follows: CaCO3+H2SO4+H2O=CO2↑+CaSO4·2H2O ↓, the reaction
Standard free enthalpy changes delta G0It is a biggish negative for -135kJ, reaction progress is very thorough, can generate CaSO4·
2H2O。
Two basic indexs requirement according to cement industry and building material industry to gypsum product, gypsum product must have height
SO3The CaSO that content and low moisture content, i.e. neutralization reaction generate4·2H2O filtering is in kind, it is necessary to have high SO3Content and compared with
Few mechanical entrapment adhesive water, is only industrial gypsum.
Firstly, to realize that gypsum product has higher SO3Content is carried secretly less as far as possible it is necessary to the gypsum product ensured
The unreacted small solid of agstone, therefore, the pH value control of reaction process are critically important.Present inventor is by a large amount of
Experimental study proves, is 3.0~5.0 by the slurry pH value control of neutralization reaction process, both can be as much as possible by Sewage from Sulphuric Acid Plants
In H2SO4It is neutralized, and may insure the CaSO that the agstone being added participates in neutralization reaction, generates neutralization reaction4·
2H2O filtering material object carries the small solid of unreacted agstone secretly less as far as possible, it is ensured that SO in obtained gypsum product3Content reaches
It is required that.
Secondly, to realize the CaSO that neutralization reaction generates4·2H2O filtering less mechanical entrapment adhesive water in kind contains
Measure the CaSO generated it is necessary to the neutralization reaction ensured4·2H2O filtering material object has lesser specific surface, by reducing product
Specific surface achieve the purpose that reduce mechanical entrapment adhesive water.And lesser specific surface is obtained, it should just obtain larger
The CaSO of grain4·2H2O filtering is in kind, this biggish CaSO4·2H2O filtering in kind is industrial gypsum product, that is, ensures to react
The CaSO of generation4·2H2O has sufficient crystal to grow up condition, grows into bulky grain CaSO4·2H2O crystal.Present invention
People proves by a large amount of experimental study, makees neutralizer with agstone, is 20 DEG C~80 DEG C, pH value 3.0 in reaction temperature
~5.0, the reaction mass residence time, can be with output larger particles continuously to be neutralized under conditions of 5h~100h
CaSO4·2H2O filtering is in kind, it is ensured that CaSO4·2H2O filters mechanical entrapment attached water rate in kind and is not higher than 12%, makes CaSO4·
2H2O filtering material object meets the quality criteria requirements of industrial gypsum, output acceptable industrial gypsum.
Machine mixer is installed in continuous neutralization reaction equipment, it is mechanical to ensure effective progress of continuous neutralization reaction
Blender can be inputting type, be also possible to side entering type.Each neutralization reaction equipment, can install separate unit blender, can also be with
More blenders are installed.Sewage from Sulphuric Acid Plants is continuously added to above consersion unit, the addition speed and flow of Sewage from Sulphuric Acid Plants, it is necessary to
Meeting residence time of the reaction mass in neutralization reaction equipment is 5h~100h, to ensure to react the CaSO generated4·2H2O is brilliant
Body has sufficient growth time, forms biggish CaSO4·2H2O crystal reduces CaSO4·2H2The specific surface of O crystal, finally
Ensure CaSO4·2H2O filters purpose of the mechanical entrapment adhesive water less than 12% in kind.Agstone is from the top of consersion unit
It is added, the addition of agstone can be continuously, be also possible to desultory.When being added intermittently, add every time
Enter interval time no more than 20 minutes.Control agstone is added speed and weight is added to ensure the slurry pH value of reaction process
3.0~5.0.If consersion unit is provided with neutralized reaction product overflow pipe, at interval of 1.0~2.0 hours, neutralized instead to overflowing to
The neutralization reaction slurries outside equipment are answered to be filtered separation.If consersion unit is not provided with neutralization reaction slurries overflow pipe,
Suitable neutralization reaction can be extracted at interval of 1.0~2.0 hours according to the neutralization reaction liquid volume capacity in consersion unit
Slurries filtering, the slurries amount of extraction and the additional amount population equilibrium of interval time.When extracting neutralization reaction slurries, from neutralization reaction
It is more reasonable than extracting from top that the bottom of equipment is extracted, the reason is that the CaSO of consersion unit bottom4·2H2O crystal grain compares top
CaSO4·2H2O crystal grain is bigger, the CaSO obtained after filtering4·2H2O filtering mechanical entrapment adhesive water in kind is lower,
It more can ensure that CaSO4·2H2O filtering material object reaches the moisture content index requirement of industrial gypsum product, forms qualified industrial gypsum.
Sometimes the neutralization reaction slurries of extraction are first also subjected to classification processing, the lesser CaSO of particle with hydrocyclone4·2H2O crystal
Go out to again return to neutralization reaction equipment from the overflow pipe of hydrocyclone and continues to grow up, the biggish CaSO of particle4·2H2O crystal from
The underflow pipe of hydrocyclone flows out, and filter plant is entered back into, in this way, further ensuring the CaSO that filter plant obtains4·
2H2O filtering in kind is bigger CaSO4·2H2O particle, more can ensure that CaSO4·2H2O filtering material object meets the moisture of gypsum product
Index request forms industrial gypsum product.
The present invention makees neutralizer using agstone, reaction temperature be 20 DEG C~80 DEG C, reacting slurry pH value be 3.0~
5.0, the reaction mass residence time be 5h~100h under conditions of continuously neutralized, obtained CaSO4·2H2O filters machine in kind
Tool carries attached water rate secretly less than 12%, SO3Content is greater than 40%, meets cement industry and building material industry to gypsum product standard base
This requirement, this CaSO4·2H2O filtering in kind is industrial gypsum product, can be sold to cement industry or building material industry, real
The purpose of Sewage from Sulphuric Acid Plants resource utilization is showed.
(2) process flow is short
Only there are two steps by the present invention, so that it may which the industrial gypsum product of output qualification, the two steps are i.e. continuous to be neutralized
Reaction process and separation of solid and liquid process.In continuous neutralization reaction, neutralizer is made using agstone, and be maintained at N-process
The pH value of middle reacting slurry solution is controlled always 3.0~5.0, can be by the H in Sewage from Sulphuric Acid Plants2SO4Complete neutralization, and can be really
Protecting CaSO42H2O filtering material object has higher SO3Content；Meanwhile control continuous neutralization reaction temperature be 20 DEG C~80 DEG C, it is anti-
Answering residence time of material is 5h~100h, it can be ensured that obtained CaSO4·2H2O filtering is in kind be biggish Jing Ti ?, it is mechanical
Attached water rate is carried secretly less than 12%, meets gypsum product standard requirements.Separation of solid and liquid process is a simple physical process,
It is easy to operate, process mechanism and automation may be implemented.
(3) production cost is low
The present invention is since process flow is short, investment reduction, also reduces equipment investment cost and process maintenance maintenance cost,
Also cost of labor is saved, while using cheap agstone and making neutralizer, reduces cost.The processing side of the prior art
Method makees neutralizer with lime, and 10.5 or more, lime is excessive for pH value control, neutralizer waste, and strict control solution of the present invention
PH value be 3.0~5.0, the utilization rate of neutralizer agstone is high, it is superfluous seldom, reduce neutralizer consumption.The present invention adopts
Make neutralizer, 1 ton of H of every processing with agstone2SO4Concentration is the Sewage from Sulphuric Acid Plants of 100g/L, only 45 yuan of consuming cost, comprising:
(1) electric energy 20kwh is consumed, cost is 12 yuan；(2) 0.12 ton of agstone is consumed, cost is 12 yuan；(3) steam consumption
0.04 ton, cost is 6 yuan；(4) investment depreciation is extracted, and being converted into this is 4 yuan；(5) maintenance of equipment cost is 5 yuan；(6) wage cost
It is 10 yuan；(7) gypsum selling cost is 3 yuan；(8) 3 yuan of other costs such as sample analysis etc.；(9) 0.2 ton of gypsum product is produced, is supported
Being fastened as this is 10 yuan.
(4) process cleans environmental protection
Firstly, traditional treatment method is neutralizer using lime, lime granularity very little is flown upward very greatly in use,
Site environment is poor.The present invention selects agstone to make neutralizer, although agstone granularity is smaller, belongs to particulate matter powder
Body, powder 0.030~0.075mm of diameter, average diameter 0.05mm fly upward in use process and are greatly lowered, site environment
Be improved significantly.
Secondly, the neutralized reaction product that traditional treatment method obtains, is the calcium sulfate slag and unreacted lime white of fine particle
Mixture, granularity is small, and aqueous up to 40% or more, adhesive force is stronger, pollutes and corrode on-site producing devices and working environment.And
That the present invention obtains is the CaSO of bulky grain4·2H2O filtering is in kind, i.e. qualified industrial gypsum product, has good permeable
Performance not only has faster separation of solid and liquid speed, but also adhesive ability is low, small to production equipment, operating environment corrosion.
Finally, the neutralized reaction product that traditional treatment method obtains, is the calcium sulfate slag and unreacted lime white of fine particle
Mixture, aqueous up to 40% or more, gypsum product standard moisture is wanted no more than 12% with cement industry or building material industry
It asks and differs greatly.Simultaneously as traditional treatment method, does not have strict control solution, lime surplus is more, causes neutralized reaction product
SO3Cement industry or building material industry is not achieved to gypsum product standard SO in content3Content is greater than 40% requirement, therefore at tradition
The neutralized reaction product that reason method obtains cannot meet cement industry or building material industry to gypsum product standard requirements, answer without market
With channel, resource utilization cannot achieve, stacking can only be taken to dispose, not only need to stack place, but also consumption management cost, and
There is also stack and manage brought environment hidden danger.And the CaSO that the present invention obtains4·2H2O filtering material object is the stone of bulky grain
Cream product meets gypsum product standard requirements, direct marketing to cement industry or building material industry, realizes Sewage from Sulphuric Acid Plants recycling
It utilizes.
Based on the above technical solution, the present invention can also be improved as follows.
Further, in step 1, in the Sewage from Sulphuric Acid Plants, H2SO4Concentration is 10g/L~300g/L；The agstone
Powder diameter is 0.030mm~0.075mm, average diameter 0.05mm；CaCO in the agstone3Content is 90%,
Moisture content < 12%, SO3Content > 40%.
It is using above-mentioned further beneficial effect: using above-mentioned parameter, it can be ensured that obtained CaSO4·2H2O, filtering
SO in kind3Content is greater than 40%, meets gypsum product standard requirements.
Further, in step 2, before the separation of solid and liquid, classification processing is also carried out using hydrocyclone.
It is using above-mentioned further beneficial effect: under the action of hydrocyclone, the lesser CaSO of particle4·2H2O
Crystal is flowed out from the overflow pipe of hydrocyclone, is again returned to neutralization reaction equipment and is continued to grow up, and the biggish CaSO of particle4·
2H2O crystal is flowed out from the underflow pipe of hydrocyclone, enters back into filter plant.In this way, further ensuring that filter plant obtains
Solid CaSO4·2H2O product has bigger granularity, CaSO4·2H2O filtering mechanical entrapment adhesive water in kind is lower, it is ensured that
Adhesive water index meets the requirement of industrial gypsum product standard, the industrial gypsum product of output qualification.
Further, in step 2, the equipment used that is separated by solid-liquid separation is filter press or belt vacuum filter.
Further, in step 2, the valuable metal is one of iron, aluminium, zinc, copper or a variety of.
Be using above-mentioned further beneficial effect: valuable metal refers in the raw material of extracting metals, in addition to main metal,
Other metals with recovery value.In the raw materials for metallurgy of nonferrous heavy metal, these valuable metals be mostly noble metal and it is dilute dissipate
Metal.
The beneficial effects of the present invention are:
(1) processing method of Sewage from Sulphuric Acid Plants of the invention, it can be ensured that Sewage from Sulphuric Acid Plants gets utilization.The present invention obtains
The CaSO arrived4·2H2O filters mechanical entrapment attached water rate in kind less than 12%, SO3Content be greater than 40%, meet cement industry and
Building material industry is to gypsum product standard basic demand, this CaSO4·2H2O filtering in kind is industrial gypsum product, Neng Gouxiao
Cement industry or building material industry are sold, the purpose of Sewage from Sulphuric Acid Plants resource utilization is realized.
(2) processing method of Sewage from Sulphuric Acid Plants of the invention, process flow are short.Only there are two steps, so that it may which output is qualified
Industrial gypsum product, the two steps, that is, continuous neutralization reaction process and separation of solid and liquid process.
(3) processing method of Sewage from Sulphuric Acid Plants of the invention, production cost are low.Since process flow is short, investment reduction also drops
Low equipment investment cost and process maintenance maintenance cost also save cost of labor, while using cheap lime stone
Powder makees neutralizer, reduces cost.
(4) processing method of Sewage from Sulphuric Acid Plants of the invention, process cleans environmental protection.The present invention selects agstone to neutralize
Agent, agstone fly upward be greatly lowered in use, site environment be improved significantly；And what the present invention obtained is big
The CaSO of particle4·2H2O filtering is in kind, i.e. qualified industrial gypsum product, has good water permeability, not only has faster
Be separated by solid-liquid separation speed, and adhesive ability is low, small to production equipment, operating environment corrosion, and can direct marketing to cement industry
Or building material industry, realize Sewage from Sulphuric Acid Plants resource utilization.
(5) processing method of Sewage from Sulphuric Acid Plants of the invention is simple, and operation is easy, wide market, is suitble to scale metaplasia
It produces.
Detailed description of the invention
Fig. 1 is the process flow chart of the processing method of Sewage from Sulphuric Acid Plants of the invention.
Specific embodiment
Principles and features of the present invention are described below in conjunction with specific attached drawing, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1
As shown in Figure 1, the processing method of the Sewage from Sulphuric Acid Plants of the present embodiment, includes the following steps:
Step 1: continuous neutralization reaction
During Copper making, the washing, purifying post of flash furnace off-gas acid making system, output H2SO4Concentration is the sulphur of 10g/L
Sour sewage.By above-mentioned Sewage from Sulphuric Acid Plants with 6m3The flow of/h, successively from effective volume 30m3Neutralization reaction slot above be added,
Reaction time of the Sewage from Sulphuric Acid Plants in neutralization reaction slot is 5h.The machine mixer of neutralization reaction slot is started, while therefrom
Agstone is continuously added to the speed of 70kg/h with above reactive tank, the powder diameter of the agstone be 0.030mm~
0.075mm, average diameter 0.05mm；CaCO in the agstone3Content is 90%, moisture content 11%, SO3Content
It is 45%, neutralization reaction is carried out under conditions of reaction temperature is 20 DEG C, pH value is 3.0, the reaction mass residence time is 5h, is obtained
To neutralized reaction product.
Step 2: being separated by solid-liquid separation
At interval of 1h, 6m is extracted from the bottom for neutralizing reactive tank with stainless steel pump3Neutralized reaction product, be put into 120m2Filters pressing
Machine is filtered.At interval of 8h, to filter press solution plate 1 time, solution plate 3 times daily.Daily output CaSO after filters pressing4·2H2O filtering
3080kg in kind, CaSO4·2H2O filtering moisture content in kind is 11.5%, is converted into dry state CaSO4·2H2O filtrate is
2726kg, dry state CaSO4·2H2O filtrate SO3Content is 43.08%.CaSO4·2H2O filtering material object meets cement industry pair
Gypsum product standard requirements are sold to cement plant by gypsum product；Obtained filtered fluid by otherwise processed recycle copper metal after,
It is recycled back to the washing, purifying post of flash furnace off-gas acid making system.
Embodiment 2
As shown in Figure 1, the processing method of the Sewage from Sulphuric Acid Plants of the present embodiment, includes the following steps:
Step 1: continuous neutralization reaction
In zinc metallurgical process, the washing, purifying post of fluidized bed furnace flue gas acid preparing system, output H2SO4Concentration is 100g/L's
Sewage from Sulphuric Acid Plants.By above-mentioned Sewage from Sulphuric Acid Plants with 3m3The flow of/h, successively from effective volume 75m3Neutralization reaction slot above plus
Enter, reaction time of the Sewage from Sulphuric Acid Plants in neutralization reaction slot is 25h.The machine mixer of neutralization reaction slot is started, simultaneously
Using spiral feeding mechanism, with the speed of 0.36t/h, agstone, the stone successively is added above neutralization reactive tank
The powder diameter of limestone flour is 0.030mm~0.075mm, average diameter 0.05mm；CaCO in the agstone3Content
It is 90%, moisture content 10%, SO3Content is 50%, under conditions of reaction temperature is 50 DEG C, pH value is 4.0 carry out in and
Reaction, reaction mass residence time are 50h, obtain neutralized reaction product.
Step 2: being separated by solid-liquid separation
At interval of 2h, 6m is extracted from the bottom for neutralizing reactive tank with stainless steel pump3Neutralized reaction product, be put into 160m2Filters pressing
Machine is filtered.At interval of 2h, to filter press solution plate 1 time, solution plate 12 times daily.Daily output CaSO after filters pressing4·2H2O filtering
15.88t in kind, CaSO4·2H2O filtering moisture content in kind is 11.1%, is converted into dry state CaSO4·2H2O filtrate is
14.12t dry state CaSO4·2H2O filtrate SO3Content is 41.6%.CaSO4·2H2O filtering material object meets cement industry to stone
The requirement of cream product standard, is sold to cement plant by gypsum product；Obtained filtered fluid otherwise processed recycles zinc therein, returns to
The washing, purifying post of fluidized bed furnace flue gas acid preparing system recycles.
Embodiment 3
As shown in Figure 1, the processing method of the Sewage from Sulphuric Acid Plants of the present embodiment, includes the following steps:
Step 1: neutralization reaction
In lead smelting process, bottom blowing aoxidizes the washing, purifying post of kiln gas acid making system, output H2SO4Concentration is 300g/
The Sewage from Sulphuric Acid Plants of L.By above-mentioned Sewage from Sulphuric Acid Plants with 2.0m3The flow of/h, successively from effective volume 200m3Neutralization reaction slot
Top is added.Reaction time of the Sewage from Sulphuric Acid Plants in neutralization reaction slot is 100h.Start 4 side entering types of neutralization reaction slot
Machine mixer, while screw fixed-weight feeder structure is used, with the speed of 0.7t/h, successively add above neutralization reactive tank
Enter agstone, the powder diameter of the agstone is 0.030mm~0.075mm, average diameter 0.05mm；The lime
CaCO in mountain flour3Content is 90%, moisture content 9%, SO3Content is 60%, reaction temperature is 80 DEG C, pH value is 5.0
Under the conditions of carry out neutralization reaction, obtain neutralized reaction product.
Step 2: being separated by solid-liquid separation
At interval of 2h, 8m is extracted from the bottom for neutralizing reactive tank with stainless steel pump3Neutralized reaction product, and be transported to by 10
The cyclone separator of hydrocyclone composition is classified.In classification process, the overflow pipe stream from hydrocyclone is obtained
Overflow slurry 4m out3.Above-mentioned 4m3Overflow slurry lesser CaSO containing particle4·2H2O crystal returns to neutralization reaction slot
Continue to grow up.In addition, flowing out slurries 4m from hydrocyclone bottom liquid pipe3, 150m is flowed to automatically using nature height difference2Band
Formula vacuum filter is filtered.After belt vacuum filter filtering, daily output CaSO4·2H2O filters material object 30.7t,
CaSO4·2H2O filters moisture content 9.6% in kind, is converted into dry state CaSO4·2H2O filtrate is 27.73t, dry state CaSO4·
2H2O filtrate SO3Content is 42.3%.CaSO4·2H2O filtering material object meets building material industry to gypsum product standard requirements, presses
Gypsum product is sold to plasterboard compacting factory；The washing of obtained filtering liquid back to bottom blowing oxidation kiln gas acid making system is net
Change post to recycle.
Comparative example 1
The processing method of the Sewage from Sulphuric Acid Plants of this comparative example 1, includes the following steps:
Step 1: continuous neutralization reaction
During Copper making, the washing, purifying post of flash furnace off-gas acid making system, output H2SO4Concentration is the sulphur of 10g/L
Sour sewage.By above-mentioned Sewage from Sulphuric Acid Plants with 6m3The flow of/h, successively from effective volume 30m3Neutralization reaction slot above be added,
Reaction time of the Sewage from Sulphuric Acid Plants in neutralization reaction slot is 5h.The machine mixer of neutralization reaction slot is started, while therefrom
CaCO is continuously added to the speed of 70kg/h with above reactive tank3Content is 90% graininess lime stone, graininess lime stone
Average diameter is 10mm, carries out neutralization reaction under conditions of reaction temperature is 20 DEG C, pH value is 3.0, obtains neutralized reaction product.
Step 2: being separated by solid-liquid separation
At interval of 1h, 6m is extracted from the bottom for neutralizing reactive tank with stainless steel pump3Neutralized reaction product, be put into 120m2Filters pressing
Machine is filtered.At interval of 8h, to filter press solution plate 1 time, solution plate 3 times daily.Daily output CaSO after filters pressing4·2H2O filtering
3780kg in kind, CaSO4·2H2O filtering moisture content in kind is 31.5%, is converted into dry state CaSO4·2H2O filtrate is
2589kg, dry state CaSO4·2H2O filtrate SO3Content is 28.59%.CaSO4·2H2O filtering SO in kind3Content and moisture
Content does not comply with the requirement of industrial gypsum product standard, and no product selling market can only take stacking to dispose, and pollutes environment.
Comparative example 2
The processing method of the Sewage from Sulphuric Acid Plants of this comparative example 2, includes the following steps:
Step 1: continuous neutralization reaction
During Copper making, the washing, purifying post of flash furnace off-gas acid making system, output H2SO4Concentration is the sulphur of 10g/L
Sour sewage.By above-mentioned Sewage from Sulphuric Acid Plants with 6m3The flow of/h, successively from effective volume 30m3Neutralization reaction slot above be added,
Reaction time of the Sewage from Sulphuric Acid Plants in neutralization reaction slot is 5h.The machine mixer of neutralization reaction slot is started, while therefrom
CaCO is continuously added to the speed of 70kg/h with above reactive tank3Content be 90% agstone, reaction temperature be 10 DEG C,
PH value carries out neutralization reaction under conditions of being 3.0, obtains neutralized reaction product.
Step 2: being separated by solid-liquid separation
At interval of 1h, 6m is extracted from the bottom for neutralizing reactive tank with stainless steel pump3Neutralized reaction product, be put into 120m2Filters pressing
Machine is filtered.At interval of 8h, to filter press solution plate 1 time, solution plate 3 times daily.Daily output CaSO after filters pressing4·2H2O filtering
3488kg in kind, CaSO4·2H2O filtering moisture content in kind is 22.1%, is converted into dry state CaSO4·2H2O filtrate is
2715kg, dry state CaSO4·2H2O filtrate SO3Content is 40.92%.CaSO4·2H2O filters moisture content in kind and does not meet
The requirement of industrial gypsum product standard, no product selling market can only take stacking to dispose, and pollute environment.
Comparative example 3
The processing method of the Sewage from Sulphuric Acid Plants of this comparative example 3, includes the following steps:
Step 1: continuous neutralization reaction
During Copper making, the washing, purifying post of flash furnace off-gas acid making system, output H2SO4Concentration is the sulphur of 10g/L
Sour sewage.By above-mentioned Sewage from Sulphuric Acid Plants with 6m3The flow of/h, successively from effective volume 30m3Neutralization reaction slot above be added,
Reaction time of the Sewage from Sulphuric Acid Plants in neutralization reaction slot is 5h.The machine mixer of neutralization reaction slot is started, while therefrom
CaCO is continuously added to the speed of 75kg/h with above reactive tank3Content be 90% agstone, reaction temperature be 20 DEG C,
PH value carries out neutralization reaction under conditions of being 5.5, obtains neutralized reaction product.
Step 2: being separated by solid-liquid separation
At interval of 1h, 6m is extracted from the bottom for neutralizing reactive tank with stainless steel pump3Neutralized reaction product, be put into 120m2Filters pressing
Machine is filtered.At interval of 8h, to filter press solution plate 1 time, solution plate 3 times daily.Daily output CaSO after filters pressing4·2H2O filtering
3275kg in kind, CaSO4·2H2O filtering moisture content in kind is 12.9%, is converted into dry state CaSO4·2H2O filtrate is
2850kg, dry state CaSO4·2H2O filtrate SO3Content is 38.47%.CaSO4·2H2O filters material object SO3Content and moisture contain
Amount does not comply with the requirement of industrial gypsum product standard, and no product selling market can only take stacking to dispose, and pollutes environment.
Comparative example 4
The processing method of the Sewage from Sulphuric Acid Plants of this comparative example 4, includes the following steps:
Step 1: continuous neutralization reaction
During Copper making, the washing, purifying post of flash furnace off-gas acid making system, output H2SO4Concentration is the sulphur of 10g/L
Sour sewage.By above-mentioned Sewage from Sulphuric Acid Plants with 6m3The flow of/h, successively from effective volume 30m3Neutralization reaction slot above be added,
Reaction time of the Sewage from Sulphuric Acid Plants in neutralization reaction slot is 2h.The machine mixer of neutralization reaction slot is started, while therefrom
CaCO is continuously added to the speed of 70kg/h with above reactive tank3Content be 90% agstone, reaction temperature be 10 DEG C,
PH value carries out neutralization reaction under conditions of being 3.0, obtains neutralized reaction product.
Step 2: being separated by solid-liquid separation
At interval of 1h, 6m is extracted from the bottom for neutralizing reactive tank with stainless steel pump3Neutralized reaction product, be put into 120m2Filters pressing
Machine is filtered.At interval of 8h, to filter press solution plate 1 time, solution plate 3 times daily.Daily output CaSO after filters pressing4·2H2O filtering
5234kg in kind, CaSO4·2H2O filtering moisture content in kind is 47.94%, is converted into dry state CaSO4·2H2O filtrate is
2725kg, dry state CaSO4·2H2O filtrate SO3Content is 43.11%.CaSO4·2H2O filters moisture content in kind and does not meet
The requirement of industrial gypsum product standard, no product selling market can only take stacking to dispose, and pollute environment.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of processing method of Sewage from Sulphuric Acid Plants, which comprises the steps of:
Step 1: continuous neutralization reaction
Sewage from Sulphuric Acid Plants and agstone are continuously put into neutralization reaction equipment, continuous neutralization reaction, control reaction are carried out
Temperature be 20 DEG C~80 DEG C, pH value is 3.0~5.0, the reaction mass residence time be 5h~100h, obtain neutralization reaction slurries
Product；
Step 2: being separated by solid-liquid separation
The neutralization reaction product slurry that step 1 is obtained, is separated by solid-liquid separation, respectively obtains industrial gypsum and filtered fluid, by work
Industry gypsum is for sale, discharges or recycles again after filtered fluid is recycled valuable metal.
2. a kind of processing method of Sewage from Sulphuric Acid Plants according to claim 1, which is characterized in that in step 1, the sulfuric acid is dirty
In water, H2SO4Concentration is 10g/L~300g/L；The powder diameter of the agstone is 0.030mm~0.075mm, average straight
Diameter is 0.05mm；CaCO in the agstone3Content is 90%, moisture content < 12%, SO3Content > 40%.
3. a kind of processing method of Sewage from Sulphuric Acid Plants according to claim 1, which is characterized in that in step 2, in the solid-liquid
Before separation, classification processing is also carried out using hydrocyclone.
4. a kind of processing method of Sewage from Sulphuric Acid Plants according to claim 1, which is characterized in that in step 2, the solid-liquid point
From the equipment used for filter press or belt vacuum filter.
5. a kind of processing method of Sewage from Sulphuric Acid Plants according to claim 1, which is characterized in that, it is described valuable in step 2
Metal is one of iron, aluminium, zinc, copper or a variety of.
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