CN208617383U - A kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling - Google Patents
A kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling Download PDFInfo
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Abstract
The utility model discloses a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling, belong to hydrochloric acid pickling waste liquor process field.A kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model, the device of its sulfonation method steel part hydrochloric acid pickling waste liquor recycling treatment is circulating treatment procedure, successively the hydrochloric acid and ferrous sulfate heptahydrate of high-purity are obtained by multiple-effect evaporation crystallization, the removal of impurities of frerrous chloride crude product, sulfonating reaction extracting sulfuric acid ferrous iron, ferrous sulfate recrystallization and absorbing hydrogen chloride gas relieving haperacidity process, obtained ferrous sulfate heptahydrate can be used as chemical products or water treatment agent is sold, and the hydrochloric acid of recycling all can directly return to workshop use.Economic benefit and environmental benefit are obvious, have the advantages that simple, easy to implement, the easy to maintain management of process, input cost are low etc..
Description
Technical field
The utility model relates to a kind of hydrochloric acid pickling waste liquor recycling and processing devices, more specifically to a kind of sulfonation method
Steel part hydrochloric acid pickling waste liquor processing equipment for recycling.
Background technique
In steel and iron industry and electroplating industry, except stainless steel is carried out clearly using mixed acid such as nitric acid, hydrofluoric acid and sulfuric acid
Outside washing, metal plating piece and ordinary steel mainly use hydrochloric acid substituted sulfuric acid ablution at present, and Cleaning principle is as follows: Fe2O3+Fe+
6HCl→ 3FeCl2+3H2O；This is because hydrochloric acid will be greater than the corrosion rate of iron from far away at identical temperature and concentration
Sulfuric acid, and the rust cleaning efficiency of hydrochloric acid is high, iron loss is low, steam consumption is few, waste liquid amount is few, in configuration and than sulfuric acid economy, safety.
Whether steel and iron industry or the hydrochloric acid pickling waste liquor of electroplating industry discharge all have iron concentration high, sour dense
The features such as degree is high, corrosivity is high, environmental pollution is high, is managed by various countries as hazardous waste at present.The U.S. by its
It is included in " protection of resources and regeneration bill ", it is also included in " National Hazard waste register " by China.Hydrochloric acid pickling waste liquor is illegal outer
Main harm caused by arranging shows themselves in that the corrosion water conservancy project structures such as sewer pipe and armored concrete；Keep crops withered, influences water
Raw plant growth；Hydrochloric acid pickling waste liquor penetrates into soil, and the time, which has been grown, will cause soil property calcification, destroys soil layer loose condition (of surface), thus
Crop growth is influenced, fish can be poisoned with poison；People and animals drink the water polluted by this, and stomach inflammation can be caused even to burn；It is to water
Pollution, the murder by poisoning to biology caused by body, so it is all finally very huge to the injury of human health.According to national environmental protection
Regulations of rules, hydrochloric acid pickling waste liquor do not allow direct emission.And the quantum of output of the such hydrochloric acid pickling waste liquor in China is surprising, row is existing steathily
As remaining incessant after repeated prohibition.
Both at home and abroad to there are many processing methods of hydrochloric acid pickling waste liquor, the specific spy according to different hydrochloric acid pickling waste liquors is needed
Point selects suitable Treatment process in conjunction with the case where She Suan enterprise itself.Currently used hydrochloric acid pickling waste liquor Treatment process
Have: neutralization precipitation method, one-step calcinations, evaporation, ion-exchange-resin process, membrane separation process, extraction, chemical transformation etc.
Deng.
1), neutralization precipitation method: acid-base neutralization processing hydrochloric acid pickling waste liquor is early stage China's steel and electroplating industry processing salt
The sour most common method of pickle liquor, it is 6~9 that hydrochloric acid pickling waste liquor is exactly neutralized to pH using alkali by basic principle, and
By a large amount of Fe in hydrochloric acid pickling waste liquor2+Precipitating is discharged by way of sludge.Typical neutralization reagent includes using carbonic acid
Sodium, sodium hydroxide, lime stone or lime, wherein most common is to use lime.Hydrochloric acid pickling waste liquor is handled using neutralization precipitation method
Although pH value can achieve requirement afterwards, remaining indices is difficult up to standard, and the body refuse dehydration generated is difficult, is not easy
Drying, post-processing difficulty are big, and most of situation is that accumulation is to be processed, occupy a large amount of soils, cause secondary pollution, while the party
Method can also waste a large amount of hydrochloric acid and iron resource.As country to the strict control of molysite sludge and is incorporated to dangerous solid waste, this
Processing method is certain to be eliminated in the future.
2), one-step calcinations: one-step calcinations are the high-temp combustions using roaster, by the chlorination in hydrochloric acid pickling waste liquor
Hydrogen becomes gaseous state, and makes ferrous salt oxydrolysis at high temperature, is converted into iron oxide and hydrochloric acid.It is a kind of most thorough hydrochloric acid acid
Wash method for treating waste liquid.The main equipment of one-step calcinations is by groups such as roaster, cyclone dust collectors, preconcentrator and absorption towers
At.During processing, the evaporation of hydrochloric acid pickling waste liquor, the dehydration of free acid, the oxidation of ferrous ion and hydrolysis, iron oxide and
The collection and absorption of hydrochloric acid are organically incorporated in a system and are completed together, and therefore, one-step calcinations have processing equipment
Advantage compact, processing capacity is big, and the regeneration rate of recovery of the method hydrochloric acid is high, and the hydrochloric acid being recovered can directly return to use,
And the iron oxide recycled can both make high-grade raw materials for metallurgy, can also make the raw materials for production of magnetic material or pigment.The only party
Method investment is big, processing cost is high, and general middle-size and small-size She Suan enterprise can not be borne by.
3), evaporation: the working principle of evaporative crystallization method is the characteristic for being easy to volatilize according to hydrochloric acid, makes its steaming by heating
Hair generates the mixed gas of hydrogen chloride and vapor, and is condensed into recycling hydrochloric acid, and byproduct can be obtained after concentrate crystallisation by cooling
Four water frerrous chlorides.The main problem of the technology be equipment corrosion and hydrochloric acid pickling waste liquor concentration to a certain extent after
Crystallization Plugging.It is external to reduce material boiling point and reduction hydrogen chloride gas frequently with negative pressure evaporation concentration technology technology in engineer application
It lets out, to extend service life of equipment and improve operating environment.
4), ion-exchange-resin process: hydrochloric acid can be absorbed from hydrochloric acid pickling waste liquor using certain ion exchange resin and arranged
Hydrochlorate separation is realized except the function of metal salt.Hydrochloric acid pickling waste liquor enters cleaning containing ferrous hydrochloric acid after filter plant filters
Tank, cleaning flow through resin bed from bottom by pipeline containing ferrous hydrochloric acid, and resin absorbs HCl, contains iron ion and other ions
Liquid be discharged, into metal salt recovery system.To realize that hydrochlorate separates.
5), membrane separation process: separation recycling can be carried out to hydrochloric acid pickling waste liquor by membrane separation technique, that is, utilize film
Ion selectivity separates molysite and hydrochloric acid, while recycling hydrochloric acid and molysite.Common membrane separating method have diffusive dialysis method,
Electroosmose process, membrane distillation method etc., the membrane separation process applied to hydrochloric acid pickling waste liquor processing is mainly diffusive dialysis method.Diffusion dialysis
Method is to realize to separate the hydrochlorate of hydrochloric acid pickling waste liquor through effect using the selection of anion-exchange membrane.The throwing of diffusive dialysis method
Enter 1/5 or so of only roasting method, and due to dialysis process not power consumption, operating cost is low, combines with membrane distillation, also can get
The lower regenerated acid of impurity content.But the most important problem of diffusive dialysis method has: treating capacity is little, leads to diffusive dialysis method
Equipment is huge；The concentration of recycling hydrochloric acid is limited by equilibrium concentration, i.e., the concentration of recycling hydrochloric acid is not above raw material chlorohydric acid pickling
Hydrogen cloride concentration in waste liquid；Raffinate after recycling hydrochloric acid is still unable to direct emission, needs to handle in next step.
6), extraction: extraction is to utilize compound solubility or distribution in the solvent of two kinds immiscible (or slightly soluble)
The difference of coefficient is transferred to compound in another solvent from a kind of solvent.Extraction is used in hydrochloric acid pickling waste liquor
Agent, it can dissolve hydrogen chloride but cannot dissolve frerrous chloride, to make the hydrogen chloride and frerrous chloride point in hydrochloric acid pickling waste liquor
From, then with water the hydrogen chloride being dissolved in extractant is stripped, obtain hydrochloric acid.The rate of recovery of this method acid compared with
Height is the 80%~90% of handled hydrochloric acid pickling waste liquor, is only second to spray roasting.Although extraction have it is easy to operate,
The features such as recovery efficiency is high, but because new organic phase, the loss of extractant and secondary pollution mesh can be introduced in its extraction process
Preceding good processing method not yet.
7) it, chemical transformation: prepares iron oxide: having been compared with the technology of hydrochloric acid pickling waste liquor production iron oxide pigment
Maturation, and be worldwide used widely.The process flow of iron oxide is prepared by taking hydrochloric acid pickling waste liquor as an example are as follows: hydrochloric acid
Pickle liquor adjustment → crystal seed preparation → crystal is grown up → separates → product (iron oxide).Hydrochloric acid pickling waste liquor adjustment is by adding
Enter appropriate scrap iron to react with free acid, generates more ferrous salts.Crystal seed preparation i.e. prepares iron oxide embryos, need to be passed through air or
Person's oxygen, and reaction temperature is controlled, make ferrous oxidising to be ferric iron, produces crystal seed.Crystal growth process need to be thrown in proportion
Enter hydrochloric acid pickling waste liquor and be passed through oxygen, ferrous iron is made constantly to be oxidized to Fe2O3, and be deposited on crystal seed, finally aoxidized
Iron.Finally by the separation that iron oxide and solution can be achieved is filtered, iron oxide is again through washing, finished product obtained by drying.In the technique
In operating process, the control of the conditions such as hydrochloric acid pickling waste liquor purity, reaction temperature, mixing speed, oxidization time is extremely important, directly
The quality for influencing iron oxide product is connect, this is exactly the deficiency of the technique, i.e. high operation requirements, and process conditions are not easy to control.
Above-mentioned hydrochloric acid pickling waste liquor processing method differs from one another, but generally existing processing cost is high, HCl recovery concentration
Low, recycling by-product sales difficulty, the less economical and three wastes generate the problems such as high.Generally acknowledge more advanced roasting method chlorine in the country
The effective rate of recovery for changing hydrogen also can only achieve 70%, and remaining 30% certainly will enter peripheral environment, cause acid rain and atmosphere pollution.
Summary of the invention
1. utility model technical problems to be solved
The purpose of the utility model is to overcome existing hydrochloric acid pickling waste liquor processing method above shortcomings, provide one
Kind sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling is efficiently solved using the technical solution of the utility model
Processing cost present in existing hydrochloric acid pickling waste liquor treatment process technology and engineering actual motion is high, recycling concentration of hydrochloric acid is low,
It recycles by-product sales difficulty and the three wastes generates the problems such as high, there is strong operability, easy to operate, economic effect and Environmental Effect
The advantages that beneficial obvious, investment and processing cost are lower.
2. technical solution
In order to achieve the above objectives, technical solution provided by the utility model are as follows:
A kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model, including evaporative crystallization system
System, impurity removed system, ferrous sulfate sulfonation synthesis system, ferrous sulfate recrystallization system and absorption acid making system, in which:
In evaporation and crystallization system, including preheater, evaporator, separator, concentration liquid distributor, frerrous chloride crystallization
Kettle, frerrous chloride centrifuge and condenser, the described preheater connection by evaporator and separator group at multiple-effect evaporation unit,
For being evaporated concentration to the hydrochloric acid pickling waste liquor from stoste pool, the concentrated solution outlet of the multiple-effect evaporation unit passes through
Liquid distributor is concentrated and connects frerrous chloride crystallization kettle, for crystallizing the frerrous chloride concentrate after concentration for frerrous chloride crystalline substance
Body, frerrous chloride crystallization kettle are connected with frerrous chloride centrifuge, for four water frerrous chloride crude products to be obtained by filtration, and pass through dress
Expect that mechanism is sent into impurity removed system system, the filtrate (liquid of the frerrous chloride centrifuge is connected in multiple-effect evaporation unit,
For making filtrate participate in being concentrated by evaporation again；The steam (vapor) outlet of multiple-effect evaporation unit is connect with condenser, for what will be evaporated
Hydrogen chloride gas and vapor condense to form dilute hydrochloric acid, and condenser is connected with diluted acid tank, for being sent into after collecting dilute hydrochloric acid
It absorbs in acid making system；
In impurity removed system, including pH adjusts reaction kettle, removal of impurities reaction kettle, tail gas absorber, frerrous chloride removal of impurities crystallization
Kettle and frerrous chloride removal of impurities centrifuge, the feed inlet that the pH adjusts reaction kettle are connected with alkali liquid tank, for adjusting to pH
Lye is added in reaction kettle to adjust the pH value of the four water frerrous chloride crude products generated from evaporation and crystallization system, the pH tune
The discharge port for saving reaction kettle is connected with the feed inlet of removal of impurities reaction kettle, for reacting removal with sulfide in removal of impurities reaction kettle
Heavy metal ion, the discharge port of the removal of impurities reaction kettle is by pump connection frerrous chloride removal of impurities crystallization kettle, after to removal of impurities
Solution of ferrous chloride crystallized, frerrous chloride removal of impurities crystallization kettle and the frerrous chloride centrifuge that cleans are connected, for filtering
Four water frerrous chloride crystal are obtained, and are sent into ferrous sulfate sulfonation synthesis system by charge mechanism, the frerrous chloride
The filtrate (liquid of removal of impurities centrifuge is connected to removal of impurities reaction kettle；The offgas outlet and removal of impurities tail gas absorption of the removal of impurities reaction kettle
Tower connection, removal of impurities tail gas absorber are connect with alkali liquid tank, are absorbed using the hydrogen sulfide tail gas that lye generates removal of impurities reaction；
In ferrous sulfate sulfonation synthesis system, including synthesis reactor, concentrated sulfuric acid head tank, mother liquor head tank, ferrous sulfate
Crystallization kettle and ferrous sulfate centrifuge, the concentrated sulfuric acid head tank are connected with synthesis reactor, for passing through concentrated sulfuric acid head tank
It is come from into synthesis reactor in four water frerrous chloride crystal made from impurity removed system and concentrated acid sulfonation reaction generation ferrous sulfate is added
And hydrogen chloride, the gas vent of synthesis reactor are connected to absorption acid making system, for high concentration to be made in the hydrogen chloride absorption of generation
Hydrochloric acid；The liquid outlet of synthesis reactor is connected with ferrous sulfate crystallization kettle, cooling for that will react the ferrous sulfate solution generated
Crystallization, ferrous sulfate crystallization kettle are connected with ferrous sulfate centrifuge, are separated by solid-liquid separation for the errous sulfate crystal after crystallizing
Ferrous sulfate heptahydrate crude product is formed, the filtrate (liquid of ferrous sulfate centrifuge is returned to by mother liquor head tank into synthesis reactor
Dilution as the concentrated sulfuric acid；
In ferrous sulfate recrystallization system, including ferrous sulfate hot melt kettle, ferrous sulfate recrystallization kettle and ferrous sulfate
Centrifuge, ferrous sulfate heptahydrate crude product obtained is passed through in ferrous sulfate hot melt kettle in ferrous sulfate sulfonation synthesis system, sulfuric acid
Ferrous hot melt kettle is connected with ferrous sulfate recrystallization kettle, for adding ferrous sulfate heptahydrate crude product in ferrous sulfate hot melt kettle
Enter pure water heating for dissolving, and dissolved ferrous sulfate solution is recrystallized to form seven water sulfuric acid by ferrous sulfate recrystallization kettle
Ferrous crystal, ferrous sulfate recrystallization kettle are connected with ferrous sulfate centrifuge, and separation of solid and liquid forms ferrous sulfate heptahydrate finished product；
In absorbing acid making system, including falling-film absorber, absorption flow container and tail gas absorber, ferrous sulfate sulfonation synthesis
The gas vent of synthesis reactor in system connects falling-film absorber, the chlorine for will generate from ferrous sulfate sulfonation synthesis system
Change hydrogen to absorb to form hydrochloric acid by falling-film absorber, the liquid outlet of falling-film absorber connects into product acid by absorbing flow container
Storage tank, the hydrochloric acid for hydrogen cloride concentration to be reached setting value squeeze into finished product acid storage tank；The offgas outlet of falling-film absorber connects
To tail gas absorber, tail gas absorber is using the dilute hydrochloric acid of the generation in evaporation and crystallization system as tail gas absorption liquid.
Further, in evaporation and crystallization system, the multiple-effect evaporation unit imitates Steaming structures, and multiple-effect using two
Evaporation element connects vacuum pump and forms negative pressure evaporation；The frerrous chloride crystallization kettle and frerrous chloride centrifuge is also separately connected
Vacuum pump set carries out the crystallization of frerrous chloride under subnormal ambient.
Further, in evaporation and crystallization system, the concentration liquid distributor is separately connected four groups of frerrous chloride knots
Brilliant kettle, and every two groups of frerrous chloride crystallization kettles share one group of frerrous chloride centrifuge.
Further, in impurity removed system, the gas vent of the tail gas absorber is connected with vacuum pump group, institute
The frerrous chloride removal of impurities crystallization kettle and frerrous chloride removal of impurities centrifuge stated also are separately connected vacuum pump set, carry out under subnormal ambient
The removal of impurities and crystallization of frerrous chloride.
Further, in ferrous sulfate sulfonation synthesis system, the synthesis reactor uses three stage structure, synthesis reactor
Bottom use enamel structure, the middle part of synthesis reactor and kettle cover are all made of steel lining graphite-structure.
Further, in absorbing acid making system, finished product hydrochloric acid is prepared using three-level falling-film absorber absorption, it is described
Falling-film absorber is all made of graphite falling film absorber.
3. beneficial effect
Using technical solution provided by the utility model, compared with existing well-known technique, there is following remarkable result:
(1) a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model, process route
Correctly, there is very strong operability, be preferably a kind of mode of steel part hydrochloric acid pickling waste liquor recycling treatment；Economic benefit
Obviously, the rate of recovery of hydrogen chloride is up to 98%, and concentration can require freely adjust according to pickling, and the ferrous sulfate of recycling can be with
It is sold as chemical products or water treatment agent；Environmental benefit is fairly obvious, since hydrogen chloride recycles substantially, and uses complete negative
Secondary environmental pollution source is not present in pressure system；
(2) a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model, it is easy to operate,
One worker of full-automatic control system per tour is convenient to operation；Investment and processing cost are lower, and investment is only the 1/2 of roasting method
Left and right, freight charges expense are 1/3 or so of roasting method；
(3) a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model, sulfonation method steel
The technique of product hydrochloric acid pickling waste liquor recycling treatment be circulating treatment procedure, three-waste free discharge, treatment process environmental protection, without dirt
Dye, low energy consumption, treatment process safety；Gained recycles product hydrochloric acid and ferrous sulfate heptahydrate purity is high, and seven obtained water sulfuric acid are sub-
Iron can be used as chemical products or water treatment agent is sold, and the hydrochloric acid of recycling all can directly return to workshop use；Tool
There are preferable economic benefit and environmental benefit；Management simple with process, easy to implement, easy to maintain, input cost are low
The advantages that.
Detailed description of the invention
Fig. 1 is a kind of process flow of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model
Schematic diagram；
Fig. 2 is the protochloride in a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model
The process flow chart of iron crude product evaporation and crystallization system；In figure: V101, original fluid container；V102, diluted acid tank；V103, knockout drum；
V104, mother liquor tank；V105, recycling flow container；V106, concentration liquid distributor；E101,1st effective evaporator；E102,2nd effect evaporator；
E103, condenser；E104, on-condensible gas condenser；E105, diluted acid cooler；E106, level-one preheater；E107, second level are pre-
Hot device；E108, three-level preheater；E109, mother liquor preheater；E110, recycling cooler；S101, an effect separator；S102, two
Imitate separator；P101, two effect circulating pumps；P102, discharging pump；P103, feed pump；P104, thin acid pump；P105, vapo(u)rization system are true
Sky pump；P106, mother liquor pump；P107, crystal system vacuum pump set one；R101, frerrous chloride crystallization kettle one；R102, frerrous chloride
Crystallization kettle two；R103, frerrous chloride crystallization kettle three；R104, frerrous chloride crystallization kettle four；M101, frerrous chloride centrifuge one；
M102, frerrous chloride centrifuge two；L101, electric block one；
Fig. 3 is the protochloride in a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model
The process flow chart of iron removing impurity by means of precipitation system；In figure: V201, alkali liquid tank one；V202, alkali liquid tank two；V203, original fluid container；V204,
Frerrous chloride mother liquor tank；V205, recycling flow container；E201, recycling cooler；P201, lye pump one；P202, punishment in advance pump； P203,
Discharging pump；P204, absorbing liquid pump；P205, lye pump two；P206, feed pump；P207, mother liquor pump；P208, crystal system vacuum
Unit two；R201, pH adjust reaction kettle；R202, removal of impurities reaction kettle；R203, frerrous chloride crystallization kettle one；R204, frerrous chloride
Crystallization kettle two；M201, frerrous chloride centrifuge；T201, tail gas absorber；L201, electric block two；
Fig. 4 is the protochloride in a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model
The iron process flow chart for taking ferrous sulfate system；In figure: V301, mother liquor tank；V302, crystal system knockout drum；V303,
Concentrated sulfuric acid head tank one；V304, mother liquor head tank one；V305, concentrated sulfuric acid head tank two；V306, mother liquor head tank two； V307,
Concentrated sulfuric acid head tank three；V308, mother liquor head tank three；V309, distributor；V310, concentrated sulfuric acid storage tank；P301, concentrated sulfuric acid pump；
P302, mother liquor pump；P303, crystal system vacuum pump set three；R301, synthesis reactor one；R302, synthesis reactor two；R303, synthesis reactor
Three；R304, ferrous sulfate crystallization kettle one；R305, ferrous sulfate crystallization kettle two；R306, ferrous sulfate crystallization kettle three；M301, sulphur
Sour ferrous iron centrifuge；L301, electric block three；
Fig. 5 is that the sulfuric acid in a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model is sub-
The process flow chart of iron recrystallization system；In figure: R401, ferrous sulfate hot melt kettle；R402, ferrous sulfate recrystallize kettle；M401,
Ferrous sulfate centrifuge；L401, electric block four；
Fig. 6 is the hydrogen chloride in a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model
The process flow chart of gas absorption acid making system；In figure: V501, first order absorption flow container；V502, second level absorb flow container；V503, three
Grade absorbs flow container；V504, absorption system knockout drum；E501, stage falling-film absorber；E502, second level falling-film absorber；
E503, three-level falling-film absorber；P501, first order absorption liquid pump；P502, second level absorbing liquid pump；P503, three-level absorbing liquid pump；
P504, absorption tower absorbing liquid pump；P505, absorption system vacuum pump set；T501, tail gas absorber.
Specific embodiment
For the content for further appreciating that the utility model, the utility model is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment
As shown in connection with fig. 1, a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the present embodiment, place
Science and engineering skill comprises the steps of:
(1) volatilization and characteristic soluble easily in water and frerrous chloride evaporative crystallization: are easy in water (hydrochloric acid) according to hydrogen chloride
The rule of solubility, using steam indirect heating, negative pressure evaporation concentration technology, by steel part hydrochloric acid pickling waste liquor after preheating
It is pumped into multi-effect evaporation system, forms dilute hydrochloric acid after the saliferous acid vapor condensation that multiple-effect evaporation generates, it is highly concentrated as recycling
Spend the acid making system absorbing liquid of hydrochloric acid；It is thick that four water frerrous chlorides are formed after crystallization by the concentrate that multiple-effect evaporation generates
Product, the frerrous chloride mother liquor for being separated by solid-liquid separation generation returns to be concentrated by evaporation again in multi-effect evaporation system.
(2) frerrous chloride crude product cleans: because general steel part hydrochloric acid pickling waste liquor has other heavy metal ion, therefore
Removal of heavy metal ions step is increased in implementation process, specifically, in the four water frerrous chloride crude products that step (1) obtains
It sequentially adds lye adjusting pH value and sulfide heavy-metal ion removal, the hydrogen sulfide tail gas for reacting generation is absorbed through lye, removed
Four water frerrous chloride crystal, the frerrous chloride of solid-liquid separation are obtained after the crystallized separation of solution of ferrous chloride that miscellaneous reaction generates
Mother liquor participates in the removal of impurities reaction of frerrous chloride crude product again；Specifically in this step, hydrogen is added in first Xiang Sishui frerrous chloride crude product
It is about 3 that sodium oxide molybdena, which adjusts pH value, and sulfide heavy-metal ion removal is then added, and the hydrogen sulfide tail gas that removal of impurities reaction generates uses
The lye that concentration is 8% carries out neutralization absorption.
(3) sulfonating reaction extracting sulfuric acid is ferrous: obtaining that concentrated sulfuric acid progress sulfonation is added in frerrous chloride crystal in step (2)
Reaction, chemical equation are as follows: FeCl2+H2SO4→FeSO4+ 2HCl ↑,
The hydrogen chloride gas generated in reaction process, which enters in absorbing hydrogen chloride gas acid making system, produces hydrochloric acid；Reaction produces
The crystallized formation ferrous sulfate heptahydrate crude product of raw ferrous sulfate, the mother liquor of solid-liquid separation participate in sulfonating reaction again；
Because being the chemical reaction of inorganic salts, the ingredient proportion of the concentrated sulfuric acid can be calculated by full response；In order to guarantee ferrous sulfate
Product quality, it is preferable that according to the ingredient proportion of weight be 1.05:1~1.15:1, and sulphur between the concentrated sulfuric acid and frerrous chloride
Reaction temperature control is combined in 110 DEG C~115 DEG C, vacuum degree control in -0.03MPa~-0.05MPa.Above-mentioned sulfuric acid is sub-
Iron crystallization is carried out according to ferrous sulfate solubility in water or referring to solubility of the ferrous sulfate in sulfuric acid, is crystallized
Journey is completed in crystallization kettle, and brine ice is passed through in crystallization kettle collet, and circulating cooling carries out solid-phase crystallization precipitation；It is separated by solid-liquid separation
Process is mentioned from the concentration magma of liquid for being separated by solid-liquid separation the ferrous sulfate magma of solid-liquid admixture
The ferrous sulfate crystallization body for taking, isolating solid phase, the ferrous sulfate crude product isolated enter recrystallization system, the sulphur separated
Dilute solution of the sour ferrous iron mother liquor as sulfate substitution synthesis reactor, or crystallized again into crystallization kettle.The step is produced
Ferrous sulfate heptahydrate be only crude product, reach the ferrous sulfate heptahydrate of feed grade or food-grade if necessary, need to carry out weight
Crystallization and cleaning.
(4) ferrous sulfate recrystallizes: ferrous sulfate crude product obtained in step (3), because crystallization is in higher concentration
It is completed in sulfuric acid, wherein the crystallization water contained is uneven and surface water is the sulfuric acid of higher concentration, packaging and storing can not be carried out
And the sale in later period, it is therefore necessary to which hot melt recrystallization is carried out to first subcrystalline ferrous sulfate crude product.Specifically, according to object
The different solubility of matter, the impurity in soluble crystal substance includes the impurity and impurity soluble easily in water for being insoluble in water, generally
First with the method for dissolution, filtering, the impurity for being insoluble in water contained in soluble crystal substance is removed, then uses recrystallization method again
Make the impurity separation soluble easily in water in soluble crystal substance.Concrete operations are, seven water sulfuric acid obtained in step (3) are sub-
Ferrous sulfate heptahydrate finished product is recrystallized to give after iron crude product hot melt.
(5) absorbing hydrogen chloride gas relieving haperacidity: according to the solubility of hydrogen chloride in water, the chlorination that will be generated in step (3)
Hydrogen absorbs to obtain concentrated hydrochloric acid by multi-stage negative pressure, more to ensure the absorptivity of hydrogen chloride gas and the concentration of hydrochloric acid
The dilute hydrochloric acid that grade negative pressure absorbing is generated using multiple-effect evaporation in step (1) ensure that the purity of hydrochloric acid, also reduce as absorbing liquid
Production cost.The step uses full negative pressure absorbing technology, both ensure that the hydrogen chloride content of finished acid, and had also ensured hydrogen chloride
Gas substantially without leaking, ensure that the cleaning in workshop and plant area's production environment, realize clean manufacturing to the full extent.
In conjunction with shown in Fig. 2 to Fig. 6, a kind of sulfonation method steel part hydrochloric acid pickling waste liquor recycling treatment of the present embodiment is filled
It sets, including evaporation and crystallization system, impurity removed system, ferrous sulfate sulfonation synthesis system, ferrous sulfate recrystallization system and absorption system
Acid system, in which:
In evaporation and crystallization system, including preheater, evaporator, separator, concentration liquid distributor, frerrous chloride crystallization
Kettle, frerrous chloride centrifuge and condenser, the described preheater connection by evaporator and separator group at multiple-effect evaporation unit,
For being evaporated concentration to the hydrochloric acid pickling waste liquor from stoste pool, the concentrated solution outlet of the multiple-effect evaporation unit passes through
Liquid distributor is concentrated and connects frerrous chloride crystallization kettle, for crystallizing the frerrous chloride concentrate after concentration for frerrous chloride crystalline substance
Body, frerrous chloride crystallization kettle are connected with frerrous chloride centrifuge, for four water frerrous chloride crude products to be obtained by filtration, and pass through dress
Expect that mechanism is sent into impurity removed system system, the filtrate (liquid of the frerrous chloride centrifuge is connected in multiple-effect evaporation unit,
For making filtrate participate in being concentrated by evaporation again；The steam (vapor) outlet of multiple-effect evaporation unit is connect with condenser, for what will be evaporated
Hydrogen chloride gas and vapor condense to form dilute hydrochloric acid, and condenser is connected with diluted acid tank, for being sent into after collecting dilute hydrochloric acid
It absorbs in acid making system.Preferably, above-mentioned multiple-effect evaporation unit is using two effect Steaming structures, and the connection of multiple-effect evaporation unit is true
Sky pump forms negative pressure evaporation；Frerrous chloride crystallization kettle and frerrous chloride centrifuge are also separately connected vacuum pump set, in subnormal ambient
The lower crystallization for carrying out frerrous chloride.Above-mentioned concentration liquid distributor is separately connected four groups of frerrous chloride crystallization kettles, and every two groups of chlorine
Change ferrous crystallization kettle and shares one group of frerrous chloride centrifuge.
In impurity removed system, including pH adjusts reaction kettle, removal of impurities reaction kettle, tail gas absorber, frerrous chloride removal of impurities crystallization
Kettle and frerrous chloride removal of impurities centrifuge, the feed inlet that the pH adjusts reaction kettle are connected with alkali liquid tank, for adjusting to pH
Lye is added in reaction kettle to adjust the pH value of the four water frerrous chloride crude products generated from evaporation and crystallization system, the pH tune
The discharge port for saving reaction kettle is connected with the feed inlet of removal of impurities reaction kettle, for reacting removal with sulfide in removal of impurities reaction kettle
Heavy metal ion, the discharge port of the removal of impurities reaction kettle is by pump connection frerrous chloride removal of impurities crystallization kettle, after to removal of impurities
Solution of ferrous chloride crystallized, frerrous chloride removal of impurities crystallization kettle and the frerrous chloride centrifuge that cleans are connected, for filtering
Four water frerrous chloride crystal are obtained, and are sent into ferrous sulfate sulfonation synthesis system by charge mechanism, the frerrous chloride
The filtrate (liquid of removal of impurities centrifuge is connected to removal of impurities reaction kettle；The offgas outlet and removal of impurities tail gas absorption of the removal of impurities reaction kettle
Tower connection, removal of impurities tail gas absorber are connect with alkali liquid tank, are absorbed using the hydrogen sulfide tail gas that lye generates removal of impurities reaction.
Preferably, the gas vent of above-mentioned tail gas absorber is connected with vacuum pump group, frerrous chloride removal of impurities crystallization kettle and protochloride
Iron removal of impurities centrifuge is also separately connected vacuum pump set, and the removal of impurities and crystallization of frerrous chloride are carried out under subnormal ambient.
In ferrous sulfate sulfonation synthesis system, including synthesis reactor, concentrated sulfuric acid head tank, mother liquor head tank, ferrous sulfate
Crystallization kettle and ferrous sulfate centrifuge, the concentrated sulfuric acid head tank are connected with synthesis reactor, for passing through concentrated sulfuric acid head tank
It is come from into synthesis reactor in four water frerrous chloride crystal made from impurity removed system and concentrated acid sulfonation reaction generation ferrous sulfate is added
And hydrogen chloride, the gas vent of synthesis reactor are connected to absorption acid making system, for high concentration to be made in the hydrogen chloride absorption of generation
Hydrochloric acid；The liquid outlet of synthesis reactor is connected with ferrous sulfate crystallization kettle, cooling for that will react the ferrous sulfate solution generated
Crystallization, ferrous sulfate crystallization kettle are connected with ferrous sulfate centrifuge, are separated by solid-liquid separation for the errous sulfate crystal after crystallizing
Ferrous sulfate heptahydrate crude product is formed, the filtrate (liquid of ferrous sulfate centrifuge is returned to by mother liquor head tank into synthesis reactor
Dilution as the concentrated sulfuric acid.Preferably, synthesis reactor uses three stage structure, and the bottom of synthesis reactor uses enamel structure, closes
It is all made of steel lining graphite-structure at the middle part and kettle cover of kettle, the kettle body bottom of synthesis reactor is the spy for considering the concentrated sulfuric acid using enamel
The characteristic of property and graphite not concentrated sulfuric acid resistant；It is to consider that the gas phase of hydrogen chloride gas is rotten that kettle body middle part and kettle cover, which use steel lining graphite,
Erosion has many advantages, such as that practicability is high, coefficient easy to use, safe is high, long service life.
In ferrous sulfate recrystallization system, including ferrous sulfate hot melt kettle, ferrous sulfate recrystallization kettle and ferrous sulfate
Centrifuge, ferrous sulfate heptahydrate crude product obtained is passed through in ferrous sulfate hot melt kettle in ferrous sulfate sulfonation synthesis system, sulfuric acid
Ferrous hot melt kettle is connected with ferrous sulfate recrystallization kettle, for adding ferrous sulfate heptahydrate crude product in ferrous sulfate hot melt kettle
Enter pure water heating for dissolving, and dissolved ferrous sulfate solution is recrystallized to form seven water sulfuric acid by ferrous sulfate recrystallization kettle
Ferrous crystal, ferrous sulfate recrystallization kettle are connected with ferrous sulfate centrifuge, and separation of solid and liquid forms ferrous sulfate heptahydrate finished product.
In absorbing acid making system, including falling-film absorber, absorption flow container and tail gas absorber, ferrous sulfate sulfonation synthesis
The gas vent of synthesis reactor in system connects falling-film absorber, the chlorine for will generate from ferrous sulfate sulfonation synthesis system
Change hydrogen to absorb to form hydrochloric acid by falling-film absorber, the liquid outlet of falling-film absorber connects into product acid by absorbing flow container
Storage tank, the hydrochloric acid for hydrogen cloride concentration to be reached setting value squeeze into finished product acid storage tank；The offgas outlet of falling-film absorber connects
To tail gas absorber, tail gas absorber ensure that using the dilute hydrochloric acid of the generation in evaporation and crystallization system as tail gas absorption liquid
The purity of hydrochloric acid, also reduces production cost.Preferably, finished product hydrochloric acid is prepared using three-level falling-film absorber absorption, falling liquid film is inhaled
It receives device and is all made of graphite falling film absorber.
For the content for further understanding the utility model, now in conjunction with Fig. 2 to Fig. 6 to a kind of sulfonation method steel of the utility model
The process flow of product hydrochloric acid pickling waste liquor processing equipment for recycling is described further.
As shown in Fig. 2, the hydrochloric acid pickling waste liquor from stoste pool enters in original fluid container V101 in evaporation and crystallization system,
The stoste in original fluid container V101 is successively passed through into level-one preheater E106, second level preheater E107, three-level using feed pump P103
Enter in an effect separator S101 after preheater E108, it is single that an effect separator S101 and 1st effective evaporator E101 forms an effect evaporation
Member, the concentrated solution outlet of an effect separator S101 are connected to two effect separator S102, two effect separator S102 and pass through two effect circulations
It pumps P101 and 2nd effect evaporator E102 and forms two effect evaporation elements, the original liquid concentration in two effect separator S102 reaches setting concentration
Frerrous chloride crystal system is squeezed by discharging pump P102 afterwards；In evaporation and crystallization system, the life steam from boiler is successively passed through
Boiler recycling, the steam in an effect separator S101 are returned after crossing 1st effective evaporator E101 and three-level preheater E108 heat exchange
Successively enter diluted acid tank V102 after 2nd effect evaporator E102, second level preheater E107 and mother liquor preheater E109 heat exchange；Two
Steam a part in effect separator S102 enters diluted acid tank V102 after entering level-one preheater E106 heat exchange, and a part is through being subcooled
Enter in diluted acid tank V102 after condenser E103 condensation, the diluted acid in diluted acid tank V102 passes through thin acid pump P104 and diluted acid cooler
E105 is sent into the tail gas absorber T501 for absorbing acid making system；Fixed gas in condenser E103 passes through on-condensible gas condenser
E104 enters knockout drum V103, and knockout drum V103 meets vapo(u)rization system vacuum pump P105.An above-mentioned effect separator
The steam exit temperature control of S101 is at 92 DEG C or so, and pressure control is in -0.03MPa, the steam (vapor) outlet of two effect separator S102
At 60 DEG C or so, pressure control is controlled in -0.088MPa, the concentrated solution outlet temperature of two effect separator S102 72 for temperature control
DEG C or so.In evaporation and crystallization system, the stoste in two effect separator S102 squeezes into chlorine by the way that liquid distributor V106 is concentrated respectively
Change one R101 of ferrous crystallization kettle, two R102 of frerrous chloride crystallization kettle, three R103 of frerrous chloride crystallization kettle and frerrous chloride crystallization kettle
Solidliquid mixture in four R104, one R101 of frerrous chloride crystallization kettle and two R102 of frerrous chloride crystallization kettle after crystallization enters chlorination
Solid-liquid in ferrous one M101 of centrifuge, in three R103 of frerrous chloride crystallization kettle and four R104 of frerrous chloride crystallization kettle after crystallization
Mixture enters in two M102 of frerrous chloride centrifuge, and the frerrous chloride crude product isolated is packaged defeated by one L101 of electric block
It send into impurity removed system, the filtrate isolated enters mother liquor tank V104, and pumps P106 and mother liquor preheater E109 by mother liquor and preheat
After squeeze into two effect evaporation elements；One R101 of frerrous chloride crystallization kettle, two R102 of frerrous chloride crystallization kettle, frerrous chloride crystallization kettle
One M101 of three R103 and four R104 of frerrous chloride crystallization kettle and frerrous chloride centrifuge, two M102 of frerrous chloride centrifuge and
Mother liquor tank V104 accesses recycling cooler E110, and recycling cooler E110 access recycling flow container V105 recycles flow container V105 and connects
Enter one P107 of crystal system vacuum pump set.
As shown in figure 3, in impurity removed system, frerrous chloride crude product obtained enters pH adjusting in evaporation and crystallization system
In reaction kettle R201, one V201 of alkali liquid tank is adjusted to pH by one P201 of lye pump and is squeezed into lye adjustment pH in reaction kettle R201
It is worth 3 or so, pH adjusting reaction kettle R201 and removal of impurities reaction kettle R202 is squeezed by punishment in advance pump P202, to removal of impurities reaction kettle R202
Interior investment sulfide heavy-metal ion removal, the solution of ferrous chloride after the interior removal of impurities of removal of impurities reaction kettle R202 pass through discharging pump P203
It is squeezed into two R204 of one R203 of frerrous chloride crystallization kettle and frerrous chloride crystallization kettle respectively, one R203 of frerrous chloride crystallization kettle and chlorine
Change the solidliquid mixture obtained after crystallization in two R204 of ferrous crystallization kettle and imports frerrous chloride centrifuge M201, isolated chlorine
Change ferrous crystal to be packaged in feeding ferrous sulfate sulfonation synthesis system by two L201 of electric block, isolated filtrate enters
Filtrate in frerrous chloride mother liquor tank V204, frerrous chloride mother liquor tank V204 pumps P207 by mother liquor and is back to removal of impurities reaction kettle
In R202；One R203 of frerrous chloride crystallization kettle, two R204 of frerrous chloride crystallization kettle, frerrous chloride centrifuge M201 and frerrous chloride
Mother liquor tank V204 access recycling cooler E201, recycling cooler E201 access recycling flow container V205, recycling flow container V205 and knot
Crystallographic system system two P208 of vacuum pump set is connected.
As shown in figure 4, in ferrous sulfate sulfonation synthesis system, frerrous chloride crystal in impurity removed system respectively into
Enter in three R303 of one R301 of synthesis reactor, two R302 of synthesis reactor and synthesis reactor, the concentrated sulfuric acid in concentrated sulfuric acid storage tank V310 is through overrich sulphur
Acid pump P301 successively squeezes into corresponding one V303 of concentrated sulfuric acid head tank of above three synthesis reactor, two V305 of concentrated sulfuric acid head tank and dense
The concentrated sulfuric acid is added into one R301 of synthesis reactor and carries out sulfonating reaction by three V307 of sulfuric acid high position tank, one V303 of concentrated sulfuric acid head tank, dense
Two V305 of sulfuric acid high position tank be added into two R302 of synthesis reactor the concentrated sulfuric acid carry out sulfonating reaction, three V307 of concentrated sulfuric acid head tank to
The concentrated sulfuric acid is added in three R303 of synthesis reactor and carries out sulfonating reaction, the hydrogen chloride gas for reacting generation, which enters, to be absorbed in acid making system,
The ferrous sulfate that reaction generates respectively enters one R304 of ferrous sulfate crystallization kettle, ferrous sulfate crystallization kettle two by distributor V309
R305 and ferrous sulfate crystallization kettle three R306, one R304 of ferrous sulfate crystallization kettle, two R305 of ferrous sulfate crystallization kettle and sulfuric acid are sub-
Solidliquid mixture after crystallizing in three R306 of iron crystallization kettle imports in ferrous sulfate centrifuge M301, and the seven water sulfuric acid isolated are sub-
Iron is packaged through three L301 of electric block and is sent into ferrous sulfate recrystallization system, and the filtrate isolated is led to after importing mother liquor tank V301
It crosses mother liquor pump P302 and squeezes into corresponding one V304 of mother liquor head tank of above three synthesis reactor, two V306 of mother liquor head tank and mother liquor height
In three V308 of slot of position, dilution of the ferrous sulfate filtrate as the concentrated sulfuric acid is added into one R301 of synthesis reactor by one V304 of mother liquor head tank
Dilution of the ferrous sulfate filtrate as the concentrated sulfuric acid is added into two R302 of synthesis reactor by liquid, two V306 of mother liquor head tank, and mother liquor is high
Dilution of the ferrous sulfate filtrate as the concentrated sulfuric acid is added into three R303 of synthesis reactor by position three V308 of slot.Mother liquor tank V301 and sulphur
Acid ferrous iron centrifuge M301 accesses crystal system knockout drum V302, and crystal system knockout drum V302 and crystal system are true
Empty three P303 of unit is connected.
As shown in figure 5, the seven water sulfuric acid in ferrous sulfate recrystallization system, in ferrous sulfate sulfonation synthesis system
Ferrous crystal is added in ferrous sulfate hot melt kettle R401, enters in ferrous sulfate recrystallization kettle R402 after adding water to dissolve by heating and carries out
It recrystallizes, the solidliquid mixture after recrystallization, which enters in ferrous sulfate centrifuge M401, to be separated by solid-liquid separation, the seven water sulfuric acid isolated
Ferrous finished product is packed in storage by four L401 of electric block.
As shown in fig. 6, in absorbing acid making system, from manufactured hydrogen chloride gas in ferrous sulfate sulfonation synthesis system
Stage falling-film absorber E501, second level falling-film absorber E502 and three-level falling-film absorber E503 are sequentially entered, stage falling-film is inhaled
Device E501 and first order absorption flow container V501 are received by first order absorption liquid pump P501 circularly absorbing hydrogen chloride gas, second level falling liquid film is inhaled
It receives device E502 and second level absorbs flow container V502 by second level absorbing liquid pump P502 circularly absorbing hydrogen chloride gas, three-level falling liquid film is inhaled
It receives device E503 and three-level absorbs flow container V503 and passes through three-level absorbing liquid pump P503 circularly absorbing hydrogen chloride gas, three-level absorbing liquid
Concentration in tank V503 reach setting concentration after by three-level absorbing liquid pump P503 squeeze into second level absorb flow container V502, second level absorb
Concentration in flow container V502, which reaches, squeezes into first order absorption liquid pump P501 by second level absorbing liquid pump P502 after setting concentration, and level-one is inhaled
It receives after the concentration in flow container V501 reaches setting concentration and finished product acid storage tank is squeezed by first order absorption liquid pump P501；Three-level falling liquid film is inhaled
The gas vent received in device E503 accesses tail gas absorber T501, is simultaneously from the dilute hydrochloric acid generated in evaporation and crystallization system and enters
In tail gas absorber T501, on absorption tower, circulated sprinkling absorbs tail gas under the action of absorbing liquid pump P504, in tail gas absorber
Concentration of hydrochloric acid in T501 reach setting concentration after by absorption tower absorbing liquid pump P504 squeeze into three-level absorb flow container V503；Tail gas is inhaled
The gas vent for receiving tower T501 accesses absorption system knockout drum V504, and absorption system knockout drum V504 access absorbs system
Unite vacuum pump set P505.
It was verified that using the above scheme, having the following characteristics that
1, this programme process route is correct, has very strong operability, is at steel part hydrochloric acid pickling waste liquor recycling
Reason is preferably a kind of.
2, economic benefit is obvious, and the rate of recovery of hydrogen chloride is up to 98%, and concentration can require freely to adjust according to pickling.
The ferrous sulfate of recycling can be used as chemical products or water treatment agent is sold.
3, environmental benefit is fairly obvious, since hydrogen chloride recycles substantially, and uses full negative pressure system, two secondary rings are not present
Border pollution sources.
4, easy to operate, one worker of full-automatic control system per tour is convenient to operation.
5, investment and processing cost are lower, and investment is only 1/2 or so of roasting method；The 1/3 of freight charges expense price roasting method
Left and right.
A kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling of the utility model, sulfonation method steel part salt
The technique of sour pickle liquor recycling treatment is circulating treatment procedure, three-waste free discharge, treatment process environmental protection, pollution-free, energy consumption
It is low, treatment process safety；Gained recycles product hydrochloric acid and ferrous sulfate heptahydrate purity is high, and obtained ferrous sulfate heptahydrate can be made
It is sold for chemical products or water treatment agent, the hydrochloric acid of recycling all can directly return to workshop use；With preferable
Economic benefit and environmental benefit；Have the advantages that simple, easy to implement, the easy to maintain management of process, input cost are low etc..
Schematically the utility model and embodiments thereof are described above, description is not limiting, attached drawing
Shown in be also one of the embodiments of the present invention, actual structure is not limited to this.So if this field
Those of ordinary skill enlightened by it, without deviating from the purpose of the present invention, without creatively designing
Frame mode similar with the technical solution and embodiment, all should belong to the protection range of the utility model.
Claims (6)
1. a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling, it is characterised in that: including evaporation and crystallization system,
Impurity removed system, ferrous sulfate sulfonation synthesis system, ferrous sulfate recrystallization system and absorption acid making system, in which:
In evaporation and crystallization system, including preheater, evaporator, separator, concentration liquid distributor, frerrous chloride crystallization kettle, chlorine
Change ferrous centrifuge and condenser, the preheater connection by evaporator and separator group at multiple-effect evaporation unit, be used for
Concentration is evaporated to the hydrochloric acid pickling waste liquor from stoste pool, the concentrated solution outlet of the multiple-effect evaporation unit passes through concentration
Liquid distributor connects frerrous chloride crystallization kettle, for crystallizing the frerrous chloride concentrate after concentration for frerrous chloride crystal, chlorine
Change ferrous crystallization kettle to be connected with frerrous chloride centrifuge, for four water frerrous chloride crude products to be obtained by filtration, and passes through charger
Structure is sent into impurity removed system system, and the filtrate (liquid of the frerrous chloride centrifuge is connected in multiple-effect evaporation unit, is used for
Filtrate is set to participate in being concentrated by evaporation again；The steam (vapor) outlet of multiple-effect evaporation unit is connect with condenser, the chlorination for will evaporate
Hydrogen and vapor condense to form dilute hydrochloric acid, and condenser is connected with diluted acid tank, absorb for being sent into after collecting dilute hydrochloric acid
In acid making system；
In impurity removed system, including pH adjust reaction kettle, removal of impurities reaction kettle, tail gas absorber, frerrous chloride removal of impurities crystallization kettle and
Frerrous chloride removal of impurities centrifuge, the feed inlet that the pH adjusts reaction kettle are connected with alkali liquid tank, react for adjusting to pH
Lye is added in kettle to adjust the pH value of the four water frerrous chloride crude products generated from evaporation and crystallization system, the pH adjusts anti-
The discharge port of kettle and the feed inlet for the reaction kettle that cleans is answered to be connected, for reacting a removal huge sum of money with sulfide in removal of impurities reaction kettle
Category ion, the discharge port of the removal of impurities reaction kettle is by pump connection frerrous chloride removal of impurities crystallization kettle, for the chlorine after removal of impurities
Change ferrous iron solution to be crystallized, frerrous chloride removal of impurities crystallization kettle is connected with frerrous chloride removal of impurities centrifuge, for being obtained by filtration
Four water frerrous chloride crystal, and be sent into ferrous sulfate sulfonation synthesis system by charge mechanism, the frerrous chloride removal of impurities
The filtrate (liquid of centrifuge is connected to removal of impurities reaction kettle；The offgas outlet and removal of impurities tail gas absorber of the removal of impurities reaction kettle connect
It connects, removal of impurities tail gas absorber is connect with alkali liquid tank, is absorbed using the hydrogen sulfide tail gas that lye generates removal of impurities reaction；
In ferrous sulfate sulfonation synthesis system, including synthesis reactor, concentrated sulfuric acid head tank, mother liquor head tank, ferrous sulfate crystallization
Kettle and ferrous sulfate centrifuge, the concentrated sulfuric acid head tank are connected with synthesis reactor, for passing through concentrated sulfuric acid head tank to conjunction
Concentrated acid sulfonation reaction generation ferrous sulfate and chlorine are added in four water frerrous chloride crystal made from impurity removed system at coming from kettle
Change hydrogen, the gas vent of synthesis reactor is connected to absorption acid making system, for concentrated hydrochloric acid to be made in the hydrogen chloride absorption of generation；
The liquid outlet of synthesis reactor is connected with ferrous sulfate crystallization kettle, for the ferrous sulfate solution crystallisation by cooling generated will to be reacted,
Ferrous sulfate crystallization kettle is connected with ferrous sulfate centrifuge, for being separated by solid-liquid separation the errous sulfate crystal after crystallization to form seven
The filtrate (liquid of aqueous ferrous sulfate crude product, ferrous sulfate centrifuge is returned into synthesis reactor by mother liquor head tank as dense
The dilution of sulfuric acid；
In ferrous sulfate recrystallization system, including ferrous sulfate hot melt kettle, ferrous sulfate recrystallization kettle and ferrous sulfate centrifugation
Machine, ferrous sulfate heptahydrate crude product obtained is passed through in ferrous sulfate hot melt kettle in ferrous sulfate sulfonation synthesis system, ferrous sulfate
Hot melt kettle is connected with ferrous sulfate recrystallization kettle, pure for ferrous sulfate heptahydrate crude product to be added in ferrous sulfate hot melt kettle
Water dissolves by heating, and dissolved ferrous sulfate solution is recrystallized to form ferrous sulfate heptahydrate by ferrous sulfate recrystallization kettle
Crystal, ferrous sulfate recrystallization kettle are connected with ferrous sulfate centrifuge, and separation of solid and liquid forms ferrous sulfate heptahydrate finished product；
In absorbing acid making system, including falling-film absorber, absorption flow container and tail gas absorber, ferrous sulfate sulfonation synthesis system
In synthesis reactor gas vent connect falling-film absorber, for will from ferrous sulfate sulfonation synthesis system generate hydrogen chloride
Gas absorbs to form hydrochloric acid by falling-film absorber, and the liquid outlet of falling-film absorber connects into the storage of product acid by absorbing flow container
Tank, the hydrochloric acid for hydrogen cloride concentration to be reached setting value squeeze into finished product acid storage tank；The offgas outlet of falling-film absorber is connected to
Tail gas absorber, tail gas absorber is using the dilute hydrochloric acid of the generation in evaporation and crystallization system as tail gas absorption liquid.
2. a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling according to claim 1, feature exist
In: in evaporation and crystallization system, the multiple-effect evaporation unit is using two effect Steaming structures, and multiple-effect evaporation unit connects vacuum
Pump forms negative pressure evaporation；The frerrous chloride crystallization kettle and frerrous chloride centrifuge is also separately connected vacuum pump set, in negative pressure
The crystallization of frerrous chloride is carried out under environment.
3. a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling according to claim 2, feature exist
In: in evaporation and crystallization system, the concentration liquid distributor is separately connected four groups of frerrous chloride crystallization kettles, and every two groups of chlorinations
Ferrous crystallization kettle shares one group of frerrous chloride centrifuge.
4. a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling according to claim 1, feature exist
In: in impurity removed system, the gas vent of the tail gas absorber is connected with vacuum pump group, the frerrous chloride removal of impurities
Crystallization kettle and frerrous chloride removal of impurities centrifuge be also separately connected vacuum pump set, under subnormal ambient carry out frerrous chloride removal of impurities and
Crystallization.
5. a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling according to claim 1, feature exist
In: in ferrous sulfate sulfonation synthesis system, the synthesis reactor uses three stage structure, and the bottom of synthesis reactor uses enamel
Structure, the middle part of synthesis reactor and kettle cover are all made of steel lining graphite-structure.
6. a kind of sulfonation method steel part hydrochloric acid pickling waste liquor processing equipment for recycling according to claim 1, feature exist
In: in absorbing acid making system, finished product hydrochloric acid is prepared using three-level falling-film absorber absorption, the falling-film absorber is all made of
Graphite falling film absorber.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108773857A (en) * | 2018-08-01 | 2018-11-09 | 江苏泰特联合环保科技有限公司 | A kind of sulfonation method steel part hydrochloric acid pickling waste liquor recycling treatment process and device |
| CN111170373A (en) * | 2020-01-07 | 2020-05-19 | 斯瑞尔环境科技股份有限公司 | Preparation method of ferrous chloride tetrahydrate |
| CN111547778A (en) * | 2020-04-03 | 2020-08-18 | 同济大学 | Device and method for continuously converting ferrous chloride solution into ferrous sulfate solution and crystals |
-
2018
- 2018-08-01 CN CN201821227836.5U patent/CN208617383U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108773857A (en) * | 2018-08-01 | 2018-11-09 | 江苏泰特联合环保科技有限公司 | A kind of sulfonation method steel part hydrochloric acid pickling waste liquor recycling treatment process and device |
| CN108773857B (en) * | 2018-08-01 | 2023-10-13 | 江苏泰特联合环保科技有限公司 | Resource treatment process and device for hydrochloric acid pickling waste liquid of steel product by sulfonation method |
| CN111170373A (en) * | 2020-01-07 | 2020-05-19 | 斯瑞尔环境科技股份有限公司 | Preparation method of ferrous chloride tetrahydrate |
| CN111547778A (en) * | 2020-04-03 | 2020-08-18 | 同济大学 | Device and method for continuously converting ferrous chloride solution into ferrous sulfate solution and crystals |
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