CN104973725A - Treatment and recycle method of phosphoric acid waste liquid - Google Patents
Treatment and recycle method of phosphoric acid waste liquid Download PDFInfo
- Publication number
- CN104973725A CN104973725A CN201410141546.9A CN201410141546A CN104973725A CN 104973725 A CN104973725 A CN 104973725A CN 201410141546 A CN201410141546 A CN 201410141546A CN 104973725 A CN104973725 A CN 104973725A
- Authority
- CN
- China
- Prior art keywords
- membrane distillation
- phosphate
- concentration
- phosphoric acid
- discharge liquid
- 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.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the field of industrial waste water treatment and particularly relates to a treatment and recycle method of a phosphoric acid waste liquid. In the method, the phosphoric acid waste liquid is successively subjected to micro-filtration, anion exchange, cation exchange and two-stage membrane distillation for recycling the phosphoric acid therefrom. The treatment and recycle method of the phosphoric acid waste liquid, in which the processes comprising the micro-filtration, the anion exchange, the cation exchange, primary membrane distillation and secondary membrane distillation are employed, can be used for treating the phosphoric acid waste liquids generated in production processes of various industries to recycle the phosphoric acid therefrom. The method not only saves energy but also protects natural ecological environment.
Description
Technical field
The present invention relates to field of industrial waste water treatment, is a kind of process recovery method of phosphate discharge liquid specifically.The process of membrane technique coupling other technologies is espespecially utilized to reclaim the method for phosphate discharge liquid.
Background technology
Phosphoric acid is widely used in the industries such as iron and steel, metallurgy, petrochemical industry, and can discharge the waste liquid (phosphate discharge liquid) containing a large amount of waste phosphoric acid in its use procedure, the direct discharge of this kind of waste liquid not only causes serious environmental pollution, and causes the great wasting of resources.Phosphorus is the important indicator of evaluating water quality.When the mass concentration of phosphorus in water body is more than 0.01m
gduring/L, just may cause the eutrophication of water.
The treatment process of existing phosphate discharge liquid mainly contains biological treatment and method of chemical treatment.Biological treatment long processing period, facility floor space are large, investment is large, and can not recycle the phosphoric acid in waste liquid; Method of chemical treatment mainly adopts the material such as carbide slag, lime to neutralize, and produces the body refuses such as a large amount of phosphoric acid salt in N-process, can not recycle the phosphoric acid in waste liquid, waste ample resources.Therefore, the phosphoric acid recycled in waste liquid is all significant in economy and environment.
In prior art, conventional recovery process has diffusion dialysis, electrodialysis, ion-exchange, extraction etc., but often produces dilute acid soln in these processes, and before recycling, these dilute acid solns have to pass through to concentrate and just can reach reuse desired concn.The method of current industrial concentrated phosphoric acid is the concentrated and vacuum evaporation of high temperature mainly.These concentration process energy consumptions are high, and equipment volume is large, and investment is large, and easily produce phenomenons such as carrying secretly.
Membrane distillation (MD) technology is a kind of new separation technology combined with distillation technique by membrane technique, and it adopts microporous hydrophobic membrane, a kind of Aspect of some new membrane processes being motivating force with film both sides steam pressure difference.The process driving force of membrane distillation is the steam pressure difference of film both sides, the water vapor of higher vapor pressure side and the steam molecule of other volatile constituents spread to low-steam pressure side through fenestra, and in the condensation of low-steam pressure side, formed and produce water, thus reach separation or concentrated object.The advantage of membrane distillation is mainly: it is good to produce water water quality, and the rate of recovery is high, can utilize industrial waste heat.Membrane distillation is compared with multiple-effect evaporation: membrane distillation can cold operation, and it is better to produce water water quality, and distillation efficiency is higher, and there is not fouling and the etching problem of evaporator tower, equipment manufacturing cost is also low than conventional distil-lation tower.
Chinese patent CN103011460A relates to a kind of dephosphorization process of metal-containing salt waste phosphoric acid, adopts the technical process of limestone vegetation+preliminary filtration+anionresin.The method of this patent effectively can remove the phosphorus in phosphate discharge liquid, makes it be transformed into calcium phosphate precipitation.Phosphate discharge liquid after this patent process, the phosphorus content in waste liquid reaches discharging standards.This patent does not relate to the recovery problem of phosphorus in phosphate discharge liquid, is only by phosphate discharge liquid process qualified discharge.
Chinese patent CN101254966A relates to a kind of recovery method of phosphate discharge liquid, adopts the technical process of filtration+ion-exchange+vacuum-evaporation.Adopt this patent, phosphate discharge liquid is after common filtration, and enter ion exchange column and carry out ion-exchange, the phosphoric acid solution after ion-exchange carries out vacuum-evaporation, and by vacuum-evaporation, the major part in phosphoric acid solution or all moisture are removed and are discharged in air.The method that this patent relates to is applicable to the lower phosphate discharge liquid process of concentration.
Summary of the invention
For the defect existed in prior art; the object of the present invention is to provide a kind of process recovery method of phosphate discharge liquid; adopt the technical process of micro-filtration+anionresin+cationic exchange+one-level membrane distillation+secondary membrane distillation; may be used for processing the phosphate discharge liquid produced in every profession and trade production process; reclaim phosphoric acid wherein; while saving resource, protect natural ecological environment.
For reaching above object, the technical scheme that the present invention takes is:
A process recovery method for phosphate discharge liquid, is characterized in that: adopt micro-filtration, anionresin, cationic exchange, two-stage membrane distillation to process successively to phosphate discharge liquid, reclaims phosphoric acid wherein.
On the basis of technique scheme, the concrete steps of micro-filtration are: described phosphate discharge liquid is entered Microfiltration Unit and processes, and remove calcium phosphate, trimagnesium phosphate and other suspended substances in phosphate discharge liquid.
On the basis of technique scheme, the concrete steps of anionresin are: the phosphate discharge liquid after micro-filtration process is entered anionite-exchange resin and carries out ion-exchange, the phosphate anion in waste liquid is made to be adsorbed on anionite-exchange resin, after anionite-exchange resin absorption, without phosphorus or containing minute quantity phosphorus salt bearing liquid wastes is discharged from anionite-exchange resin, then directly discharges or merging treatment together with other processing wastewaters;
After anionite-exchange resin uses for some time, carry out manipulation of regeneration, the phosphoric acid on resin is eluted.
On the basis of technique scheme, the concrete steps of cationic exchange are: the elutriant that anionite-exchange resin manipulation of regeneration produces enters Zeo-karb and carries out ion-exchange, to remove the salt ion in elutriant, the pure phosphoric acid solution that final acquisition is denseer;
After Zeo-karb uses for some time, carry out manipulation of regeneration, after Zeo-karb manipulation of regeneration, without phosphorus or containing minute quantity phosphorus the salt bearing liquid wastes of discharge directly discharges or merging treatment together with other processing wastewaters.
On the basis of technique scheme, the concrete steps of two-stage membrane distillation are:
One-level membrane distillation: denseer pure phosphoric acid solution is carried out the process of one-level membrane distillation concentration, after the dehydration of one-level membrane distillation concentration, trapped fluid as one-level membrane distillation unit does not reach setting concentration, after then the trapped fluid of one-level membrane distillation unit mixes with denseer pure phosphoric acid solution, again carry out the process of one-level membrane distillation concentration, trapped fluid as one-level membrane distillation unit reaches setting concentration, then enter secondary membrane distillation;
Secondary membrane is distilled: the trapped fluid of the one-level membrane distillation unit reaching setting concentration is carried out the process of secondary membrane distillation and concentration, trapped fluid as secondary membrane distillation unit does not reach setting concentration, after then the trapped fluid of secondary membrane distillation unit mixes with the trapped fluid of one-level membrane distillation unit, again carry out the process of secondary membrane distillation and concentration, trapped fluid as secondary membrane distillation unit reaches setting concentration, then recycled by the pure phosphoric acid solution reaching reuse requirement concentration;
The membrane distillation produced in one-level membrane distillation and secondary membrane still-process produces water combination treatment and recycles or directly discharge.
On the basis of technique scheme, the water quality characteristic of described phosphate discharge liquid is: PO
4 3-50000 ~ 100000mg/l, Na
+200 ~ 500mg/l, K
+50 ~ 200mg/l, Mg
2+2000 ~ 5000mg/l, Ca
2+200 ~ 500mg/l.
On the basis of technique scheme, described micro-filtration form adopts Ge Er micro-filtration;
Ge Er microfiltration membrane material is PTFE film material, and membrane pore size 0.2 μm, micro-filtration flux controls at 400 ~ 600L/m
2h.
On the basis of technique scheme, described anionite-exchange resin adopts strongly basic anion exchange resin;
The operation flow velocity of phosphate discharge liquid after micro-filtration process in anionite-exchange resin is 10 ~ 30m/h.
On the basis of technique scheme, after described anionite-exchange resin uses 12 ~ 15 days, l ~ 2mol/L sodium hydroxide solution is adopted to carry out manipulation of regeneration.
On the basis of technique scheme, described anionite-exchange resin is at least two groups.
On the basis of technique scheme, described Zeo-karb adopts storng-acid cation exchange resin;
The operation flow velocity of elutriant in Zeo-karb is 10 ~ 30m/h.
On the basis of technique scheme, after described Zeo-karb uses 12 ~ 15 days, 3 ~ 4mol/L hydrochloric acid soln is adopted to carry out manipulation of regeneration.
On the basis of technique scheme, described Zeo-karb is at least two groups.
On the basis of technique scheme, one-level membrane distillation and secondary membrane distillation all adopt inner pressed vacuum membrane distillation;
The operational condition of inner pressed vacuum membrane distillation is:
The temperature range of one-level membrane distillation process is 67 ~ 85 DEG C, one-level membrane distillation crossflow velocity 0.1 ~ 0.6m/s,
The temperature range of secondary membrane still-process is 65 ~ 83 DEG C, secondary membrane distillation crossflow velocity 0.5 ~ 1.0m/s,
Cold side vacuum tightness-0.075 ~-0.095MPa of one-level membrane distillation and secondary membrane distillation.
On the basis of technique scheme, the membrane component form of described two-stage membrane distillation is board-like, hollow fiber form or tubular type;
The mould material of described membrane component is tetrafluoroethylene, and membrane component is one or more groups serial or parallel connection.
On the basis of technique scheme, the membrane pore size of described membrane component is 0.1 ~ 0.3 μm.
The process recovery method of phosphate discharge liquid of the present invention; adopt the technical process of micro-filtration+anionresin+cationic exchange+one-level membrane distillation+secondary membrane distillation; may be used for processing the phosphate discharge liquid produced in every profession and trade production process; reclaim phosphoric acid wherein; while saving resource, protect natural ecological environment.
The process recovery method of phosphate discharge liquid of the present invention, has following beneficial effect:
1, the present invention adopts ion-exchange to be coupled two-stage film distillation technology process phosphate discharge liquid, in Recycling of waste liquid to greatest extent while phosphoric acid, has also reclaimed the water resources in phosphate discharge liquid, has solved the process of phosphate discharge liquid, discharge and recovery problem;
2, the ion exchange treatment phosphate discharge liquid process operation in the present invention is easy, and ion exchange resin is easy to regeneration;
3, the present invention adopts the advantage of two-stage membrane distillation process process phosphate discharge liquid to be, the concentrated of different phosphate acid waste liquid concentration range is completed by adopting two-stage membrane distillation process, effectively slow down the fouling membrane of two-stage membrane distillation process, extend the stable operation cycle of two-stage membrane distillation process;
4, the membrane distillation process in the present invention do not need impressed pressure or outer pressure pressure very little, method is simple, easily operates;
5, the fouling membrane in the membrane distillation process in the present invention is comparatively light, extends the continuous and steady operation time of membrane distillation process;
6, the distillation device in the present invention adopts plastic piping, and interchanger adopts polytetrafluoroethylplastic plastic interchanger, effectively prevent the etching problem of phosphate discharge liquid to pipeline, and improves heating efficiency;
7, the recovery method of phosphate discharge liquid of the present invention is more simple, efficient, adopts the method for the invention process to reclaim phosphate discharge liquid, while turning waste into wealth, solves problem of environmental pollution, have important environmental benefit.
Accompanying drawing explanation
The present invention has following accompanying drawing:
Fig. 1 process flow diagram of the present invention,
The process flow diagram of Fig. 2 two-stage membrane distillation.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
The process recovery method of phosphate discharge liquid of the present invention, adopts the technical process of micro-filtration+anionresin+cationic exchange+two-stage membrane distillation (one-level membrane distillation+secondary membrane distillation) to process, reclaims phosphoric acid wherein.Wherein:
Microfiltration Unit removes calcium phosphate, trimagnesium phosphate and other suspended substances in phosphate discharge liquid.
Anionite-exchange resin adsorb phosphate ion, elutes the phosphoric acid on resin when manipulation of regeneration.
Salt ion in Zeo-karb removing elutriant, the pure phosphoric acid solution that final acquisition is denseer.
The denseer pure phosphoric acid solution obtained will be exchanged through anions and canons, send into one-level membrane distillation unit and carry out the process of one-level membrane distillation concentration, the trapped fluid of one-level membrane distillation unit enters secondary membrane distillation unit and carries out the process of secondary membrane distillation and concentration, by the process of secondary membrane distillation and concentration, the trapped fluid of one-level membrane distillation unit is concentrated to reuse concentration further, obtain the pure phosphoric acid solution that concentration is higher, be back to production technique.In two-stage membrane distillation process, the membrane distillation produced in one-level membrane distillation and secondary membrane still-process produces water combination treatment and recycles or directly discharge.
Concrete steps are:
(1) micro-filtration; Described phosphate discharge liquid is entered Microfiltration Unit process, remove calcium phosphate, trimagnesium phosphate and other suspended substances in phosphate discharge liquid;
(2) anionresin; Phosphate discharge liquid after step (1) process is entered anionite-exchange resin and carries out ion-exchange, the phosphate anion in waste liquid is made to be adsorbed on anionite-exchange resin, after anionite-exchange resin absorption, without phosphorus or containing minute quantity phosphorus salt bearing liquid wastes is discharged from anionite-exchange resin, then directly discharges or merging treatment together with other processing wastewaters;
After anionite-exchange resin uses for some time, carry out manipulation of regeneration, eluted by the phosphoric acid on resin, elutriant enters step (3) process;
(3) cationic exchange; Elutriant enters Zeo-karb and carries out ion-exchange, to remove the salt ion in elutriant, and the pure phosphoric acid solution that final acquisition is denseer;
After Zeo-karb uses for some time, carry out manipulation of regeneration, after Zeo-karb manipulation of regeneration, without phosphorus or containing minute quantity phosphorus the salt bearing liquid wastes of discharge directly discharges or merging treatment together with other processing wastewaters;
(4) two-stage membrane distillation.
On the basis of technique scheme, described two-stage membrane distillation concrete steps are:
(41) one-level membrane distillation; The denseer pure phosphoric acid solution obtained after step (3) process is carried out the process of one-level membrane distillation concentration, after the dehydration of one-level membrane distillation concentration, trapped fluid as one-level membrane distillation unit does not reach setting concentration, after then the trapped fluid of one-level membrane distillation unit mixes with denseer pure phosphoric acid solution, again carry out the process of one-level membrane distillation concentration, trapped fluid as one-level membrane distillation unit reaches setting concentration, then enter step (42);
(42) secondary membrane distillation; The trapped fluid of the one-level membrane distillation unit reaching setting concentration is carried out the process of secondary membrane distillation and concentration, trapped fluid as secondary membrane distillation unit does not reach setting concentration, after then the trapped fluid of secondary membrane distillation unit mixes with the trapped fluid of one-level membrane distillation unit, again carry out the process of secondary membrane distillation and concentration, trapped fluid as secondary membrane distillation unit reaches setting concentration, then recycled by the pure phosphoric acid solution reaching reuse requirement concentration;
The membrane distillation produced in one-level membrane distillation and secondary membrane still-process produces water combination treatment and recycles or directly discharge.
The setting concentration of one-level membrane distillation counts 30% ~ 40% by mass concentration.
The setting concentration of secondary membrane distillation is counted by mass concentration and is more than or equal to 50%.
On the basis of technique scheme, the water quality characteristic of step (1) described phosphate discharge liquid is: PO
4 3-50000 ~ 100000mg/l, Na
+200 ~ 500mg/l, K
+50 ~ 200mg/l, Mg
2+2000 ~ 5000mg/l, Ca
2+200 ~ 500mg/l.
On the basis of technique scheme, the described micro-filtration form of step (1) adopts Ge Er micro-filtration;
Ge Er microfiltration membrane material is PTFE film material, and membrane pore size 0.2 μm, micro-filtration flux controls at 400 ~ 600L/m
2h.
On the basis of technique scheme, the described anionite-exchange resin of step (2) adopts strongly basic anion exchange resin;
The operation flow velocity of phosphate discharge liquid in anionite-exchange resin after step (1) process is 10 ~ 30m/h.
On the basis of technique scheme, after the described anionite-exchange resin of step (2) uses 12 ~ 15 days, l ~ 2mol/L sodium hydroxide solution is adopted to carry out manipulation of regeneration.
On the basis of technique scheme, step (2) described anionite-exchange resin is at least two groups.
On the basis of technique scheme, the described Zeo-karb of step (3) adopts storng-acid cation exchange resin;
The operation flow velocity of elutriant in Zeo-karb is 10 ~ 30m/h.
On the basis of technique scheme, after the described Zeo-karb of step (3) uses 12 ~ 15 days, 3 ~ 4mol/L hydrochloric acid soln is adopted to carry out manipulation of regeneration.
On the basis of technique scheme, step (3) described Zeo-karb is at least two groups.
On the basis of technique scheme, one-level membrane distillation and secondary membrane distillation all adopt inner pressed vacuum membrane distillation;
The operational condition of inner pressed vacuum membrane distillation is:
The temperature range of one-level membrane distillation process is 67 ~ 85 DEG C, one-level membrane distillation crossflow velocity 0.1 ~ 0.6m/s,
The temperature range of secondary membrane still-process is 65 ~ 83 DEG C, secondary membrane distillation crossflow velocity 0.5 ~ 1.0m/s,
Cold side vacuum tightness-0.075 ~-0.095MPa of one-level membrane distillation and secondary membrane distillation.
The denseer pure phosphoric acid solution obtained after step (3) process, before carrying out the process of one-level membrane distillation concentration, adopt type of heating to be heated to 67 ~ 85 DEG C, then carry out the process of one-level membrane distillation concentration, concrete type of heating can be implemented by prior art; Or as shown in Figure 2, adopt the trapped fluid heat exchange of plastic heat exchanger 12 and secondary membrane distillation unit, the denseer pure phosphoric acid solution obtained after step (3) process is heated to 67 ~ 85 DEG C, denseer pure phosphoric acid solution after heating pumps into one-level membrane distillation unit 13 as feeding liquid and carries out concentration, and then pump into secondary membrane distillation unit 14 carry out concentration.
On the basis of technique scheme, the membrane component form of described two-stage membrane distillation is board-like, hollow fiber form or tubular type;
The mould material of described membrane component is tetrafluoroethylene, and membrane component is one or more groups serial or parallel connection.
On the basis of technique scheme, the membrane pore size of described membrane component is 0.1 ~ 0.3 μm.
The process recovery method of phosphate discharge liquid of the present invention, adopts ion-exchange coupling two-stage membrane distillation process, processes for low phosphorus acid waste liquid, and the phosphoric acid in Recycling of waste liquid.By adopting Ge Er microfiltration membrane, eliminate the calcium phosphate in phosphate discharge liquid, trimagnesium phosphate and other suspended substances; Exchanged by anions and canons afterwards, obtain comparatively pure phosphoric acid solution, comparatively pure phosphoric acid solution is again by the further concentration of two-stage membrane distillation, the dense pure phosphoric acid solution of final acquisition is back to production technique, and the moisture in the phosphoric acid solution obtained after two-stage membrane distillation concentration be condensed after combination treatment recycle or directly discharge.Adopt method of the present invention, may be used for processing the phosphate discharge liquid produced in every profession and trade production process, reclaim phosphoric acid wherein, while saving resource, protect natural ecological environment.
The recovery method of phosphate discharge liquid of the present invention is more simple, efficient, in Recycling of waste liquid to greatest extent while phosphoric acid, and the water resources reclaimed in phosphate discharge liquid can be processed, solve the process of phosphate discharge liquid, discharge and recovery problem.Adopt the method for the invention process to reclaim phosphate discharge liquid, while turning waste into wealth, solve problem of environmental pollution, there is important environmental benefit.
It is easy that ion exchange treatment in the present invention reclaims phosphate discharge liquid process operation, and ion exchange resin is easy to regeneration.
Membrane distillation process in the present invention do not need impressed pressure or outer pressure pressure very little, method is simple, easily operates.Fouling membrane in membrane distillation process is comparatively light, extends the continuous and steady operation time of membrane distillation process.Distillation device adopts plastic piping, effectively prevent the etching problem of phosphate discharge liquid to pipeline.
Fig. 1 is process flow diagram of the present invention.In figure: 1 is phosphate discharge liquid; 2 is micro-filtration; 3 is anion-exchange column; 4 is cationic exchange coloum; 5 is one-level membrane distillation; 6 is secondary membrane distillation; 7 is membrane distillation concentration liquid, namely reaches the pure phosphoric acid solution of reuse requirement concentration; 8 is solid slag; 9 is the without phosphorus of anion-exchange column discharge or the salt bearing liquid wastes containing minute quantity phosphorus; 10 is the without phosphorus of cationic exchange coloum discharge or the salt bearing liquid wastes containing minute quantity phosphorus; 11 is membrane distillation product water, the water that namely specific conductivity is very low.
Fig. 2 is the process flow diagram of two-stage membrane distillation.In figure: 12 is interchanger; 13 is one-level membrane distillation unit; 14 is secondary membrane distillation unit.
It is below specific embodiment.
Embodiment 1
Process flow diagram is shown in Fig. 1.In figure, the water quality characteristic of phosphate discharge liquid is: PO
4 3-50000 ~ 100000mg/l, Na
+200 ~ 500mg/l, K
+50 ~ 200mg/l, Mg
2+2000 ~ 5000mg/l, Ca
2+200 ~ 500mg/l;
Operation steps is as follows:
(1) micro-filtration.Described phosphate discharge liquid is entered Microfiltration Unit process, remove calcium phosphate, trimagnesium phosphate and other suspended substances in phosphate discharge liquid;
(2) anionresin.Phosphate discharge liquid after step (1) process is entered anionite-exchange resin (anion-exchange column) and carries out ion-exchange, the phosphate anion in waste liquid is made to be adsorbed on anionite-exchange resin, after anionite-exchange resin absorption, without phosphorus or containing minute quantity phosphorus salt bearing liquid wastes discharges anionite-exchange resin, then directly discharges or merging treatment together with other processing wastewaters.
After anionite-exchange resin uses 12 days, adopt lmol/L sodium hydroxide solution to carry out manipulation of regeneration, eluted by the phosphoric acid on resin, elutriant enters step (3) process;
(3) cationic exchange.The elutriant produced in step (2) is entered Zeo-karb and carries out ion-exchange, to remove the salt ion in elutriant, the pure phosphoric acid solution that final acquisition is denseer;
After Zeo-karb uses 12 days, adopt 3mol/L hydrochloric acid soln to carry out manipulation of regeneration, after Zeo-karb manipulation of regeneration, without phosphorus or containing minute quantity phosphorus the salt bearing liquid wastes of discharge directly discharges or merging treatment together with other processing wastewaters;
(4) one-level membrane distillation.The denseer pure phosphoric acid solution obtained after step (3) process is carried out the process of one-level membrane distillation concentration.
First, denseer pure phosphoric acid solution adopts heating or adopts the concentrated solution heat exchange of the board-like interchanger 12 of tetrafluoroethylene and secondary membrane distillation unit to 67 DEG C, then pump into one-level membrane distillation unit and carry out concentration, after one-level membrane distillation circulation concentration, when Phosphoric Acid Concentration liquid concentration reaches 30%, primary concentration liquid enters step (5) and proceeds the process of secondary membrane distillation and concentration;
(5) secondary membrane distillation.The primary concentration liquid pump of temperature after one-level membrane distillation concentration about 65 DEG C is entered secondary membrane distillation unit and proceed concentration, when secondary concentration liquid is recycled to during phosphoric acid quality concentration 50% by secondary membrane distillation circulation concentration.
In the process, the membrane distillation produced in one-level membrane distillation and secondary membrane still-process produces water combination treatment and recycles or directly discharge.
In above-mentioned steps, micro-filtration used is Ge Er micro-filtration, and Ge Er microfiltration membrane material is PTFE film material, membrane pore size 0.2 μm; Anionite-exchange resin used is polystyrene strongly basic anion exchange resin; Zeo-karb used is polystyrene storng-acid cation exchange resin; Membrane component used is polytetrafluoroethylene (PTFE) hollow fiber hydrophobic membrane assembly, and membrane pore size is 0.2 μm, and membrane distillation form is inner pressed vacuum membrane distillation;
In above-mentioned steps, the micro-filtration flux constant of step (1) is at 500L/m
2h, under this constant flux, in the operational process of continuous 15 days, the working pressure of micro-filtration is risen to the 0.12MPa in later stage by initial 0.04MPa;
In above-mentioned steps, the operation flow velocity that the anions and canons of step (2) and step (3) exchanges is 10m/h;
In above-mentioned steps, other operational conditions of membrane distillation process are: one-level membrane distillation crossflow velocity 0.1m/s, secondary membrane distillation crossflow velocity 0.5m/s, cold side vacuum tightness-0.095MPa.Under these conditions, in operational process for three days on end, one-level membrane distillation membrane flux remains on 10 ~ 14L/m
2h, secondary membrane distillation membrane flux remains on 6 ~ 9L/m
2h;
The concentrated phosphoric acid reclaimed after the inventive method process, can be back to production technique.
Embodiment 2
Process flow diagram is shown in Fig. 1.In embodiment 2, the water quality characteristic of phosphate discharge liquid is with embodiment 1.
Operation steps is with embodiment 1.Wherein as different from Example 1:
After anionite-exchange resin uses 13 days, 1.5mol/L sodium hydroxide solution is adopted to carry out manipulation of regeneration;
After Zeo-karb uses 13 days, 3.5mol/L hydrochloric acid soln is adopted to carry out manipulation of regeneration;
Denseer pure phosphoric acid solution adopts heating or adopts the concentrated solution heat exchange of polytetrafluoroethylhollow hollow fiber formula interchanger 12 and secondary membrane distillation unit to 75 DEG C, then pump into one-level membrane distillation unit and carry out concentration, after one-level membrane distillation circulation concentration, when concentrated solution mass concentration reaches 35%, primary concentration liquid enters step (5) and proceeds the process of secondary membrane distillation and concentration;
The primary concentration liquid pump of temperature after one-level membrane distillation concentration about 73 DEG C is entered secondary membrane distillation unit and proceed concentration, when secondary membrane distillation circulation concentration is recycled to during phosphoric acid quality concentration 55%.
In above-mentioned steps, micro-filtration used is Ge Er micro-filtration, and Ge Er microfiltration membrane material is PTFE film material, membrane pore size 0.2 μm; Anionite-exchange resin used is polystyrene strongly basic anion exchange resin; Zeo-karb used is polystyrene storng-acid cation exchange resin; Membrane component used is polytetrafluoroethylene (PTFE) hollow fiber hydrophobic membrane assembly, and membrane pore size is 0.1 μm, and membrane distillation form is inner pressed vacuum membrane distillation;
In above-mentioned steps, the micro-filtration flux constant of step (1) is at 400L/m
2h, under this constant flux, in the operational process of continuous 15 days, the working pressure of micro-filtration is risen to the 0.09MPa in later stage by initial 0.03MPa;
In above-mentioned steps, the operation flow velocity that the anions and canons of step (2) and step (3) exchanges is 20m/h;
In above-mentioned steps, other operational conditions of membrane distillation process are: one-level membrane distillation crossflow velocity 0.3m/s, secondary membrane distillation crossflow velocity 0.7m/s, cold side vacuum tightness-0.085MPa.Under these conditions, in operational process for three days on end, one-level membrane distillation membrane flux remains on 11 ~ 14L/m
2h, secondary membrane distillation membrane flux remains on 5 ~ 8L/m
2h;
The concentrated phosphoric acid reclaimed after the inventive method process, can be back to production technique.
Embodiment 3
Process flow diagram is shown in Fig. 1.In embodiment 3, the water quality characteristic of phosphate discharge liquid is with embodiment 1.
Operation steps is with embodiment 1.Wherein as different from Example 1:
After anionite-exchange resin uses 14 days, 1.5mol/L sodium hydroxide solution is adopted to carry out manipulation of regeneration;
After Zeo-karb uses 14 days, 3.5mol/L hydrochloric acid soln is adopted to carry out manipulation of regeneration;
Denseer pure phosphoric acid solution adopts heating or adopts the concentrated solution heat exchange of polytetrafluoroethylhollow hollow fiber formula interchanger 12 and secondary membrane distillation unit to 80 DEG C, then pump into one-level membrane distillation unit and carry out concentration, after one-level membrane distillation circulation concentration, when concentrated solution mass concentration reaches 40%, primary concentration liquid enters step (5) and proceeds the process of secondary membrane distillation and concentration;
The primary concentration liquid pump of temperature after one-level membrane distillation concentration about 78 DEG C is entered secondary membrane distillation unit and proceed concentration, when secondary membrane distillation circulation concentration is recycled to during phosphoric acid quality concentration 60%.
In above-mentioned steps, micro-filtration used is Ge Er micro-filtration, and Ge Er microfiltration membrane material is PTFE film material, membrane pore size 0.2 μm; Anionite-exchange resin used is polystyrene strongly basic anion exchange resin; Zeo-karb used is polystyrene storng-acid cation exchange resin; Membrane component used is polytetrafluoroethylene (PTFE) hollow fiber hydrophobic membrane assembly, and membrane pore size is 0.3 μm, and membrane distillation form is inner pressed vacuum membrane distillation.
In above-mentioned steps, the micro-filtration flux constant of step (1) is at 600L/m
2h, under this constant flux, in the operational process of continuous 15 days, the working pressure of micro-filtration is risen to the 0.15MPa in later stage by initial 0.05MPa;
In above-mentioned steps, the operation flow velocity that the anions and canons of step (2) and step (3) exchanges is 30m/h;
In above-mentioned steps, other operational conditions of membrane distillation process are: one-level membrane distillation crossflow velocity 0.4m/s, secondary membrane distillation crossflow velocity 0.8m/s, cold side vacuum tightness-0.075MPa.Under these conditions, in operational process for three days on end, one-level membrane distillation membrane flux remains on 10 ~ 13L/m
2h, secondary membrane distillation membrane flux remains on 5 ~ 7L/m
2h;
The concentrated phosphoric acid reclaimed after the inventive method process, can be back to production technique.
Embodiment 4
Process flow diagram is shown in Fig. 1.In embodiment 4, the water quality characteristic of phosphate discharge liquid is with embodiment 1.
Operation steps is with embodiment 1.Wherein as different from Example 1:
After anionite-exchange resin uses 15 days, 2mol/L sodium hydroxide solution is adopted to carry out manipulation of regeneration;
After Zeo-karb uses 15 days, 4mol/L hydrochloric acid soln is adopted to carry out manipulation of regeneration;
Denseer pure phosphoric acid solution adopts heating or adopts the concentrated solution heat exchange of the board-like interchanger 12 of tetrafluoroethylene and secondary membrane distillation unit to 85 DEG C, then pump into one-level membrane distillation unit and carry out concentration, after one-level membrane distillation circulation concentration, when concentrated solution mass concentration reaches 30%, primary concentration liquid enters step (5) and proceeds the process of secondary membrane distillation and concentration;
The primary concentration liquid pump of temperature after one-level membrane distillation concentration about 83 DEG C is entered secondary membrane distillation unit and proceed concentration, when secondary membrane distillation circulation concentration is recycled to during phosphoric acid quality concentration 50%.
In above-mentioned steps, micro-filtration used is Ge Er micro-filtration, and Ge Er microfiltration membrane material is PTFE film material, membrane pore size 0.2 μm; Anionite-exchange resin used is polystyrene strongly basic anion exchange resin; Zeo-karb used is polystyrene storng-acid cation exchange resin; Membrane component used is polytetrafluoroethylene (PTFE) hollow fiber hydrophobic membrane assembly, and membrane pore size is 0.2 μm, and membrane distillation form is inner pressed vacuum membrane distillation;
In above-mentioned steps, the micro-filtration flux constant of step (1) is at 400L/m
2h, under this constant flux, in the operational process of continuous 15 days, the working pressure of micro-filtration is risen to the 0.09MPa in later stage by initial 0.03MPa;
In above-mentioned steps, the operation flow velocity that the anions and canons of step (2) and step (3) exchanges is 15m/h;
In above-mentioned steps, other operational conditions of membrane distillation process are: one-level membrane distillation crossflow velocity 0.5m/s, secondary membrane distillation crossflow velocity 1.0m/s, cold side vacuum tightness-0.085MPa.Under these conditions, in operational process for three days on end, one-level membrane distillation membrane flux remains on 8 ~ 11L/m
2h, secondary membrane distillation membrane flux remains on 6 ~ 9L/m
2h;
The concentrated phosphoric acid reclaimed after the inventive method process, can be back to production technique.
Embodiment 5
Process flow diagram is shown in Fig. 1.In embodiment 5, the water quality characteristic of phosphate discharge liquid is with embodiment 1.
Operation steps is with embodiment 1.Wherein as different from Example 1:
After anionite-exchange resin uses 15 days, 2mol/L sodium hydroxide solution is adopted to carry out manipulation of regeneration;
After Zeo-karb uses 15 days, 4mol/L hydrochloric acid soln is adopted to carry out manipulation of regeneration;
Denseer pure phosphoric acid solution adopts heating or adopts the concentrated solution heat exchange of the board-like interchanger 12 of tetrafluoroethylene and secondary membrane distillation unit to 85 DEG C, then pump into one-level membrane distillation unit and carry out concentration, after one-level membrane distillation circulation concentration, when concentrated solution mass concentration reaches 30%, primary concentration liquid enters step (5) and proceeds the process of secondary membrane distillation and concentration;
The primary concentration liquid pump of temperature after one-level membrane distillation concentration about 83 DEG C is entered secondary membrane distillation unit and proceed concentration, when secondary membrane distillation circulation concentration is recycled to during phosphoric acid quality concentration 50%.
In above-mentioned steps, micro-filtration used is Ge Er micro-filtration, and Ge Er microfiltration membrane material is PTFE film material, membrane pore size 0.2 μm; Anionite-exchange resin used is polystyrene strongly basic anion exchange resin; Zeo-karb used is polystyrene storng-acid cation exchange resin; Membrane component used is the board-like hydrophobic membrane assembly of polytetrafluoroethylene (PTFE), and membrane pore size is 0.2 μm, and membrane distillation form is inner pressed vacuum membrane distillation;
In above-mentioned steps, the micro-filtration flux constant of step (1) is at 400L/m
2h, under this constant flux, in the operational process of continuous 15 days, the working pressure of micro-filtration is risen to the 0.09MPa in later stage by initial 0.03MPa;
In above-mentioned steps, the operation flow velocity that the anions and canons of step (2) and step (3) exchanges is 15m/h;
In above-mentioned steps, other operational conditions of membrane distillation process are: one-level membrane distillation crossflow velocity 0.6m/s, secondary membrane distillation crossflow velocity 1.0m/s, cold side vacuum tightness-0.085MPa.Under these conditions, in operational process for three days on end, one-level membrane distillation membrane flux remains on 10 ~ 14L/m
2h, secondary membrane distillation membrane flux remains on 8 ~ 11L/m
2h;
The concentrated phosphoric acid reclaimed after the inventive method process, can be back to production technique.
The foregoing is only better possible embodiments of the present invention, not thereby limit to the scope of the claims of the present invention, therefore the equivalence change that every utilization specification sheets of the present invention and accompanying drawing content are done, be all contained in protection scope of the present invention.
The content be not described in detail in this specification sheets belongs to the known prior art of professional and technical personnel in the field.
Claims (16)
1. a process recovery method for phosphate discharge liquid, is characterized in that: adopt micro-filtration, anionresin, cationic exchange, two-stage membrane distillation to process successively to phosphate discharge liquid, reclaims phosphoric acid wherein.
2. the process recovery method of phosphate discharge liquid as claimed in claim 1, is characterized in that: the concrete steps of micro-filtration are: described phosphate discharge liquid is entered Microfiltration Unit and processes, and removes calcium phosphate, trimagnesium phosphate and other suspended substances in phosphate discharge liquid.
3. the process recovery method of phosphate discharge liquid as claimed in claim 2, it is characterized in that: the concrete steps of anionresin are: the phosphate discharge liquid after micro-filtration process is entered anionite-exchange resin and carries out ion-exchange, the phosphate anion in waste liquid is made to be adsorbed on anionite-exchange resin, after anionite-exchange resin absorption, without phosphorus or containing minute quantity phosphorus salt bearing liquid wastes is discharged from anionite-exchange resin, then directly discharges or merging treatment together with other processing wastewaters;
After anionite-exchange resin uses for some time, carry out manipulation of regeneration, the phosphoric acid on resin is eluted.
4. the process recovery method of phosphate discharge liquid as claimed in claim 3, it is characterized in that: the concrete steps of cationic exchange are: the elutriant that anionite-exchange resin manipulation of regeneration produces enters Zeo-karb and carries out ion-exchange, to remove the salt ion in elutriant, the pure phosphoric acid solution that final acquisition is denseer;
After Zeo-karb uses for some time, carry out manipulation of regeneration, after Zeo-karb manipulation of regeneration, without phosphorus or containing minute quantity phosphorus the salt bearing liquid wastes of discharge directly discharges or merging treatment together with other processing wastewaters.
5. the process recovery method of phosphate discharge liquid as claimed in claim 4, is characterized in that: the concrete steps of two-stage membrane distillation are:
One-level membrane distillation: denseer pure phosphoric acid solution is carried out the process of one-level membrane distillation concentration, after the dehydration of one-level membrane distillation concentration, trapped fluid as one-level membrane distillation unit does not reach setting concentration, after then the trapped fluid of one-level membrane distillation unit mixes with denseer pure phosphoric acid solution, again carry out the process of one-level membrane distillation concentration, trapped fluid as one-level membrane distillation unit reaches setting concentration, then enter secondary membrane distillation;
Secondary membrane is distilled: the trapped fluid of the one-level membrane distillation unit reaching setting concentration is carried out the process of secondary membrane distillation and concentration, trapped fluid as secondary membrane distillation unit does not reach setting concentration, after then the trapped fluid of secondary membrane distillation unit mixes with the trapped fluid of one-level membrane distillation unit, again carry out the process of secondary membrane distillation and concentration, trapped fluid as secondary membrane distillation unit reaches setting concentration, then recycled by the pure phosphoric acid solution reaching reuse requirement concentration;
The membrane distillation produced in one-level membrane distillation and secondary membrane still-process produces water combination treatment and recycles or directly discharge.
6. the process recovery method of phosphate discharge liquid as claimed in claim 5, is characterized in that: the water quality characteristic of described phosphate discharge liquid is: PO
4 3-50000 ~ 100000mg/l, Na
+200 ~ 500mg/l, K
+50 ~ 200mg/l, Mg
2+2000 ~ 5000mg/l, Ca
2+200 ~ 500mg/l.
7. the process recovery method of phosphate discharge liquid as claimed in claim 5, is characterized in that: described micro-filtration form adopts Ge Er micro-filtration;
Ge Er microfiltration membrane material is PTFE film material, and membrane pore size 0.2 μm, micro-filtration flux controls at 400 ~ 600L/m
2h.
8. the process recovery method of phosphate discharge liquid as claimed in claim 5, is characterized in that: described anionite-exchange resin adopts strongly basic anion exchange resin;
The operation flow velocity of phosphate discharge liquid after micro-filtration process in anionite-exchange resin is 10 ~ 30m/h.
9. the process recovery method of phosphate discharge liquid as claimed in claim 5, is characterized in that: after described anionite-exchange resin uses 12 ~ 15 days, adopts l ~ 2mol/L sodium hydroxide solution to carry out manipulation of regeneration.
10. the process recovery method of phosphate discharge liquid as claimed in claim 5, is characterized in that: described anionite-exchange resin is at least two groups.
The process recovery method of 11. phosphate discharge liquids as claimed in claim 5, is characterized in that: described Zeo-karb adopts storng-acid cation exchange resin;
The operation flow velocity of elutriant in Zeo-karb is 10 ~ 30m/h.
The process recovery method of 12. phosphate discharge liquids as claimed in claim 5, is characterized in that: after described Zeo-karb uses 12 ~ 15 days, adopts 3 ~ 4mol/L hydrochloric acid soln to carry out manipulation of regeneration.
The process recovery method of 13. phosphate discharge liquids as claimed in claim 5, is characterized in that: described Zeo-karb is at least two groups.
The process recovery method of 14. phosphate discharge liquids as claimed in claim 5, is characterized in that: one-level membrane distillation and secondary membrane distillation all adopt inner pressed vacuum membrane distillation;
The operational condition of inner pressed vacuum membrane distillation is:
The temperature range of one-level membrane distillation process is 67 ~ 85 DEG C, one-level membrane distillation crossflow velocity 0.1 ~ 0.6m/s,
The temperature range of secondary membrane still-process is 65 ~ 83 DEG C, secondary membrane distillation crossflow velocity 0.5 ~ 1.0m/s,
Cold side vacuum tightness-0.075 ~-0.095MPa of one-level membrane distillation and secondary membrane distillation.
The process recovery method of 15. phosphate discharge liquids as claimed in claim 5, is characterized in that: the membrane component form of described two-stage membrane distillation is board-like, hollow fiber form or tubular type;
The mould material of described membrane component is tetrafluoroethylene, and membrane component is one or more groups serial or parallel connection.
The process recovery method of 16. phosphate discharge liquids as claimed in claim 5, is characterized in that: the membrane pore size of described membrane component is 0.1 ~ 0.3 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410141546.9A CN104973725B (en) | 2014-04-09 | 2014-04-09 | A kind of processing recovery method of phosphate discharge liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410141546.9A CN104973725B (en) | 2014-04-09 | 2014-04-09 | A kind of processing recovery method of phosphate discharge liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104973725A true CN104973725A (en) | 2015-10-14 |
| CN104973725B CN104973725B (en) | 2018-04-10 |
Family
ID=54270755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410141546.9A Active CN104973725B (en) | 2014-04-09 | 2014-04-09 | A kind of processing recovery method of phosphate discharge liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104973725B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111268848A (en) * | 2020-03-27 | 2020-06-12 | 浙江迪萧环保科技有限公司 | Clean and efficient phosphoric acid recovery process |
| CN113830744A (en) * | 2021-09-14 | 2021-12-24 | 成都市科隆化学品有限公司 | Method for efficiently concentrating and dechlorinating phosphoric acid |
| CN116621402A (en) * | 2023-07-26 | 2023-08-22 | 杭州永洁达净化科技有限公司 | Near-zero emission recovery method and system for phosphorus-containing polishing waste acid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041649A (en) * | 2007-04-10 | 2007-09-26 | 三达膜科技（厦门）有限公司 | Production method of reclaiming vitamin C and gulonic acid from vitamin C mother liquid |
| CN101254966A (en) * | 2008-04-14 | 2008-09-03 | 北京特斯顿新材料技术发展有限公司 | Recovery method of phosphate discharge liquid |
| CN102030441A (en) * | 2009-09-29 | 2011-04-27 | 天津膜科力科技有限公司 | Method for treating wastewater in production of sebacic acid |
| CN202390205U (en) * | 2011-04-14 | 2012-08-22 | 瓮福（集团）有限责任公司 | Electronic-level phosphoric acid production device |
| CN103466872A (en) * | 2013-08-30 | 2013-12-25 | 中建安装工程有限公司 | Wastewater treatment method for producing hydrogenation catalyst of heavy oil |
| CN103525535A (en) * | 2013-09-27 | 2014-01-22 | 奥克化学扬州有限公司 | Method for purifying PEG (polyethylene glycol) in waste wire-cutting mortar |
-
2014
- 2014-04-09 CN CN201410141546.9A patent/CN104973725B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041649A (en) * | 2007-04-10 | 2007-09-26 | 三达膜科技（厦门）有限公司 | Production method of reclaiming vitamin C and gulonic acid from vitamin C mother liquid |
| CN101254966A (en) * | 2008-04-14 | 2008-09-03 | 北京特斯顿新材料技术发展有限公司 | Recovery method of phosphate discharge liquid |
| CN102030441A (en) * | 2009-09-29 | 2011-04-27 | 天津膜科力科技有限公司 | Method for treating wastewater in production of sebacic acid |
| CN202390205U (en) * | 2011-04-14 | 2012-08-22 | 瓮福（集团）有限责任公司 | Electronic-level phosphoric acid production device |
| CN103466872A (en) * | 2013-08-30 | 2013-12-25 | 中建安装工程有限公司 | Wastewater treatment method for producing hydrogenation catalyst of heavy oil |
| CN103525535A (en) * | 2013-09-27 | 2014-01-22 | 奥克化学扬州有限公司 | Method for purifying PEG (polyethylene glycol) in waste wire-cutting mortar |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111268848A (en) * | 2020-03-27 | 2020-06-12 | 浙江迪萧环保科技有限公司 | Clean and efficient phosphoric acid recovery process |
| CN113830744A (en) * | 2021-09-14 | 2021-12-24 | 成都市科隆化学品有限公司 | Method for efficiently concentrating and dechlorinating phosphoric acid |
| CN116621402A (en) * | 2023-07-26 | 2023-08-22 | 杭州永洁达净化科技有限公司 | Near-zero emission recovery method and system for phosphorus-containing polishing waste acid |
| CN116621402B (en) * | 2023-07-26 | 2023-10-20 | 杭州永洁达净化科技有限公司 | Near-zero emission recovery method and system for phosphorus-containing polishing waste acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104973725B (en) | 2018-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104445755B (en) | A kind of method for ammonium chloride waste-water recycling treatment | |
| CN106315991B (en) | A kind of point salt technique for industrial wastewater | |
| CN103304088B (en) | Recycling method of high brine waste water based on forward osmosis | |
| CN105236661B (en) | The system and method for preparing ultra-pure water of no effuent discharge | |
| CN103073146A (en) | Waste water treatment method and device based on forward osmosis and membrane distillation | |
| CN105000737A (en) | Industrial sewage treatment system and sewage treatment method | |
| CN106517632A (en) | Concentration device and method for reverse osmosis membrane concentrated ammonium nitrate waste water | |
| CN107512806A (en) | Ion exchange resin waste water zero discharge processing method | |
| CN100376472C (en) | Method for utilizing low concentration waste sulfuric acid using multiple condensation and flash distillation | |
| CN105198144A (en) | High-salinity high-hardness wastewater zero-discharging method | |
| CN104973725A (en) | Treatment and recycle method of phosphoric acid waste liquid | |
| CN104973581A (en) | Treatment method of phosphoric acid waste liquid | |
| CN203007081U (en) | Low-temperature multi-effect distillation desalination system | |
| CN104973658A (en) | Concentrating method of low-concentration phosphoric acid waste liquid | |
| CN204614460U (en) | Boron-containing radioactive waste liquid deep purifying reclaims the equipment of boric acid simultaneously | |
| CN107365003A (en) | A kind of processing method of coal chemical industry brine waste | |
| CN204125277U (en) | A kind of portable ultra-pure-water treatment system | |
| CN116573813A (en) | System and method for treating regenerated wastewater by coupling degassing membrane with bipolar membrane | |
| CN105601012A (en) | Method for treating acid-containing waste liquid by condensation and distillation purification | |
| CN108726769A (en) | A kind of advanced treatment and reclamation method of flue gas desulfurization liquid | |
| CN211311148U (en) | High-difficulty sewage treatment system | |
| CN204939035U (en) | Tertiary iron phosphate wastewater zero discharge treatment unit | |
| CN204529600U (en) | A kind of system of thick-oil waste water treatment for reuse station boiler | |
| CN204325043U (en) | A kind of separating and treating apparatus of thermal treatment waste water | |
| CN103420439A (en) | Treatment method for realizing leachate pollutant zero-discharge and recycling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |