CN104030496B - A kind of dense oil extraction wastewater degree of depth sofening treatment reuse method - Google Patents
A kind of dense oil extraction wastewater degree of depth sofening treatment reuse method Download PDFInfo
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Abstract
The invention discloses a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method, belong to sewage treatment area.This dense oil extraction wastewater degree of depth sofening treatment reuse method is: (1) carries out pre-treatment to dense oil extraction wastewater; (2) cascade filtration process; (3) dense oil extraction wastewater is imported resin cation exchange device and carry out sofening treatment, then carry out degree of depth sofening treatment by resin interchanger, make its calcium ion, magnesium ion content≤0.02mg/L, then imported reuse in thick oil heat-collecting steam boiler; Described resin interchanger includes alpha-amino phosphonate type resin switching layer and imido oxalic acid type chelate resin switching layer.Its advantage is: the method does not need silica removal unit; The operation scheme of resin interchanger used has various type; Save clear water resource, protection of the environment, has significant economic benefit, good social benefit and environmental benefit.
Description
Technical field
The present invention relates to a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method, belong to sewage treatment area.
Background technology
Dense oil extraction wastewater is the water that oil field mining liquid goes out through oily water separation.The water quality of dense oil extraction wastewater is complicated, not only contains a large amount of positively charged ions (as Ca
2+, Mg
2+, Fe
2+deng), a large amount of negatively charged ion is (as Cl
-, SO4
2-, CO
3 2-, HCO
3 -deng), also containing a small amount of as heavy metal compound and U such as chromium, copper, lead, mercury
238, Th
232, Ra
226deng the Radiochemicals of trace; And there is the features such as water temperature is high, viscosity large, profit density difference is little, emulsification is serious, biodegradability is poor, intractability is large.The waste of resource and the pollution of other water body can be caused if be directly discharged into by dense oil extraction wastewater in water surrounding, and even pollute whole environment.Along with the change of oil field at home heavy crude heat extraction mode, dense oil extraction wastewater amount is increasing.The process of dense oil extraction wastewater is the Tough questions that oil field faces.In order to saving water resource and protection of the environment, be badly in need of dense oil extraction wastewater effectively to process.
At present, have three kinds: one to be done advanced treatment to the method for disposal of dense oil extraction wastewater both at home and abroad, be back to thick oil heat-collecting steam boiler; Two is on the basis of oil removing process, increases biochemical treatment, qualified discharge; It three is can meet oil-field flooding water-quality guideline after being processed, for the stratum re-injection of thin oil block.
Dense oil extraction wastewater outlet is different, and require that the water quality standard reached is also different, treatment scheme, treatment process are not identical yet.Although dense oil extraction wastewater matter composition more complicated, stability is better, after treatment as thermal recovery boiler feedwater, has very large economic benefit, social benefit and environmental benefit, therefore can carry out cycling and reutilization to it, accomplish resource utilization, rationalization.Be back to thick oil heat-collecting steam boiler, only need remove the impurity (oil and suspended substance, hardness, silicon-dioxide etc.) in recovered water, keep water conditioning just passable.No matter the method is from environment protection, or making full use of from the viewpoint of water resources and the energy, is all preferred plan.
At present, the leading portion purification process technique of domestic and international dense oil extraction wastewater reuse heat-collecting steam boiler is substantially identical with reinjection technology, is all to adopt the ripe treatment process such as physico-chemical process, the oil in main removal water and suspended substance.Domestic and international viscous crude extraction treatment technology mainly adopts oil trap technology, the combination of the gentle flotation technology of liquid-liquid rotational flow technology etc., and treatment scheme comprises oil removing, oil removal, silica removal and softening 4 links, and equipment is many, and treatment scheme is long.In dense oil extraction wastewater, the concentration of silicon is higher, and hardness residual in water at high temperature forms silicate scale with the pasc reaction of different shape.Therefore remain in some problems in this link of silica removal, as silica removal equipment is complicated, dosing kind is many, chemical feeding quantity is large, sludge quantity that is that produce is large, cost is high and subsequent filter produces fouling or corrosion etc.Boiler water quality is the harshest to the requirement of the content of calcium ions and magnesium ions, because the halfway words of removal of calcium ions and magnesium ions in the water after softening, with the appearance of other ion, serious fouling or etching problem will be caused, so successive depths process is mainly conceived to dirty water softening.Dense oil extraction wastewater after the process of traditional storng-acid cation exchange resin softening process, still residual minim calcium ions and magnesium ions.Operative practice shows, these positively charged ions still can be combined with silicon and easily cause Experiment of Scaling in Stream Injection Generator.
Summary of the invention
The object of the invention is complicated for the silicon removing process equipment of traditional dense oil extraction wastewater treatment process, dosing kind is many, chemical feeding quantity large, the sludge quantity that produces is large, costly, and softening after water not thorough to the removal of calcium ions and magnesium ions, the fouling of strainer or the problem of corrosion, provide a kind of do not need silica removal, only need on the basis of former ion-exchange unit the method for further degree of depth sofening treatment.
Object of the present invention is achieved through the following technical solutions:
A kind of dense oil extraction wastewater degree of depth sofening treatment reuse method, comprises the steps:
(1) pre-treatment is carried out to dense oil extraction wastewater;
(2) carry out cascade filtration process to through step (1) pretreated dense oil extraction wastewater, make the content≤2.0mg/L of the oil in its water outlet, suspended solids content≤5.0mg/L;
(3) dense oil extraction wastewater after step (2) filtration is imported resin cation exchange device and carry out sofening treatment, make the total hardness≤0.1mg/L of water outlet, then under the flow velocity of 15 ~ 25BV/h, degree of depth sofening treatment is carried out by resin interchanger, make its calcium ion, magnesium ion content≤0.02mg/L, then imported reuse in thick oil heat-collecting steam boiler; Described resin interchanger includes alpha-amino phosphonate type resin switching layer and imido oxalic acid type chelate resin switching layer.
Described pre-treatment comprises oil removing buffering, cyclone reaction and inclined plate sedimentation successively; Described cyclone reaction is add scavenging agent in the recovered water after oil removing buffered, and input amount is 150 ~ 200mg/L, is then passed in Cyclonic reactor by recovered water, and to add alkaline matter regulation system pH value be 8.0 ~ 9.0.
The time of described oil removing buffering is 8 ~ 10 hours, and the time of cyclone reaction is 30 ~ 45min, and the time of inclined plate sedimentation is 2 ~ 4 hours.
Described scavenging agent contains the mixture of in polymerize aluminum chloride, Tai-Ace S 150 and polysilicate aluminum chloride any two kinds, and its mass ratio is 1:3 ~ 3:1.
Described alkaline matter is sodium hydroxide or calcium hydroxide or both mixtures; When it is mixture, mass ratio is 1:4 ~ 4:1.
Described cascade filtration process comprises one-level double filtering filtration treatment and secondary fiber ball filtration treatment.
Described resin cation exchange device is strongly-acid sodium ionomer resin interchanger, and its resin is hud typed strong acid polystyrene gel type resin.
The mass ratio of described alpha-amino phosphonate type resin and imido oxalic acid type chelate resin is 1:5 ~ 5:1.
Described resin interchanger is single-column two-chamber-type, the two room two-stage series connection type of single-column or single-column single chamber two-stage series connection type.
Described resin reproducible utilization, its renovation process comprises the steps: to carry out backwash 20 ~ 30 minutes with one-level softening water; Mass percent concentration is 5% ~ 8% salt acid soak 30 ~ 40 minutes; One-level softening water soaks 30 ~ 40 minutes; Mass percent concentration is 4% ~ 6% soaking with sodium hydroxide 30 ~ 40 minutes; Just wash with one-level softening water.
Hardness of the present invention is with calcium carbonate.
The present invention's dioxide-containing silica in water is under the condition of 100 ~ 300mg/L, maintains system run all right, non-scaling, and effluent quality can meet oilfield sewage reuse wet steam generator water-quality guideline simultaneously.Cyclone reaction precipitation, high efficiency filter, ion-exchange three operating unit cooperation, complete task of the present invention jointly.
As shown in Figure 1, technical process of the present invention is followed successively by process flow sheet of the present invention: dense oil extraction wastewater → oil removing surge tank → Cyclonic reactor → inclined plate sedimentation tank → grade one filter → secondary filter → one-level interchanger → secondary interchanger → injection boiler.
Hud typed strong acid polystyrene gel type resin used is with the polymkeric substance of non-vinylbenzene and divinylbenzene for core, is the shell be coated on outside core with the polymkeric substance of vinylbenzene and divinylbenzene.
Resin reproducible utilization, its renovation process one-level softening water carries out backwash, and one-level softening water is intake by bottom ion-exchanger, top water outlet, backwash 20 ~ 30 minutes.Regeneration of hydrochloric acid, hydrochloric acid soln enters ion-exchanger by bottom, soaks 30 ~ 40 minutes; Then enter the residual acid of replacing ion-exchanger with softening water from bottom, soak 30 ~ 40 minutes.Sodium hydroxide solution regenerates, and alkali lye enters ion-exchanger by bottom, soaks 30 ~ 40 minutes.Finally adopt one-level softening water just to wash, one-level softening water is intake by top, bottom water outlet.
Degree of depth sofening treatment reuse method of the present invention middle soluble solids concentration of disposing of sewage is 2000 ~ 7000mg/L, and total hardness is no more than the Heavy Oil High Temperature recovered water of 300mg/L.
Under the high-temperature operation condition of thick oil heat-collecting steam boiler, calcium ions and magnesium ions and silicon easily form insoluble complex compound, separate out and form fouling from solution.And resin has special functional group, dative bond can be formed to single metal atom.Adopt resin, calcium ions and magnesium ions concentration in Heavy Oil High Temperature recovered water is reduced to trace ppb level, does not have, with the material of pasc reaction, therefore also just to limit this fouling mechanisms, thus steam boiler can be made to operate under high silicon content, avoid lime soften for sewage silicon removing process.Adopt the water quality of the method process of this invention, reach the requirement of oilfield sewage reuse wet steam generator water quality standard.The degree of depth sofening treatment system that this technique adopts, instead of complicated operation, sludge quantity be large, chemical agent melded system that processing costs is high, making operation more simple and convenient, because this invention technology greatly reduces calcium ions and magnesium ions, achieving good effect to preventing the scale formation of boiler.Compare with the silicon removing process of routine, this process costs saves more than 40%, solves the unmanageable problem of dense oil extraction wastewater silica removal, brings again good Social benefit and economic benefit.
A kind of dense oil extraction wastewater degree of depth sofening treatment reuse method provided by the invention, the sludge quantity efficiently solve silicon removing process equipment complexity, dosing kind is many, chemical feeding quantity large, producing is large, costly, and softening after water not thorough to the removal of calcium ions and magnesium ions, the fouling of strainer or the problem of corrosion reach the effect to dense oil extraction wastewater process recycling, for industry energy conservation consumption reduction has made demonstration.
Method provided by the invention; the degree of depth is carried out to dense oil extraction wastewater and softens Treatment for Reuse; reach QSY1275-2010 oilfield sewage reuse wet steam generator water-quality guideline; the method achieve the recycle of dense oil extraction wastewater; save clear water resource; protection of the environment, has significant economic benefit, good social benefit and environmental benefit.
Beneficial effect of the present invention is:
(1) recovered water after dense oil extraction wastewater degree of depth sofening treatment reuse method provided by the invention process is adopted to reach the requirement of oilfield sewage reuse wet steam generator water quality standard; the method achieve the recycle of dense oil extraction wastewater; save clear water resource; protection of the environment, has significant economic benefit, good social benefit and environmental benefit.
(2) the present invention is by dense oil extraction wastewater process, is back to heat-collecting steam boiler and has practicality and economy, both saved clear water resource and again saved heat energy.
(3) the resin interchanger that dense oil extraction wastewater degree of depth sofening treatment reuse method provided by the invention is used has various type, comprise single-column two-chamber-type, the two room two-stage series connection type of single-column or single-column single chamber two-stage series connection type, corresponding operation scheme is single-column two rooms monopolar operation, single-column two rooms two-stage series connection runs or single-column single chamber two-stage series connection runs.
(4) degree of depth sofening treatment in the present invention uses mixed type resin melded system, does not need silica removal unit, instead of complicated operation, sludge quantity is large, chemical agent melded system that processing costs is high, makes operation more simple and convenient.If adopt silica removal processing unit, cost is 8 yuan/m
3~ 10 yuan/m
3, and degree of depth sofening treatment technology, cost is less than 3 yuan/m
3.Designed capacity 50000m every day of heat-collecting steam boiler is entered according to sewage
3calculate, within 1 year, will save processing cost 1.3 hundred million yuan, add sludge treatment expense 100,000,000 yuan after silica removal, total cost-saved 2.3 hundred million yuan every year.Year reduces discharging about 300,000 tons, mud, develops a circular economy significant to environment protection and oil field.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention is further described.
Fig. 1 is the process flow sheet of dense oil extraction wastewater degree of depth sofening treatment reuse method.
Fig. 2 is the schematic diagram of single-column two-chamber-type resin interchanger.
Fig. 3 is the schematic diagram of single-column two rooms two-stage series connection type resin interchanger.
Fig. 4 is the schematic diagram of single-column single chamber two-stage series connection type resin interchanger.
Wherein 1 is alpha-amino phosphonate type resin switching layer, and 2 is imido oxalic acid type chelate resin switching layer.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
Certain oil-field thick-oil recovered water temperature 90 DEG C, pH value is 7.5, and soluble solids content is 4000 mg/L, and oleaginousness is 520 mg/L, and suspended solids content is 362 mg/L, total hardness (with calcium carbonate) 106mg/L, dioxide-containing silica 253mg/L.
Dense oil extraction wastewater enters in oil removing surge tank and carries out buffering oil removal treatment, and the residence time is 8 hours.Add scavenging agent oil removing oil removal in the ingress of Cyclonic reactor, the dosage 160mg/L of scavenging agent, scavenging agent is the mixture of polymerize aluminum chloride and Tai-Ace S 150, and polymerize aluminum chloride and Tai-Ace S 150 mass ratio are 2:1; Add alkaline matter regulation system pH in the centre of Cyclonic reactor 8.0, alkaline matter is the mixture of sodium hydroxide and calcium hydroxide, and mass ratio is 4:1.After eddy flow hybrid reaction 30min, enter inclined plate sedimentation tank precipitation and disgorging, 4 hours settling times; Remove most oil and suspended substance.Through two-stage filtration (two-stage filtration carries out respectively in one-level Double-filter material filter and secondary fiber ball strainer), remove surplus oil and suspended substance in water, make its water outlet oleaginousness≤2.0mg/L, suspended solids content≤5.0mg/L; Enter one-level sodium form cationic exchange softening agent (its resin is hud typed strong acid polystyrene gel type resin), use total hardness of water≤0.1mg/L; Then under flow velocity is 15BV/h, enter second stage resin interchanger, this is that the two room mixing resin interchanger of single-column carries out single-stage operation, fill in the chamber up and down of interchanger by alpha-amino phosphonate type and imido oxalic acid type two kinds of resins respectively according to mass ratio 1:5, the schematic diagram of its single-column two-chamber-type resin interchanger used as shown in Figure 2, arrow in figure is the flow direction of recovered water, recovered water first through alpha-amino phosphonate type resin switching layer, through imido oxalic acid type chelate resin switching layer.Calcium ion in the water outlet of degree of depth sofening treatment, magnesium ion content all≤0.02mg/L, finally enter heat-collecting steam boiler reuse.
The regeneration of resin: carry out backwash with one-level softening water, one-level softening water is intake by bottom ion-exchanger, top water outlet, backwash 20 minutes; Regeneration of hydrochloric acid, mass percent concentration be 5% hydrochloric acid soln enter ion-exchanger by bottom, soak 30 minutes; Then softening water is entered the residual acid displacement ion-exchanger from bottom, soak 30 minutes; Mass percent concentration is the sodium hydroxide solution regeneration of 4%, and alkali lye enters ion-exchanger by bottom, soaks 30 minutes; Finally adopt one-level softening water just to wash, one-level softening water is intake by top, bottom water outlet.
Embodiment 2
Certain oil-field thick-oil recovered water temperature is 80 DEG C, and pH is 7.8, and salinity is 3500 mg/L, and oleaginousness is 620mg/L, and suspended solids content is 435mg/L, and hardness is 129mg/L, and dioxide-containing silica is 280mg/L.
Dense oil extraction wastewater enters oil removing surge tank, 8.5h is stopped in surge tank, scavenging agent oil removing oil removal is added in the import of Cyclonic reactor, the dosage 200mg/L of scavenging agent, scavenging agent is the mixture of polymerize aluminum chloride and polysilicate aluminum chloride, and the mass mixing ratio of polymerize aluminum chloride and polysilicate aluminum chloride is 3:1; Add alkaline matter regulation system pH in the centre of Cyclonic reactor 9.0, alkaline matter is the mixture of sodium hydroxide and calcium hydroxide, and wherein the mass ratio of sodium hydroxide and calcium hydroxide is 1:3.After eddy flow hybrid reaction 45min, enter inclined plate sedimentation tank precipitation and disgorging, 2 hours settling times; Remove most oil and suspended substance.Through two-stage filtration (two-stage filtration carries out respectively in one-level Double-filter material filter and secondary fiber ball strainer), remove surplus oil and suspended substance in water, make its water outlet oleaginousness≤2.0mg/L, suspended solids content≤5.0mg/L, enter one-level sodium form cation exchanger (its resin is hud typed strong acid polystyrene gel type resin), make total hardness≤0.1mg/L, then second stage resin interchanger is entered, this is that the two room mixing resin interchanger of single-column carries out series operation, resin by alpha-amino phosphonate type and imido oxalic acid type proportionally 5:1 fill in the chamber up and down of interchanger respectively, the schematic diagram of its single-column used two rooms two-stage series connection type resin interchanger as shown in Figure 3, arrow in figure is the flow direction of recovered water, the alpha-amino phosphonate type resin switching layer of recovered water first successively in first exchange column and imido oxalic acid type chelate resin switching layer, alpha-amino phosphonate type resin switching layer again successively in second exchange column and imido oxalic acid type chelate resin switching layer, wherein the flow velocity of water outlet is 20BV/h, calcium ion in water outlet after degree of depth sofening treatment, magnesium ion content all≤0.02mg/L, finally enter heat-collecting steam boiler.
The regeneration of resin: carry out backwash with one-level softening water, one-level softening water is intake by bottom ion-exchanger, top water outlet, backwash 30 minutes; Regeneration of hydrochloric acid, mass percent concentration be 8% hydrochloric acid soln enter ion-exchanger by bottom, soak 40 minutes; Then enter the residual acid of replacing ion-exchanger with softening water from bottom, soak 40 minutes; Mass percent concentration is the sodium hydroxide solution regeneration of 5%, and alkali lye enters ion-exchanger by bottom, soaks 40 minutes.Finally adopt one-level softening water just to wash, one-level softening water is intake by top, bottom water outlet.
Embodiment 3
Certain oil-field thick-oil recovered water temperature is 85 DEG C, and pH is 8.1, and salinity is 2900 mg/L, and oleaginousness is 451mg/L, and suspended solids content is 392 mg/L, and hardness is 96mg/L, and dioxide-containing silica is 261mg/L.
Dense oil extraction wastewater enters oil removing surge tank, 9h is stopped in surge tank, scavenging agent oil removing oil removal is added in the ingress of Cyclonic reactor, the dosage 150mg/L of scavenging agent, scavenging agent is the mixture of polymerize aluminum chloride and polysilicate aluminum chloride, and the mass mixing ratio of polymerize aluminum chloride and polysilicate aluminum chloride is 1:3; Add alkaline matter regulation system pH in the centre of Cyclonic reactor 8.5, alkaline matter is the mixture of sodium hydroxide and calcium hydroxide, and the mass ratio of sodium hydroxide and calcium hydroxide is 1:4.After eddy flow hybrid reaction 40min, enter inclined plate sedimentation tank precipitation and disgorging, 3 hours settling times, remove most oil and suspended substance, through two-stage filtration (two-stage filtration carries out respectively in one-level Double-filter material filter and secondary fiber ball strainer), remove surplus oil and suspended substance in water, make its water outlet oleaginousness≤2.0mg/L, suspended solids content≤5.0mg/L, enter one-level sodium form cation exchanger (its resin is hud typed strong acid polystyrene gel type resin), make total hardness≤0.1mg/L, then second stage resin interchanger is entered, this is the series operation of two kinds of resin exchange columns, flow velocity is 25BV/h, fill in 2 softening posts respectively by alpha-amino phosphonate type resin and imido oxalic acid type chelate resin and carry out series operation, it is single-column single chamber two-stage series connection type resin interchanger (as shown in Figure 3), arrow in figure is the flow direction of recovered water, recovered water is first through filling the exchange column of alpha-amino phosphonate type resin again through filling imido oxalic acid type chelate resin exchange column, calcium ion after degree of depth sofening treatment in water outlet, magnesium ion content all≤0.02mg/L, finally enter heat-collecting steam boiler.
The regeneration of resin: carry out backwash with one-level softening water, one-level softening water is intake by bottom ion-exchanger, top water outlet, backwash 25 minutes; Regeneration of hydrochloric acid, mass percent concentration be 7% hydrochloric acid soln enter ion-exchanger by bottom, soak 35 minutes; Then enter the residual acid of replacing ion-exchanger with softening water from bottom, soak 35 minutes; Mass percent concentration is the sodium hydroxide solution regeneration of 6%, and alkali lye enters ion-exchanger by bottom, soaks 35 minutes; Finally adopt one-level softening water just to wash, one-level softening water is intake by top, bottom water outlet.
Embodiment 4
Certain oil-field thick-oil recovered water temperature is 80 DEG C, and pH is 7.8, and salinity is 3500 mg/L, and oleaginousness is 620mg/L, and suspended solids content is 435mg/L, and hardness is 129mg/L, and dioxide-containing silica is 280mg/L.
Dense oil extraction wastewater enters oil removing surge tank, 9h is stopped in surge tank, scavenging agent oil removing oil removal is added in the import of Cyclonic reactor, the dosage 200mg/L of scavenging agent, scavenging agent is the mixture of polymerize aluminum chloride and polysilicate aluminum chloride two kinds, and the mass mixing ratio of polymerize aluminum chloride and polysilicate aluminum chloride is 3:1; Add alkaline matter regulation system pH in the centre of Cyclonic reactor 8.0, alkaline matter is sodium hydroxide.After eddy flow hybrid reaction 30min, enter inclined plate sedimentation tank precipitation and disgorging, 4 hours settling times; Remove most oil and suspended substance.Through two-stage filtration (two-stage filtration carries out respectively in one-level Double-filter material filter and secondary fiber ball strainer), remove surplus oil and suspended substance in water, make its water outlet oleaginousness≤2.0mg/L, suspended solids content≤5.0mg/L, enter one-level sodium form cation exchanger (its resin is hud typed strong acid polystyrene gel type resin), make total hardness≤0.1mg/L, then second stage resin interchanger is entered, this is that the two room mixing resin interchanger of single-column carries out series operation, resin by alpha-amino phosphonate type and imido oxalic acid type proportionally 5:1 fill in the chamber up and down of interchanger respectively, the schematic diagram of its single-column used two rooms two-stage series connection type resin interchanger as shown in Figure 3, arrow in figure is the flow direction of recovered water, the alpha-amino phosphonate type resin switching layer of recovered water first successively in first exchange column and imido oxalic acid type chelate resin switching layer, alpha-amino phosphonate type resin switching layer again successively in second exchange column and imido oxalic acid type chelate resin switching layer, wherein the flow velocity of water outlet is 20BV/h, calcium ion in water outlet after degree of depth sofening treatment, magnesium ion content all≤0.02mg/L, finally enter heat-collecting steam boiler.
The regeneration of resin: carry out backwash with one-level softening water, one-level softening water is intake by bottom ion-exchanger, top water outlet, backwash 20 minutes.Regeneration of hydrochloric acid, mass percent concentration is that 5% hydrochloric acid soln enters ion-exchanger by bottom, soaks 30 minutes; Then enter the residual acid of replacing ion-exchanger with softening water from bottom, soak 40 minutes.Mass percent concentration is 5% sodium hydroxide solution regeneration, and alkali lye enters ion-exchanger by bottom, soaks 40 minutes.Finally adopt one-level softening water just to wash, one-level softening water is intake by top, bottom water outlet.
Embodiment 5
Certain oil-field thick-oil recovered water temperature is 80 DEG C, and pH value is 7.8, and salinity is 3500 mg/L, and oleaginousness is 620mg/L, and suspended solids content is 435mg/L, and hardness is 129mg/L, and dioxide-containing silica is 280mg/L.
Dense oil extraction wastewater enters oil removing surge tank, in surge tank, stop 9h, add scavenging agent oil removing oil removal in the import of Cyclonic reactor, the dosage 200mg/L of scavenging agent, scavenging agent is polymerize aluminum chloride and polysilicate aluminum chloride two kinds, and mass mixing ratio when using two kinds of scavenging agents is 3:1; Add alkaline matter regulation system pH in the centre of Cyclonic reactor 8.0, alkaline matter is calcium hydroxide.After eddy flow hybrid reaction 30min, enter inclined plate sedimentation tank precipitation and disgorging, 4 hours settling times; Remove most oil and suspended substance.Through two-stage filtration (two-stage filtration carries out respectively in one-level Double-filter material filter and secondary fiber ball strainer), remove surplus oil and suspended substance in water, make its water outlet oleaginousness≤2.0mg/L, suspended solids content≤5.0mg/L, enter one-level sodium form cation exchanger (its resin is hud typed strong acid polystyrene gel type resin), make total hardness≤0.1mg/L, then second stage resin interchanger is entered, this is that the two room mixing resin interchanger of single-column carries out series operation, resin by alpha-amino phosphonate type and imido oxalic acid type proportionally 5:1 fill in the chamber up and down of interchanger respectively, the schematic diagram of its single-column used two rooms two-stage series connection type resin interchanger as shown in Figure 3, arrow in figure is the flow direction of recovered water, the alpha-amino phosphonate type resin switching layer of recovered water first successively in first exchange column and imido oxalic acid type chelate resin switching layer, alpha-amino phosphonate type resin switching layer again successively in second exchange column and imido oxalic acid type chelate resin switching layer, wherein the flow velocity of water outlet is 20BV/h, calcium ion in water outlet after degree of depth sofening treatment, magnesium ion content all≤0.02mg/L, finally enter heat-collecting steam boiler.
The regeneration of resin: carry out backwash with one-level softening water, one-level softening water is intake by bottom ion-exchanger, top water outlet, backwash 30 minutes.Regeneration of hydrochloric acid, mass percent concentration is that 5% hydrochloric acid soln enters ion-exchanger by bottom, soaks 40 minutes; Then enter the residual acid of replacing ion-exchanger with softening water from bottom, soak 30 minutes.Mass percent concentration is 5% sodium hydroxide solution regeneration, and alkali lye enters ion-exchanger by bottom, soaks 30 minutes.Finally adopt one-level softening water just to wash, one-level softening water is intake by top, bottom water outlet.
Single-column two rooms tandem type resin interchanger in the present invention, being not limited to two-stage, also can be more than two-stage, and same single-column single chamber tandem type resin interchanger is also not limited to two-stage, also can be more than two-stage.
Claims (9)
1. a dense oil extraction wastewater degree of depth sofening treatment reuse method, is characterized in that comprising the steps:
(1) pre-treatment is carried out to dense oil extraction wastewater;
(2) carry out cascade filtration process to through step (1) pretreated dense oil extraction wastewater, make the content≤2.0mg/L of the oil in its water outlet, suspended solids content≤5.0mg/L;
(3) dense oil extraction wastewater after step (2) filtration is imported resin cation exchange device and carry out sofening treatment, make the total hardness≤0.1mg/L of water outlet, then under the flow velocity of 15 ~ 25BV/h, degree of depth sofening treatment is carried out by resin interchanger, make its calcium ion, magnesium ion content≤0.02mg/L, then imported reuse in thick oil heat-collecting steam boiler; Described resin interchanger includes alpha-amino phosphonate type resin switching layer and imido oxalic acid type chelate resin switching layer; Described resin cation exchange device is strongly-acid sodium ionomer resin interchanger, and its resin is hud typed strong acid polystyrene gel type resin.
2. a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method according to claim 1, is characterized in that: described pre-treatment comprises oil removing buffering, cyclone reaction and inclined plate sedimentation successively; Described cyclone reaction is add scavenging agent in the recovered water after oil removing buffered, and input amount is 150 ~ 200mg/L, is then passed in Cyclonic reactor by recovered water, and to add alkaline matter regulation system pH value be 8.0 ~ 9.0.
3. a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method according to claim 2, is characterized in that: the time of described oil removing buffering is 8 ~ 10 hours, and the time of cyclone reaction is 30 ~ 45min, and the time of inclined plate sedimentation is 2 ~ 4 hours.
4. a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method according to Claims 2 or 3, it is characterized in that: described scavenging agent contains the mixture of in polymerize aluminum chloride, Tai-Ace S 150 and polysilicate aluminum chloride any two kinds, its mass ratio is 1:3 ~ 3:1.
5. a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method according to Claims 2 or 3, is characterized in that: described alkaline matter is sodium hydroxide or calcium hydroxide or both mixtures; When it is mixture, mass ratio is 1:4 ~ 4:1.
6. a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method according to claim 1, is characterized in that: described cascade filtration process comprises one-level double filtering filtration treatment and secondary fiber ball filtration treatment.
7. a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method according to claim 1, is characterized in that: the mass ratio of described alpha-amino phosphonate type resin and imido oxalic acid type chelate resin is 1:5 ~ 5:1.
8. a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method according to claim 1, is characterized in that: described resin interchanger is single-column two-chamber-type, the two room two-stage series connection type of single-column or single-column single chamber two-stage series connection type.
9. a kind of dense oil extraction wastewater degree of depth sofening treatment reuse method according to claim 1 or any one of 6-8, is characterized in that: described resin reproducible utilization, and its renovation process comprises the steps: to carry out backwash 20 ~ 30 minutes with one-level softening water; Mass percent concentration is 5% ~ 8% salt acid soak 30 ~ 40 minutes; One-level softening water soaks 30 ~ 40 minutes; Mass percent concentration is 4% ~ 6% soaking with sodium hydroxide 30 ~ 40 minutes; Just wash with one-level softening water.
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| CN107758717B (en) * | 2017-09-08 | 2020-03-13 | 中国神华能源股份有限公司 | Method for removing calcium from aluminum chloride solution |
| CN110316863A (en) * | 2019-07-03 | 2019-10-11 | 湖北君集水处理有限公司 | A kind of system and method for Produced Water In Oil-gas Fields, Ngi modification reuse |
| CN115448486A (en) * | 2021-06-09 | 2022-12-09 | 中国石油天然气集团有限公司 | Method and system for reusing silicon-free heavy oil produced water in steam injection boiler |
| WO2022257842A1 (en) * | 2021-06-09 | 2022-12-15 | 中国石油天然气集团有限公司 | Method and system for recycling heavy oil produced water for use in steam injection boiler without desilication |
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| CN102815765A (en) * | 2012-08-30 | 2012-12-12 | 中国石油天然气股份有限公司 | Deep softening method of thick oil sewage |
| CN102826680A (en) * | 2012-08-30 | 2012-12-19 | 中国石油天然气股份有限公司 | High silicon-containing waste water in oil field reuse boiler pretreatment technology and apparatus |
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| CN102815765A (en) * | 2012-08-30 | 2012-12-12 | 中国石油天然气股份有限公司 | Deep softening method of thick oil sewage |
| CN102826680A (en) * | 2012-08-30 | 2012-12-19 | 中国石油天然气股份有限公司 | High silicon-containing waste water in oil field reuse boiler pretreatment technology and apparatus |
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Address after: 430072 Hubei Province, Wuhan city Wuchang District of Wuhan University Luojiashan Co-patentee after: KARAMAY SANDA NEW TECHNOLOGY CO., LTD. Patentee after: Wuhan University Address before: 430072 Hubei Province, Wuhan city Wuchang District of Wuhan University Luojiashan Co-patentee before: Karamay Sanda New Technology Development Co., Ltd. Patentee before: Wuhan University |