CN206069459U - A kind of recycle device of industrial acidic wastewater - Google Patents
A kind of recycle device of industrial acidic wastewater Download PDFInfo
- Publication number
- CN206069459U CN206069459U CN201620790002.XU CN201620790002U CN206069459U CN 206069459 U CN206069459 U CN 206069459U CN 201620790002 U CN201620790002 U CN 201620790002U CN 206069459 U CN206069459 U CN 206069459U
- Authority
- CN
- China
- Prior art keywords
- membrane
- reverse osmosis
- acid
- acidic wastewater
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The utility model is related to a kind of recycle device of industrial acidic wastewater, is more particularly to dissolved with the recycling of the sulfuric acid wastewater containing of impurity inorganic salts, belongs to water-treatment technology field.Include：Reverse osmosis membrane, for filtering to industrial acidic wastewater；First NF membrane, for filtering to industrial acidic wastewater；Mixing unit, carries out batch mixing for the penetrating fluid to reverse osmosis membrane and the first NF membrane.Can realize that by device of the present utility model the composition of the acid waste water containing inorganic salts is recycled, multivalence salt ion and concentrated acid can be effectively obtained, and reverse osmosis membrane load can be mitigated.
Description
Technical field
The utility model is related to a kind of recycle device of industrial acidic wastewater, is more particularly to dissolved with impurity inorganic
The recycling of the sulfuric acid wastewater containing of salt, belongs to water-treatment technology field.
Background technology
As national energy-saving reduces discharging the enforcement of policy, allow substantial amounts of process water to carry out reuse, be Industrial Wastewater Treatment
A direction.In industrial processes, particularly metallurgy, intermetallic composite coating, field of inorganic chemical engineering, have substantial amounts of acid waste water
Produce, wherein it is in the majority with sulfuric acid, in these acid waste waters in addition to containing a certain amount of sulfuric acid, can also contain a certain amount of molten
The inorganic salts of solution.
It is illustrated below：
1、Titanium White Production By Sulfuric Acid Process industry
During Production By Sulfuric Acid Process titanium white, 1t titanium whites are often produced by produce 40～60t 2～6% acid waste water,
Waste water essentially from washing workshop section and washing tail gas workshop section, except containing main component H in acid waste water2SO4Outward, also contain one
The sulfate of quantitative ferrous sulfate, metatitanic acid and other heavy metal ion.These waste water are not only measured greatly, and acid concentration is low,
And contain certain density iron and other heavy metal ion sulfate.Therefore the value for reclaiming is little.These waste water are big at this stage
Lime neutralization precipitation method is all adopted to process.But substantial amounts of lime is not only consumed after neutralization precipitation, processing cost is increased, and
Generate substantial amounts of lime mud, it is impossible to using and cause secondary pollution, therefore substantial amounts of low concentration acid waste water is treated as
One bottleneck of restriction Titanium White Production By Sulfuric Acid Process.
UF membrane early has research as a kind of new separation means, in the process of titanium dioxide acid waste water.
CN103663547A discloses this membrane separation treating process, and it is to first pass through 10～1000nm filter membranes to remove metatitanic acid ion
Afterwards, then with reverse osmosis concentration is entered after nanofiltration and ion-exchange-resin process desalination, counter-infiltration filtrate water can be reverse osmosis concentrated with reuse
Liquid is, through concentrated sulfuric acid, to use as complex acid, bleaching and washing.This technics comparing typical case, on the one hand eliminates sulfuric acid
In molysite, on the other hand concentrate sulfuric acid reuse.But this technique haves the shortcomings that certain, i.e. single-stage membrane process rate of recovery
It is low, especially counter-infiltration.And the operating pressure of counter-infiltration is big, single membrane flux is low, and the waste water after whole nanofiltrations enters counter-infiltration
Ton water investment and operating cost can be caused higher.CN104692456A also discloses science and engineering at a kind of titanium pigment waste acid of NF membrane
Skill, it is reclaimed after metatitanic acid particle with 50～500nm microfiltration membranes, then is washed for two with clear liquid reuse after acid-resistant disintegration removal ferrous salt
Water circulation is used, and dope then can acidleach operation.This technique removal metatitanic acid membrane process as a patent above,
But following acid-resistant disintegration is exactly NF membrane in fact, due to NF membrane to acid rejection it is low, thus result in acid washing as two
, there is accumulation in concentration more and more higher during water circulation use, on the one hand have impact on the Acidity of Aikalinity of titanium dioxide entrained with after washing,
Later process is affected, the rate of recovery on the other hand causing acid is low, acid loss increase.
2. the acid process of metal material production process
With the continuous development that China's industrial economy is built, the scale of metallurgy industry also constantly expands, used as important rear place
The production scale of the pickling of metal of science and engineering sequence also constantly expands, and pickling of metal process needs to use sulfuric acid, the sulfuric acid after use into
For acid pickle.At present, the enterprise that major part is engaged in pickling of metal process is all useless dilute sulfuric acid to be added in liquid caustic soda or directly useless
Process is abandoned, and the cost of useless dilute sulfuric acid is processed than larger, is the useless of 20% or so weight percent concentration as often processed one ton of sulfur acid
Acid solution, will additionally increase the thousands of units of entreprise cost, and also result in the waste of raw material.Except containing in these sulfuric acid wastewater containings
Outside sulfuric acid, the inorganic metal salt also containing a certain amount of dissolving, such as ferrous sulfate etc..If desired waste water is carried out reclaiming profit
With, when using reverse osmosis process, as the concentration of acid and salt in waste water is big, reverse osmosis pressure being caused excessive.For example, patent
CN101759315A discloses a kind of circulation utilization method of waste diluted sulfuric acid from steel washing and comprises the steps：(1) just precipitated
Filter：Acid pickle after acid washing rolled steel is passed through in first stage precipitation tank, room temperature is cooled to, acid pickle is passed through second-level settling pond again；(2)
Secondary precipitation：Calcium hypochlorite is added in the acid pickle in second-level settling pond and is stirred, go the removal of impurity；(3) crystallisation by cooling：
Acid pickle in cooler crystallizer is carried out into cooling treatment；(4) acid solution is matched somebody with somebody again：Persulfuric acid ferrous iron water will be separated in cooler crystallizer
The dilute sulfuric acid mother liquor for closing crystalline solid is passed through pickle again with container, is configured to meet the pickle of technological requirement.But
Step complexity, poor continuity are there is when this technique is for Sewage treatment.
3. metallurgy industry
In the production process of non-ferrous metal, the acid waste liquid of substantial amounts of sulphate-containing ion can be produced, the high dirt of its concentration
Acid waste liquid pH value even as low as less than 1, with extremely strong corrosivity, in not only sulfur acid, but also contain substantial amounts of heavy metal,
Such as lead, zinc, cadmium, fluorine, chlorine etc., it is a kind of industrial wastes for having very big destructive power to environment.Process the spent acid at present to adopt substantially
All it is lime neutralisation, i.e.,：Lime is added several times, the pH value of waste acid is promoted to after neutrality and is adjusted to 10～11 or so again
Process again.For example：In lead, zinc abstraction technique off-gas recovery SO2While production sulfuric acid is as byproduct, it will produce a large amount of
Leaded plasma waste acid water, lead, the continuous expansion of zinc abstraction scope of the enterprise so as to which the discharge rate of waste acid water also gradually increases
It is many.
The content of the invention
The purpose of this utility model is used using nanofiltration and reverse osmosis membrane hybrid integrated technology, processes industrial production mistake
On the one hand impurity inorganic salts in substantial amounts of acid waste water are being removed by the sulfuric acid waste water containing impurity inorganic salts in journey
While, improve concentration of the inorganic salts in concentrated acid, can improve to inorganic salts utilization ratio, also can be by concentrated acid Water circulation；
On the other hand high-quality less salt and the diluted acid water of low acid concentration is obtained carries out reuse.And this technique is due to by counter-infiltration
Concentrated by certain charge proportion with nanofiltration simultaneously, and desalination recovery is carried out using NF membrane again to concentrate after concentration
Clear liquid therein, using this technique, reduces the load and fouling possibility of reverse osmosis membrane, so as to reducing investment and running
Cost.The energy-saving and emission-reduction of environmental protection are not only improved, save the water consumption of technique again, reuse sulfuric acid generates good economy
Environmental benefit.
Technical scheme：
A kind of recoverying and utilizing method of industrial acidic wastewater, described industrial acidic wastewater are containing sulfuric acid and containing dissolving
The waste water of property polyvalent mineral salt, comprises the steps：
A part for industrial acidic wastewater is sent into the first NF membrane carries out filtration treatment, then remaining part is sent into anti-
Osmosis membrane filters process；
The permeate of the first NF membrane and reverse osmosis membrane is mixed.
In one embodiment, the concentrate of the first NF membrane and reverse osmosis membrane is sent into the second NF membrane is carried out at filtration
Reason, obtains the concentrate and permeate of the second NF membrane.
In one embodiment, the permeate of the second NF membrane is sent in reverse osmosis membrane and is filtered.
In one embodiment, the main acid ingredient of described industrial acidic wastewater is sulfuric acid；Described sulfuric acid
Concentration range can be in 1～100g/L, or 5～80g/L, 20～50g/L etc..
In one embodiment, described polyvalent mineral salt refers to the inorganic salts containing divalent above cation.
In one embodiment, described polyvalent mineral salt refers to Fe2+、Fe3+、Zn2+、Mg2+、Mn2+、Ni2+、Cd2+Nothing
Machine salt.
In one embodiment, the concentration of polyvalent mineral salt can be 0.01～10g/L, or 0.1～5g/L,
Can be 1～3g/L etc..
In one embodiment, industrial acidic wastewater needs to process through pre-filtering and/or secondary filter.
In one embodiment, industrial acidic wastewater sends into the first NF membrane and the volume ratio in reverse osmosis membrane（60～
99）：（40～1).
In one embodiment, the first NF membrane refers to two-stage above nanofiltration, and the penetrating fluid of upper level sends into next stage mistake
Filter, the concentrate of next stage return the fed filtration of upper level.
In one embodiment, reverse osmosis membrane refers to two-stage above counter-infiltration, and next stage mistake is sent in the counter-infiltration of upper level
Filter, the concentrate of next stage return the fed filtration of upper level.
A kind of recycle device of industrial acidic wastewater, includes：
Reverse osmosis membrane, for filtering to industrial acidic wastewater；
First NF membrane, for filtering to industrial acidic wastewater；
Mixing unit, carries out batch mixing for the penetrating fluid to reverse osmosis membrane and the first NF membrane.
In one embodiment, prefilter and/or accurate filter are also included, for into reverse osmosis membrane and
The industrial acidic wastewater of one NF membrane is filtered, and removes particulate matter.
In one embodiment, the second NF membrane is also included, for the concentrate to reverse osmosis membrane and the first NF membrane
Filtered.
In one embodiment, the penetrating fluid side of the second NF membrane is connected with the feed liquid port of reverse osmosis membrane.
Beneficial effect
Method of the present utility model, reverse osmosis membrane and NF membrane is used simultaneously together as the method for desalination, by adjusting
Process combination in the charge ratio and two systems of both sections, had both obtained the filtrate of the low acid concentration of less salt, had alleviated system again anti-
The pressure of infiltration, improves the concentration of the rate of recovery and acid.Reduce investment and operating cost.Finally and by above counter-infiltration and receive
The dope of filter system uses NF membrane desalination again, and the filtrate after desalination returns to the water inlet of counter-infiltration one-level.Water is more improve so
The rate of recovery.Overall recovery more than 80%.
Description of the drawings
Fig. 1 is the installation drawing of the industrial acidic wastewater that the utility model is provided.
Fig. 2 is the operating flux schematic diagram of counter-infiltration in embodiment 1 and embodiment 2.
Wherein, 1, prefilter；2nd, accurate filter；3rd, equipment for separating liquid from solid；4th, first-stage reverse osmosis film；5th, two grades of reverse osmosis
Permeable membrane；6th, the first NF membrane of one-level；7th, two grade of first NF membrane；8th, the second NF membrane.
Specific embodiment
The utility model acid waste water to be dealt with is mainly the waste water containing sulfuric acid, and the source of these waste water can be
The sulfuric acid in acid washing water, the sulfuric acid corrosion liquid in intermetallic composite coating manufacture process, metallurgy industry in finger sulfuric acid method titanium pigment industry
Acid waste liquid, or the SO in metallurgy industry after infiltration ore2Sour gas absorbed after waste water.These waste water
General character is：Predominantly contain a certain amount of sulfuric acid, the concentration range of sulfuric acid can be in 1～100g/L, or 5～80g/L,
20～50g/L etc., in addition in the acid waste water, due to also carrying out reacting, infiltrating with ore, metal in industrial processes, or
Be derived from the ore containing polyvalent metal, so still contain polyvalent metal ion in waste water, multivalence here refer to divalent with
On, these metal ions may refer to Fe2+、Fe3+、Zn2+、Mg2+、Mn2+、Ni2+、Cd2+Deng these polyvalent metal inorganic salts have
Certain values, can further reuse, the concentration range of these deliquescent polyvalent mineral salt is not particularly limited, Ke Yishi
0.01～10g/L, or 0.1～5g/L, or 1～3g/L etc..
Before nanofiltration and counter-infiltration operation are carried out to industrial acidic wastewater, pre-filtering process is carried out to which preferably, to go
Some particulate matters, fine impurities in eliminating water etc., mainly can be by accurate filter and are filtered to realize, described here
Accurate filter, may refer to microfiltration membranes or milipore filter etc., microfiltration membranes of the present utility model are 0.01 for average pore size
～5 μm of film, in addition, milipore filter is film that molecular cut off is 1000～200000.Here, due to the aperture of milipore filter it is too small
And the aperture for being difficult to electron microscope etc. determine film surface, so replace average pore size with the value of referred to as molecular cut off come
As the index of pore size.With regard to molecular cut off, as described in the textbook of this area：" will be with molecular weight solute
It is the longitudinal axis for transverse axis, prevention rate, molecular cut off curve is referred to as to the curve that data carry out drawing.And by prevention rate be
90% molecular weight is referred to as the molecular cut off of film ", index of the molecular cut off as the film properties for representing milipore filter, is ability
Known to field technique personnel.As these microfiltration membranes or the material of milipore filter, as long as can realize that removing above-mentioned commercial acid gives up
Particulate contaminant in water, is not particularly limited, and can enumerate：Cellulose, cellulose esters, polysulfones, polyether sulfone, polychlorostyrene second
The organic materials such as alkene, chloropropene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene (PTFE),
Or the inorganic material such as metal or ceramics such as stainless steel.The material of microfiltration membranes or milipore filter can consider the proterties of hydrolysate
Or operating cost is suitably selecting.
In addition before the filtration carried out using secondary filter film and/or milipore filter, for contaminant restraining matter, Ke Yijin
The process of row separation of solid and liquid is used as pre-treatment.With regard to solid-liquid separating method, it is not particularly limited.As the process of specific separation of solid and liquid
Method, centrifugation mode, expression separation mode, filter type, floating separate mode, sedimentation separation mode can be enumerated.Make
For centrifugation mode, can illustrate horizontal continuous centrifuge (process of spiral decanter), separate board-like centrifugal separator,
Filter centrifugal, tall building Pu Lesi type UCF ultracentrifuges, as filter type, can illustrate band filter, belt press, screw rod
Press, precoat filter, filter press, as floating separate mode, can illustrate continuous floating separator, as sedimentation separation
Mode, can illustrate aggegation sedimentation separation machine, rapid sedimentation separation machine etc., but be not particularly limited in above-mentioned any one.But
Load during secondary filter film process to film can be reduced by above-mentioned any one or its combination.
After pre-filtering has been carried out for above-mentioned waste water, then two parts are classified as, a part is entered in sending into NF membrane
Row is filtered, and another part is filtered in sending into reverse osmosis membrane, and reverse osmosis membrane is obtained in that with the rejection higher to sulfuric acid
The very low counter-infiltration permeate of acid concentration, but due to having certain density sulfuric acid in handled waste water, also have in addition
Certain density polyvalent mineral salt ion, therefore operationally load is higher to cause reverse osmosis membrane, flux is little, and due to many
Valency salt ion can cause reverse osmosis membrane surface to there is fouling；Therefore, another part waste water was carried out in being re-fed into NF membrane
Filter, nanofiltration can have higher rejection to polyvalent mineral salt, therefore can get rid of dissolubility inorganic salts in waste water, and receive
The operating pressure of filter is less than counter-infiltration, therefore can be operated under less load, more due to containing in waste water
Sulfuric acid, and NF membrane is relatively low to its rejection, therefore, having more sulfuric acid in industrial processes, can need through NF membrane
Reuse is carried out to the water after process, and if when adopting NF membrane, can cause to have be back in system compared with polyacid, can cause reuse
Acid concentration in system is improved constantly；Therefore, after by the permeate of counter-infiltration and nanofiltration is remixed, reuse can be mitigated
Acid concentration in water, it is to avoid acid accumulation in systems.The ratio of both inlets is counter-infiltration inlet amount：Nanofiltration charging amount is
（60～99）：（40～1), reverse osmosis membrane and NF membrane are used simultaneously together as the method for desalination, by adjusting both
Process combination in charge ratio and two systems, had both obtained the filtrate of the low acid concentration of less salt, alleviated the pressure of system counter-infiltration again
Power, improves the concentration of the rate of recovery and acid, by using counter-infiltration and NF membrane desalination process simultaneously, and adjusts certain to enter
Water ratio, makes the multivalence salt ion in acid waste water be reduced to below 2mg/L；Acid concentration is reduced to below 20g/L, or even 5g/L
Hereinafter, this can cause the inorganic salts in acid waste water to be substantially completely removed, and the acid concentration in penetrating fluid is very low, can be by
Sour water is for example applied to slurry in titanium white production industry as direct reuse, or through other purified treatments
Afterwards, it is applied to Water circulation direction.
NF membrane is defined as " preventing the pressure drive membrane of the particle and the macromolecular for dissolving less than 2nm " herein
Film.Suitable for the preferably such film of effective NF membrane of the present utility model：There is electric charge on the film surface, thus pass through pore
Separate（Particle size separation）Combination with the electrostatic separation of the electric charge having benefited from the film surface and show the separative efficiency for improving.
Therefore, it is necessary to adopt such NF membrane, the NF membrane can using as reclaim the alkali metal ion of target with have it is different
Macromolecule class material is removed while other ions of charge characteristic are separated by electric charge, by particle size separation.As
The material of the NF membrane used in the utility model, it is possible to use cellulose acetate based polymer, polyamide, SPSF, poly-
Acrylonitrile, polyester, polyimides and polyvinyl Polymer material.It is described to be not limited to what is be only made up of a kind of material
Film, can be the film comprising various materials.With regard to membrane structure, the film can be anisotropic membrane, its in film at least one
There is on face compacted zone, and the micropore become larger with inside from compacted zone to film or another side aperture；Or it is multiple
Film is closed, which is on the compacted zone of anisotropic membrane with the very thin functional layer formed by other materials.
Herein reverse osmosis membrane is to make a part of composition in liquid, and for example solvent is passed through so as to its composition be not through half
Permeable membrane. as the material of reverse osmosis membrane, generally use cellulose acetate and birds of the same feather flock together compound, polyamide, polyester, polyimides, second
Alkenyl polymer Polymer material.In addition, as its construction, having and there is compacted zone at least side of film, from the compacted zone
To the inside of film or the surface of opposite side has the anisotropic membrane of the minute aperture for slowly becoming big aperture and in the anisotropic membrane
Compacted zone on composite membrane of very thin active layer formed by other materials etc..Wherein, as the shape of reverse osmosis membrane
Formula, has macaroni yarn, flat film etc. generally, it is preferred to the thickness of macaroni yarn peace film is 10 μm～1mm, the external diameter of macaroni yarn is 50 μm
～4mm.In addition, as flat film, preferred anisotropic membrane, as composite membrane preferably by substrate supports such as fabric, braid, non-woven fabrics
But film., method of the present utility model can not rely on the material of reverse osmosis membrane, film construction or form be used,
It is all effective for any one situation.As representational reverse osmosis membrane, for example, can enumerate cellulose acetate class or polyamide
Class anisotropic membrane, the composite membrane with polyamide-based, polyureas active layer etc..Wherein, method of the present utility model is for acetic acid
Cellulose family anisotropic membrane, polyamide-based composite membrane are especially effective.
Particularly above-mentioned NF membrane and reverse osmosis membrane when being filtered, can be filtered by the way of one-level,
Can also be filtered by the way of two-stage or the above, i.e. the permeate of upper level is re-fed into next stage filtration, next stage it is dense
Contracting liquid returns again to upper level filter again reuse.
Another improvement embodiment of the present utility model is by the concentrate and reverse osmosis obtained by above-mentioned NF membrane
Concentrate obtained by permeable membrane is filtered is re-fed into another NF membrane（Also referred herein as " the second NF membrane "）In carried out
Filter.NF membrane can produce crown_interception to the sulfuric acid in least a portion of solution when filtering, and to most polyvalent mineral
Salt ion is retained, and reverse osmosis membrane all has preferable crown_interception to sulfuric acid and polyvalent mineral salt ion, therefore at it
Concentrate in still can keep a certain amount of polyvalent mineral salt and sulfuric acid, this this partial concentration liquid is dense through NF membrane again
After contracting, this part of sulfuric acid can be passed through NF membrane and can be by polyvalent mineral salt further concentrate, inorganic salts are carried
It is dense that there is great benefit in engineering for being recycled, after the raising of multivalent salts ion concentration, can improve
The treatment effeciency of recycling metal ion, in addition, this part feed liquid have passed through the concentration of nanofiltration and counter-infiltration, sulfuric acid therein is dense
Degree is also improved, for for the demand of concentrated acid reuse, and having great advantage in the industries such as metallurgy, inorganic chemical industry.
In permeate obtained by this part nanofiltration, relatively low polyvalent metal ion and more sulfuric acid are maintained, alternatively improved
In embodiment, be will this part nanofiltration permeate liquid send into above-mentioned counter-infiltration in filtered, such improved procedure can be with
More effect is embodied, on the one hand can be due to being removed to polyvalent metal ion in concentrate, in the penetrating fluid of nanofiltration
Relatively low polyvalent mineral salt can be contained, and containing more sulfuric acid, therefore when being sent to counter-infiltration again, these contain relatively low nothing
When the sulfuric acid waste of machine salinity enters reverse osmosis membrane, the concentration dilution of original inorganic salts can be fallen, effectively can be subtracted
The problem of the light fouling on counter-infiltration surface, improves membrane flux, mitigates the load of reverse osmosis membrane；In addition, this part permeate is again
After osmosis filtration, sulfuric acid therein can be effectively removed, the water during on the one hand can making obtains reuse, separately
On the one hand the sulfuric acid content in recycle-water can also be reduced, it is to avoid sulfuric acid accumulation in systems.By above counter-infiltration and nanofiltration system
The dope of system uses NF membrane desalination again, and the filtrate after desalination returns to the water inlet of counter-infiltration one-level.Returning for water is more improve so
Yield.Overall recovery more than 80%.After have passed through the concentration of the second above-mentioned NF membrane, it is higher to obtain inorganic salt content,
And the concentrated acidic waste water with certain acid concentration, these waste water can be recycled in practice, such as in sulfuric acid process titanium
Acidleach workshop section dispensing is can apply in white powder industry；In addition, if being in metallurgy industry waste water, it is also possible to will be therein dense
The inorganic salts of contracting are again separate out, so as to which obtains inorganic salts be fully used；Gelled acid can also be applied to metal watch
Face pickling processes program.
In above procedure, counter-infiltration service condition used is that temperature is 15～40 DEG C, 2～8MPa of pressure, and cycles of concentration is
2.5～5 times, reverse osmosis membrane iron ion rejection with this understanding is more than 97.5%, is more than 90% to the rejection of sulfuric acid；
It is 15～40 DEG C that the service condition of NF membrane is temperature, and 0.5～5MPa of pressure, cycles of concentration are 5～10 times, and NF membrane is at this
Iron ion rejection under part is more than 97.5%.
According to more than method, the apparatus structure that can be adopted as shown in figure 1,
Prefilter 1 is included, which is used to pre-filtering is carried out to acid waste water, to remove wherein larger particle suspensions
Effect；
Accurate filter 2 is also included, and particulate matter is removed for making secondary filter to the water inlet of NF membrane and reverse osmosis membrane
Effect；
Equipment for separating liquid from solid 3 is included also, for further reclaiming therein to the concentrate of accurate filter 2
Grain；
Device includes：First NF membrane and reverse osmosis membrane, all carry out filtration treatment for acidic industrial effluent, and right
The mixing unit that the penetrating fluid of the first NF membrane and reverse osmosis membrane is mixed；First NF membrane and reverse osmosis membrane can be one-levels,
Can be as shown in Figure 1 that for two-stage, the first NF membrane includes the first NF membrane of one-level 6 and two grade of first NF membrane 7, one
The penetrating fluid of the first NF membrane 6 of level is sent into two grade of first NF membrane 7 and is filtered, and the concentrate of two grade of first NF membrane 7 is returned
The first NF membrane of one-level 6 is filtered, the filtrate of the penetrating fluid of two grade of first NF membrane 7 as overall first NF membrane, one-level first
Dope of the concentrate of NF membrane 6 as the first NF membrane；Similarly, reverse osmosis membrane includes first-stage reverse osmosis film 4 and two grades
Reverse osmosis membrane 5, the penetrating fluid of first-stage reverse osmosis film 4 are sent into two-pass reverse osmosis film 5 and are filtered, the concentration of two-pass reverse osmosis film 5
Liquid returns first-stage reverse osmosis film 4 and filters, the filtrate of the penetrating fluid of two-pass reverse osmosis film 5 as overall reverse osmosis membrane；One-level reverse osmosis
Dope of the penetrating fluid of permeable membrane 4 as overall reverse osmosis membrane.
In a device, the second NF membrane 8 can also be included, for the first NF membrane and the concentration obtained by reverse osmosis membrane
Liquid carries out filtering the filtrate side unhurried reverse osmosis membrane raw material again removed obtained by polyvalent mineral salt, and the second NF membrane 8
Liquid import connects, and its filtrate is filtered.
Embodiment 1
The acid waste water for being adopted comes from the pickling waste waters in sulfate process titanium dioxide powder craft, main component composition such as following table
It is shown：
Acid waste water constitutes (g/L)
After acid waste water first passes through prefilter 1, enter into, its pottery for adopting
The aperture of porcelain film is 200nm.It is to be concentrated to after 200 times, 3 plate and frame filter press of ceramic membrane dope equipment for separating liquid from solid is squeezed out partially
Metatitanic acid, sheet frame filtrate return again to ceramic membrane and are reclaimed metatitanic acid again, and ceramic membrane clear liquid is sent to nanofiltration/counter-infiltration system and carries out
Process.
In organic membrane system, first by ceramic membrane clear liquid by volume 65：35 ratios respectively enter reverse osmosis membrane and
One NF membrane.
In reverse osmosis membrane, feed liquid is entered in first-stage reverse osmosis film 4 first, and control pressure is 5.0MPa, and the rate of recovery is
75%, the clear liquid of first-stage reverse osmosis film 4 enters two-pass reverse osmosis film 5, and first-stage reverse osmosis dope then returns to entering for the second NF membrane 8
In water；Through desalination again and the retention of acid of two-pass reverse osmosis film 5, control pressure is 3.0MPa, and the rate of recovery is 80%, two grades
The molysite content of counter-infiltration clear liquid drops to 0.35mg/L, and the concentration of acid is 2.5g/L, meets the reuse requirement of washings.And two grades
The dope of counter-infiltration is then returned in the water inlet of first-stage reverse osmosis film 4.
In nanofiltration membrane system, feed liquid is entered in the first NF membrane of one-level 6 first, and control pressure is 2.8MPa, the rate of recovery
For 80%, the clear liquid of the first NF membrane of one-level 6 enters two grade of first NF membrane 7, the dope of the first NF membrane of one-level 6 then with one-level
Counter-infiltration dope is mixed together the water inlet as the second NF membrane 8；Through the desalination again of two grade of first NF membrane 7, control pressure
Power is 0.5MPa, and the rate of recovery is 80%, and the molysite content of the clear liquid of two grade of first NF membrane drops to below 1.5mg/L, also complies with
The reuse standard of washings, together as the water after system process after mixing with the clear liquid of two-pass reverse osmosis（Iron salt concentration is
0.74mg/L, acid concentration 20g/L) reuse is washings, and the dope of two grade of first NF membrane then returns to the first nanofiltration of one-level
In the water inlet of film.
Wherein, the concentrate obtained by reverse osmosis membrane and the first NF membrane is all back to the second NF membrane 8 and is filtered
Desalination, operating pressure 3.5Mpa, the rate of recovery 60%, permeate are filtered in returning first-stage reverse osmosis film 4 again.
First NF membrane, the second NF membrane and reverse osmosis membrane after filter process terminates, successively using water rinse, 2wt%
EDTA-0.5 wt %NaOH cleanings, 2 wt % citric acid cleanings, washing after, film pure water flux difference recovery rate be 87%, 85%,
86%。
Embodiment 2
Difference with embodiment 1 is：The concentrate of the first NF membrane and reverse osmosis membrane is dense without the second NF membrane
Contracting filtration treatment.
The acid waste water for being adopted comes from the pickling waste waters in sulfate process titanium dioxide powder craft, main component composition such as following table
It is shown：
Acid waste water constitutes (g/L)
After acid waste water first passes through prefilter 1, enter into, its pottery for adopting
The aperture of porcelain film is 200nm.It is to be concentrated to after 200 times, 3 plate and frame filter press of ceramic membrane dope equipment for separating liquid from solid is squeezed out partially
Metatitanic acid, sheet frame filtrate return again to ceramic membrane and are reclaimed metatitanic acid again, and ceramic membrane clear liquid is sent to nanofiltration/counter-infiltration system and carries out
Process.
In organic membrane system, first by ceramic membrane clear liquid by volume 65：35 ratios respectively enter reverse osmosis membrane and
One NF membrane.
In reverse osmosis membrane, feed liquid is entered in first-stage reverse osmosis film 4 first, and control pressure is 5.0MPa, and the rate of recovery is
75%, the clear liquid of first-stage reverse osmosis film 4 enters two-pass reverse osmosis film 5；Through the desalination again of two-pass reverse osmosis film 5 and cutting for acid
Stay, control pressure is 3.0MPa, and the rate of recovery is 80%, the molysite content of two-pass reverse osmosis clear liquid drops to 0.32mg/L, the concentration of acid
For 2.1g/L, meet the reuse requirement of washings.And the dope of two-pass reverse osmosis is then returned in the water inlet of first-stage reverse osmosis film 4.
In nanofiltration membrane system, feed liquid is entered in the first NF membrane of one-level 6 first, and control pressure is 2.8MPa, the rate of recovery
For 80%, the clear liquid of the first NF membrane of one-level 6 enters two grade of first NF membrane 7；Through the desalination again of two grade of first NF membrane 7,
Control pressure is 0.5MPa, and the rate of recovery is 80%, and the molysite content of the clear liquid of two grade of first NF membrane drops to below 1.8mg/L,
The reuse standard of washings is met, together as the water after system process after mixing with the clear liquid of two-pass reverse osmosis（Molysite is dense
Spend for 0.96mg/L, acid concentration 17g/L) reuse is washings, and the dope of two grade of first NF membrane then returns to one-level first
In the water inlet of NF membrane.
First NF membrane, the second NF membrane and reverse osmosis membrane after filter process terminates, successively using water rinse, 2wt%
EDTA-0.5%NaOH cleanings, 2 wt % citric acid cleanings, washing after, film pure water flux difference recovery rate be 82%, 80%, 82%.
The operating flux curve of the first-stage reverse osmosis film of embodiment 1 and embodiment 2 is as shown in fig. 2, it can be seen that by by the second nanofiltration
After the clear liquid of film returns reverse osmosis membrane filtration, on the one hand can mitigate counter-infiltration load, improve membrane flux, on the other hand can make
Sour water is recycled.
Embodiment 3
The acid waste water for being adopted comes from steel pickling waste liquor, and main component composition is as shown in the table：
Acid waste water constitutes (g/L)
After acid waste water first passes through prefilter 1, enter into, its pottery for adopting
The aperture of porcelain film is 200nm.To be concentrated to be filtered out particle precipitation to after 300 times, ceramic membrane clear liquid is sent to nanofiltration/counter-infiltration system
System is processed.
In organic membrane system, first by ceramic membrane clear liquid by volume 55：45 ratios respectively enter reverse osmosis membrane and
One NF membrane.
In reverse osmosis membrane, feed liquid is entered in first-stage reverse osmosis film 4 first, and control pressure is 5.0MPa, and the rate of recovery is
75%, the clear liquid of first-stage reverse osmosis film 4 enters two-pass reverse osmosis film 5, and first-stage reverse osmosis dope then returns to entering for the second NF membrane 8
In water；Through desalination again and the retention of acid of two-pass reverse osmosis film 5, control pressure is 2.6MPa, and the rate of recovery is 70%, two grades
The molysite content of counter-infiltration clear liquid drops to 0.67mg/L, and the concentration of acid is 2.9g/L, meets the reuse requirement of washings.And two grades
The dope of counter-infiltration is then returned in the water inlet of first-stage reverse osmosis film 4.
In nanofiltration membrane system, feed liquid is entered in the first NF membrane of one-level 6 first, and control pressure is 2.4MPa, the rate of recovery
For 75%, the clear liquid of the first NF membrane of one-level 6 enters two grade of first NF membrane 7, the dope of the first NF membrane of one-level 6 then with one-level
Counter-infiltration dope is mixed together the water inlet as the second NF membrane 8；Through the desalination again of two grade of first NF membrane 7, control pressure
Power is 0.6MPa, and the rate of recovery is 75%, and the molysite content of the clear liquid of two grade of first NF membrane drops to below 3.6mg/L, also complies with
The reuse standard of washings, together as the water after system process after mixing with the clear liquid of two-pass reverse osmosis（Iron salt concentration is
0.74mg/L, acid concentration 20g/L) reuse is washings, and the dope of two grade of first NF membrane then returns to the first nanofiltration of one-level
In the water inlet of film.
Wherein, the concentrate obtained by reverse osmosis membrane and the first NF membrane is all back to the second NF membrane 8 and is filtered
Desalination, operating pressure 3.1Mpa, the rate of recovery 55%, permeate are filtered in returning first-stage reverse osmosis film 4 again.
First NF membrane, the second NF membrane and reverse osmosis membrane after filter process terminates, successively using water rinse, 2wt%
EDTA-0.5 wt %NaOH cleanings, 2 wt % citric acid cleanings, washing after, film pure water flux difference recovery rate be 87%, 88%,
89%。
Embodiment 4
Acid waste water comes from zinc abstraction technique off-gas recovery SO2Leaded, cadmium that production sulfuric acid is produced as byproduct etc.
The waste acid water of ion.Main component composition is as shown in the table：
Acid waste water constitutes (g/L)
After acid waste water first passes through prefilter 1, enter into, its pottery for adopting
The aperture of porcelain film is 200nm.To be concentrated to be filtered out particle precipitation to after 300 times, ceramic membrane clear liquid is sent to nanofiltration/counter-infiltration system
System is processed.
In organic membrane system, first by ceramic membrane clear liquid by volume 60：40 ratios respectively enter reverse osmosis membrane and
One NF membrane.
In reverse osmosis membrane, feed liquid is entered in first-stage reverse osmosis film 4 first, and control pressure is 4.0MPa, and the rate of recovery is
70%, the clear liquid of first-stage reverse osmosis film 4 enters two-pass reverse osmosis film 5, and first-stage reverse osmosis dope then returns to entering for the second NF membrane 8
In water；Through desalination again and the retention of acid of two-pass reverse osmosis film 5, control pressure is 2.5MPa, and the rate of recovery is 70%, two grades
The zinc salt content of counter-infiltration clear liquid drops to 0.31mg/L, and the concentration of acid is 2.6g/L, meets the reuse requirement of washings.And two grades
The dope of counter-infiltration is then returned in the water inlet of first-stage reverse osmosis film 4.
In nanofiltration membrane system, feed liquid is entered in the first NF membrane of one-level 6 first, and control pressure is 3.2MPa, the rate of recovery
For 70%, the clear liquid of the first NF membrane of one-level 6 enters two grade of first NF membrane 7, the dope of the first NF membrane of one-level 6 then with one-level
Counter-infiltration dope is mixed together the water inlet as the second NF membrane 8；Through the desalination again of two grade of first NF membrane 7, control pressure
Power is 0.6MPa, and the rate of recovery is 75%, and the zinc salt content of the clear liquid of two grade of first NF membrane drops to below 2.3mg/L, anti-with two grades
Together as the water after system process after the clear liquid mixing of infiltration（Zinc salt concentration be 0.42mg/L, acid concentration 16g/L) reuse, and
The dope of two grade of first NF membrane is then returned in the water inlet of the first NF membrane of one-level.
Wherein, the concentrate obtained by reverse osmosis membrane and the first NF membrane is all back to the second NF membrane 8 and is filtered
Desalination, operating pressure 3.1Mpa, the rate of recovery 55%, permeate are filtered in returning first-stage reverse osmosis film 4 again.
First NF membrane, the second NF membrane and reverse osmosis membrane after filter process terminates, successively using water rinse, 2wt%
EDTA-0.5 wt %NaOH cleanings, 2 wt % citric acid cleanings, washing after, film pure water flux difference recovery rate be 87%, 88%,
89%。
Claims (7)
1. a kind of recycle device of industrial acidic wastewater, it is characterised in that include：
Reverse osmosis membrane, for filtering to industrial acidic wastewater；
First NF membrane, for filtering to industrial acidic wastewater；
Mixing unit, carries out batch mixing for the penetrating fluid to reverse osmosis membrane and the first NF membrane.
2. the recycle device of industrial acidic wastewater according to claim 1, it is characterised in that also include pre-filtering
Device and/or accurate filter, for filtering to the industrial acidic wastewater into reverse osmosis membrane and/or the first NF membrane, go
Except particulate matter.
3. the recycle device of industrial acidic wastewater according to claim 1, it is characterised in that also include second and receive
Filter membrane, for filtering to the concentrate of reverse osmosis membrane and the first NF membrane；The penetrating fluid side of the second NF membrane and counter-infiltration
The feed liquid port connection of film.
4. the recycle device of industrial acidic wastewater according to claim 1, it is characterised in that the first NF membrane is referred to
Two-stage above nanofiltration, the penetrating fluid of upper level are sent into next stage and are filtered, and the concentrate of next stage returns the fed filtration of upper level.
5. the recycle device of industrial acidic wastewater according to claim 1, it is characterised in that reverse osmosis membrane refers to two
Level above counter-infiltration, the counter-infiltration of upper level are sent into next stage and are filtered, and the concentrate of next stage returns the fed filtration of upper level.
6. the recycle device of industrial acidic wastewater according to claim 2, it is characterised in that accurate filter is referred to
With microfiltration membranes or milipore filter.
7. the recycle device of industrial acidic wastewater according to claim 1, it is characterised in that microfiltration membranes are average hole
Footpath is 0.01～5 μm of film, and milipore filter is film that molecular cut off is 1000～200000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201620790002.XU CN206069459U (en) | 2016-07-25 | 2016-07-25 | A kind of recycle device of industrial acidic wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201620790002.XU CN206069459U (en) | 2016-07-25 | 2016-07-25 | A kind of recycle device of industrial acidic wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN206069459U true CN206069459U (en) | 2017-04-05 |
Family
ID=58425436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201620790002.XU Active CN206069459U (en) | 2016-07-25 | 2016-07-25 | A kind of recycle device of industrial acidic wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN206069459U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470649A (en) * | 2019-01-23 | 2020-07-31 | 上海旷宇环境科技有限公司 | Recovery treatment method of industrial acidic wastewater |
-
2016
- 2016-07-25 CN CN201620790002.XU patent/CN206069459U/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470649A (en) * | 2019-01-23 | 2020-07-31 | 上海旷宇环境科技有限公司 | Recovery treatment method of industrial acidic wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106044951A (en) | Recycling method and device of industrial acidic wastewater | |
| AU2021277661B2 (en) | Process for recovery of lithium from brine | |
| US9085477B2 (en) | Process for reducing the sulfate concentration in a wastewater stream | |
| US5039428A (en) | Waste water treatment process using improved recycle of high density sludge | |
| JP5471054B2 (en) | Methods for recovering water and metals from plating cleaning wastewater | |
| CN103030175B (en) | Device and method applied to metatitanic acid washing room | |
| CN105439341B (en) | A kind of brine waste processing system and processing method | |
| CN105439105B (en) | The integrated processing recovery process of spent acid film and device in a kind of production process of titanium pigment | |
| CA1249885A (en) | Membrane processes for metal recovery and pollution control in metal process industries | |
| CN105540960B (en) | The processing method and system of limestone/lime-gypsum method flue gas desulfurization waste-water | |
| US10040709B2 (en) | Process for reducing the sulfate concentration in a wastewater stream by employing regenerated gibbsite | |
| CN113443736A (en) | Method and device for treating titanium dioxide acidic wastewater and by-producing high-quality titanium gypsum | |
| CN205575837U (en) | Processing system of lime stone / lime - gypsum method flue gas desulfurization waste water | |
| CN109437444A (en) | Deposition vanadium mother liquid and wash water processing equipment for recycling and its method | |
| CN206069459U (en) | A kind of recycle device of industrial acidic wastewater | |
| KR20220006564A (en) | Method of recovering water and chemicals from a plant for treating effluent from a pulp and paper manufacturing plant | |
| CN112624189B (en) | Method and system for recycling waste acid and white water of titanium dioxide produced by sulfuric acid process | |
| JP5224380B2 (en) | Manufacturing method of low grade Ni recycled sludge | |
| CN211921154U (en) | Zero-discharge treatment device for reclaimed water | |
| CN209368011U (en) | Deposition vanadium mother liquid and wash water processing equipment for recycling | |
| CN205381963U (en) | Spent acid membrane integrated process recovery unit in titanium white powder production process | |
| CN206970386U (en) | High salinity sewage disposal system | |
| CN111003859A (en) | Zero-discharge treatment method and device for reclaimed water | |
| CN214990723U (en) | Device for treating titanium dioxide acidic wastewater and by-producing high-quality titanium gypsum | |
| CN114890595A (en) | Waste incineration fly ash washing filtrate treatment system and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |