CN110240315A - The method and device thereof that boron processing cycle recycles are removed for guanidine glue fracturing outlet liquid - Google Patents

The method and device thereof that boron processing cycle recycles are removed for guanidine glue fracturing outlet liquid Download PDF

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CN110240315A
CN110240315A CN201910529851.8A CN201910529851A CN110240315A CN 110240315 A CN110240315 A CN 110240315A CN 201910529851 A CN201910529851 A CN 201910529851A CN 110240315 A CN110240315 A CN 110240315A
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glue
boron
processing
fracturing outlet
outlet liquid
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徐乾均
徐萍
张桂泉
刘小明
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CHENGDU GUOSHENG ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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CHENGDU GUOSHENG ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/108—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention belongs to oil gas field field of environment pollution control, boron processing cycle reuse method and its device are removed for guanidine glue fracturing outlet liquid more particularly to one kind, after the method is by efficiently breaking the de- steady and hard-off pretreatment of glue, solid-liquid separation treatment to the progress of guanidine glue fracturing outlet liquid, removing boron processing and the processing such as sedimentation filtration is handled, recycled to achieve the purpose that guanidine glue fracturing outlet liquid is secondary with liquid.Compared with the conventional method, integrated artistic process of the present invention is simple, clear thinking, strong innovation, stability are high, easy to operate, on influencing the secondary main component with liquid cycling and reutilization in guanidine glue fracturing outlet liquid such as: boron, Ca2+, Mg2+, Al3+, Fe2+ are effectively removed and unmasked, it is adversely affected caused by thoroughly eliminating because of shielding failure, solves guanidine gum fracturing fluid environmental pollution.It is suitble to scale, the mobile processing of the processing of industrialized sewage treatment plant or scene.

Description

The method and device thereof that boron processing cycle recycles are removed for guanidine glue fracturing outlet liquid
Method field
The invention belongs to oil gas field field of environment pollution control, and in particular to one kind is for guanidine glue fracturing outlet liquid except at boron Manage the method and device thereof of cycling and reutilization.
Background method
(1) guanidine glue fracturing outlet liquid source
Well fracturing operation is the main means of low-permeability oil deposit and non-conventional oil gas reservoir development.Hydroxypropyl guar is The water-based fracturing thickener being most widely used at present has become by constantly developing with progress, boron cross-linked hydroxypropyl base guanidine glue The mainstream system of current aqueous fracturing fluid.Because hydroxypropyl guar pressure break system, which has, preferably takes sand, leak-off and rheology control Performance processed.
It can be generated after the completion of fracturing work and largely return drain, fracturing outlet liquid is arranged after pressure break is completed in underground work It is put into the waste water of earth's surface, is a kind of multiphase dispersion of complexity and the thick liquid high with viscosity.Due to various additions The addition of agent, such as thickener, crosslinking agent, fungicide, cleanup additive, clay stabilizer and gel breaker, into stratum after with stratum It is increasingly complex that the contact of water leads to return drain ingredient, return in drain containing a large amount of guanidine glue, remaining crosslinking agent or frozen glue, salt, The substances such as oils, suspended solid particle and bacterium, it is difficult to degrade to have the characteristics that salinity content is high, stability is strong, viscosity is high etc., It is the extremely intractable high pollution waste of oil/gas well, in decades, all none preferable processes split guanidine glue laminated to return Drain qualified discharge and recycling, it is very harmful to ecological environment.
On the one hand, a large amount of water resource is needed when underground work preparing fracturing fluid, to some (such as new in outlying water-deficient area Boundary, Inner Mongol etc.) construction bring certain economic pressures；On the other hand, if being carried out will cause underground with liquid with underground water Water is exhausted, seriously affects ecological environment.Therefore, research and probe is by guanidine glue fracturing outlet liquid waste water except boron processing cycle recycles one It is directly the emphasis of Environment protection of oil field research, protection environment, saving water resource is all had a very important significance.
(2) disposal status and there are the problem of
1. waste liquid pool stores: the fracturing waste liquor that construction operation generates being stored in waste liquid pool, using the side of natural evaporation Formula desiccation finally directly fills.Not only time-consuming for this extensive processing mode, and be concentrated after pollutant for example organic matter, oil, Heavy metal, aldehyde, phenol etc., harm is bigger, and there are serious secondary pollutions.
2. burning: although this mode can control the discharge for returning drain to a certain extent, needing a large amount of fuel (natural gas), energy consumption is extra-high.Processing cost is difficult to bear, and also will cause secondary pollution (atmosphere pollution), and one kind is extremely Extensive processing mode.
3. re-injection: fracturing waste liquor is collected, concentration such as is flocculated, is aoxidized at the pretreatment, then according to a certain percentage with adopt Oily water blending is reprocessed, and re-injection is carried out after processing.This method only adapts to oil reservoir.Re-injection can injure stratum, destructively under Water mends row's balance, influences drinking water safety, causes water resource waste.
4. qualified discharge: using the methods of physics, chemistry, biology to row up to standard after a series of processing of fracturing outlet liquid progress It puts.Since fracturing outlet liquid waste component is complicated, concentration is high, especially the guar gum of ring shaped molecule structure, very not degradable, Even if treatment effect is unsatisfactory, guar gum using multiple combinations techniques such as broken glue, coagulation, advanced oxidation, UF membrane and biologies Keep its extremely unstable the injury of film, to reach " integrated wastewater discharge standard " (GB8978-1996) primary standard (COD≤ 100mg/l, ammonia nitrogen≤15mg/l), processing cost is in 300 yuan/m3More than, so high handling is to oil field and operation commercial city It is difficult to receive, and the condition that many places are not discharged at all.
Therefore, above-mentioned several method handles guanidine glue fracturing outlet liquid, all there is serious secondary pollution, processing cost height etc. Problem not can solve its serious pollution problem, it has also become an important factor for restricting oil field development and environmental protection returns pressure break Drain is carried out except reusing after boron processing in secondary preparing fracturing fluid, is the impartings such as current protection environment, energy-saving and emission-reduction Important mission.
(3) the secondary factor with liquid of guanidine glue fracturing outlet liquid is influenced
Fracturing outlet liquid composition and property is complicated, and there are many factor for influencing the recycling of guanidine glue fracturing outlet liquid, there is pH, Na+、 K+、Ca2+、Mg2+、Fe2+、Fe3+、Cl-、SO4 2-, remaining crosslinking agent, suspended solid (SS) and residue content etc., pass through grinding for many years Study carefully and test, principal element is remaining crosslinking agent (boron), pH value, Ca2+、Fe2+、Al3+、S2-, peroxide and solid phase particles, close Key factor is boron.
Guanidine glue laminated is split system and is returned in drain, and due to the presence of boron, guanidine glue solution is just crosslinked in advance during alkali tune, makes Obtaining fracturing fluid can not normal use.Therefore, total boron content after processing in water must be controlled in≤5mg/l.The removal of boron is very It is difficult.Ca2+The increase of concentration on Matrix viscosity without influence, but will increase crosslinking time, and the heatproof shearing property of frozen glue is deteriorated.Cause This, the Ca after processing in water2+Content must control≤500mg/l；Mg2+The increase of concentration, on Matrix viscosity without influence, but meeting Shorten crosslinking time, the heatproof shearing property of frozen glue is deteriorated.Therefore, Mg must be controlled in water after processing2+Content≤250mg/l. Ca2+、Mg2+It removes simpler.
Work as Fe2+> 1mg/l, with Fe2+The increase of concentration, guanidine gumminess are successively substantially reduced, and illustrate Fe2+Guanidine glue is thickened Capacity is larger, and Fe3+On guanidine glue thickening capabilities without influence.Therefore, in order to guarantee the viscosity of guanidine glue, after processing in water Fe2+≤ 5mg/l must be controlled；S2-And Fe2+Reproducibility ion is belonged to, therefore, S in processing water should be controlled2-≤5mg/l。Fe2+、 S2- removal is simpler.
Al3+On guanidine glue thickening capabilities without influence；Work as Al3+>=10mg/l, with Al3+The increase of concentration, crosslinking time contracting It is short；Work as Al3+>=50mg/l weak can be crosslinked, but hang bad under alkaline condition without crosslinking agent.Therefore, in order to guarantee to press Going on smoothly for construction is split, the Al after handling in water should be controlled3+≤10mg/l。Al3+It removes simpler.
With the increase of peroxide concentrations, Matrix viscosity becomes smaller, and crosslinking time extends, the heatproof resistant to shearing ability of frozen glue It is deteriorated, after 30mg/L, the influence to fracturing fluid property is clearly.Peroxide≤10mg/l should be controlled.Ordinary circumstance Under, return the storage of drain waste water after a few days, due to high organic content in waste water, peroxide lowers soon.
(4) except boron process status and there are the problem of
Boron in guanidine glue fracturing outlet liquid is to influence the secondary main factor with liquid reuse, the content of boron generally 20~ 50mg/l, some meetings are higher, secondary with liquid to will drop to 5mg/l hereinafter, people generally use following several method at present comes pair Boron is removed processing.
1. coagulation sedimentation: being to add coagulant and flocculation aid into fracturing fluid, pass through absorption, bridge formation and cohesion, form wadding Body precipitating.This is the common method of people.Medicament includes lime, aluminium polychloride, aluminum sulfate, polymeric aluminum sulfate iron etc..Advantage It is simple process, medicament purchase is convenient；The disadvantage is that technique is single, powder performance is poor, removes boron low efficiency, it is difficult to realize and repeat benefit With.
2. electric flocculation method: electric flocculation method, that is, electrochemical process, it converts electric energy using electric field, the electrolysis of high current For chemical energy, occur some column physical-chemical reactions and radical chain reaction, generate a large amount of ecosystems [H], [O], [OH], [Fe2+] etc., essence is generated to be adsorbed with the hydroxide colloid of iron, aluminium.There is certain removal effect to boron, but also because of technique list One, boron low efficiency is removed, is not achieved secondary with liquid standard, it is also difficult to realize recycling, and electrical control requirement is high, pole plate is easily blunt Change, energy consumption height, generates H2、O2Equal gases can bring serious security risk to well site or plant stand.
3. RO hyperfiltration: RO reverse osmosis is the UF membrane filter method using osmotic pressure difference for power.RO is anti- Permeate membrane aperture as low as nanoscale (1 nanometer=10-9Rice), under pressure, hydrone can be by RO film, and in raw water The impurity such as inorganic salts, heavy metal ion, organic matter, colloid, bacterium, virus can not be by RO film, to make can to penetrate Pure water and the condensed water that can not be penetrated strictly distinguish.Since the molecular weight of boron is smaller, easily by RO film, therefore, to film It is required that high；Again because guanidine glue has high viscosity characteristic, blocks film easily, influence membrane lifetime or even systemic breakdown；In addition, meeting A large amount of concentrate is generated, the processing of concentrate needs MVR again, and can generate crystal salt (dangerous waste).Not only except effect of boron is poor, also It will increase great deal of investment and generate secondary pollution.
4. ion-exchange resin (IE): being to be exchanged and separated with different ions in water using the peculiar group of ion-exchanger Method.There is special selective chelating resin to appear on the market boron, it is preferable to boron removal effect, but regenerate complicated, difficult, resin Continued depletion, residual boron will cause secondary pollution.Small scale experiments are fine, and large-scale industrial is using to be improved.
5. screen method: also known as masking method, refer to lewis' acid need not be separated and merely through certain chemical reaction (being typically formed complex compound) can no longer generate the process of interference.The processing fracturing outlet liquid such as screen method is at present using more Method, but since shielding medicament dosage, pH value, temperature and additive etc. make the extremely difficult control of technique, complexing power etc., Seriously affect shield effectiveness and performance, control boron content in water body can not quantitatively, so, will lead to crosslinking or in advance or It delays or the problems such as heat resistance is poor.Maximum the disadvantage is that boron is still in water body, possible " escaping from prison " is come out at any time, is repeating benefit Used time loses shielding action with the variation of the conditions such as temperature, pH value, eventually brings to pressing crack construction operation unpredictalbe Risk.In addition, being shielded again very difficult after shielding twice due to the superposition of boron content.
In conclusion oil field is to the used one of the above of processing of the fracturing outlet liquid of guanidine colloid system or several joints in the past Method, either handle after discharge, or except boron it is secondary with liquid reuse, process it is immature or be place Reason cost it is too high or be treatment effect be not obvious or be can not scale chemical plant operation ... etc., all in initial Conceptual phase, it is sharp to ecological environmental pollution and repetition that none effective method can solve a large amount of fracturing outlet liquids at present Problem causes current a large amount of guanidine glue fracturing outlet liquids to be temporarily stored into the pond of hole, and illegal row's event steathily is commonplace, to locality The great Environmental security hidden danger of the compositions such as ecological environment, underground water.Therefore, more efficient, the more economical boron that removes of one kind is explored to handle Process makes guanidine glue fracturing outlet liquid solve its pollution problem to environment, saving water by scale recycling, thoroughly Resource is very important.
Summary of the invention
Aiming at the shortcomings of the existing method, the present invention provides one kind for guanidine glue fracturing outlet liquid except boron processing follows The method and device thereof that ring recycles.
To achieve the goals above, present invention scheme with the following method:
A method of for guanidine glue fracturing outlet liquid except boron processing cycle recycles, the method is by splitting guanidine glue laminated After returning the de- steady and hard-off pretreatment of the efficiently broken glue of drain waste water progress, solid-liquid separation treatment, removing boron processing and sedimentation filtration processing, Obtain can be used for secondary preparing fracturing fluid recycles water.
Further, it includes the broken glue processing of strong oxidizer oxidative cleavage that the efficiently broken glue, which takes off the pretreatment of steady and hard-off to include, Glue destablizing is broken with dedicated gel breaker, the strong oxidizer oxidative cleavage breaks glue processing and refers to in guanidine glue fracturing outlet liquid The oxidative cleavage that remaining crosslinking agent and frozen glue carry out breaks glue processing, and the dedicated gel breaker breaks glue destablizing and refers to guanidine glue laminated Split the aggregation for returning the progress of the colloidal suspended substance in drain, cohesion, net are caught and gantry breaks glue destablizing.
Using above-mentioned further method scheme the utility model has the advantages that
Strong oxidizer oxidative cleavage breaks glue processing can be by the remaining crosslinking agent and frozen glue in guanidine glue fracturing outlet liquid waste water Oxidative cleavage is carried out again and breaks glue, makes the crosslinking boron in remaining crosslinking agent and frozen glue all with borate ion B [OH]4 –Form release It is put in waste water, is more advantageous to B [OH]4 –It is removed with except boron agent is reacted completely；Dedicated gel breaker breaks glue destablizing can With by guanidine glue fracturing outlet liquid waste water suspended matter, colloidal organic matter carry out aggregation, cohesion, net is caught and the broken glue such as gantry take off Steady processing, while the removal of suction-operated part also is caught by net to borate ion；This dual broken glue pretreatment, is this technique It is different from one of most prominent innovative point of other processes, the single coagulation of the sector has been filled up, has ignored remaining crosslinking agent and frozen glue Again break glue treatment process blank.
Further, the strong oxidizer includes persulfate, and the dedicated gel breaker is YPJJ-1.
Located in advance using above-mentioned further method scheme the utility model has the advantages that carrying out dual broken glue using persulfate and YPJJ-1 Reason can significantly improve brokenly the de- steady and pretreated efficiency of hard-off of glue.
Further, the solid-liquid separation treatment includes concentration pre-separation and the diaphragm plate frame filter press of sludge concentration tank Dehydration separation.
Using above-mentioned further method scheme the utility model has the advantages that first passing through the concentration pre-separation of sludge concentration tank can remove Most of water in sludge, then the dehydration separation of diaphragm plate frame filter press is carried out, be conducive to improve diaphragm plate frame filter press in this way Efficiency simultaneously lightens the load.
Further, described to match except boron processing including hydroxide colloid absorption and polyhydroxy for body complexing, the hydrogen-oxygen The absorption of compound colloid refers to using hydroxide colloid to B [OH]4 –Form big micelle after absorption and rapid subsidence from water point It leaves away and removes, the hydroxide colloid, which derives from, removes boron agent 1, and it is that body complexing refers to that matching using polyhydroxy is body that the polyhydroxy, which is matched, In multiple hydroxyl ligands to B [OH]4 –Complex reaction after form big micelle and rapid subsidence after adsorption bridging effect again It is separated from the water removal, the polyhydroxy, which matches to derive from for body, removes boron agent 2.It is described poly- for multi-functional composite high-molecular except boron agent 1 Object is closed, it is described except 1 main component of boron agent is Al2O3、Fe2O3And C element, it is described except 2 main component of boron agent be polyacrylamide and Containing with the polyol for body.
Using above-mentioned further method scheme the utility model has the advantages that
1. what the adsorption bridging of hydroxide colloid acted on removes boron: hydroxide colloid is derived from except boron agent 1, because of B [OH]4 – Bear electricity, it is easy to by the X (OH) of lotus positive electricity2Colloid or Y (OH)3Colloid is adsorbed, and is then caught and is built bridge by absorption, net again Removal is separated from the water after effect sedimentation.
Reaction equation is as follows:
2OH-+X2+→X(OH)2↓
mX(OH)2+nX2+→{[X(OH)2]m·nX2+}2n+↓
{[X(OH)2]m·nX2+}2n++eB[OH]4 –→{[X(OH)2]m·nX2+·eB[OH]4 –}2n-e↓
Or
3OH-+Y3+→Y(OH)3↓
mY(OH)3+nY3+→{[Y(OH)3]m·nY3+}3n+↓
{[Y(OH)3]m·nY3+}3n++eB[OH]4 –→{[Y(OH)3]m·nY3+·eB[OH]4 –}3n-e↓
2. composite flocculation agent removes boron: the polyhydroxy in composite flocculation agent, which matches to derive from for body, removes boron agent 2, B [OH]4 –With remove The LGD of multiple hydroxyls reacts under certain condition in boron agent 2, and generating product is that the tiny colloidal solid containing multiple boron ions suspends Object, i.e. colloidal particle.This boron ion colloidal solid is under the action of flocculant, after settling the effects of absorption and bridge formation It is separated from the water removal.
Reaction equation is as follows:
Two kinds carry out simultaneously except boron mode, cooperate, have effects that it is dual remove boron, obtain boron in water body effectively Removal, content can be lower than 3mg/l hereinafter, fully meeting secondary with liquid requirement.It is this dual except boron processing and this technique have Not in one of most prominent innovative point of other processes, the blank that guanidine glue fracturing outlet liquid removes boron hardly possible has been filled up.
Removing there are two types of boron agent in this technique is respectively designated as except boron agent 1 and except boron agent 2.Except boron agent 1 is alite, work Property the substances such as carbon powder by a kind of high-performance, multi-functional compound macromolecular polymer made of special process, main component Al2O3、 Fe2O3And C element etc..Except boron agent 1 is the main source of hydroxide colloid, suction-operated is not only played, also there is coagulant precipitation Effect；Except boron agent 2 be composite flocculation agent, main component be polyacrylamide and containing be body polyol, polyhydroxy The ligand and B [OH] of based compound4 –Reaction, generating product is the tiny colloidal solid suspended matter containing multiple boron ions, meanwhile, The addition of polyol enhances the adsorption capacity of flocculant, is more advantageous to adsorption bridging effect.
Further, it the described method comprises the following steps:
Step 1 is adjusted modifier treatment and guanidine glue fracturing outlet liquid waste water is adjusted using circulating pump in storage pool Modifier treatment, it is ensured that influent quality is stablized；
Step 2, the efficiently broken de- steady and hard-off pretreatment of glue, takes off steady hard-off processing unit in broken glue, guanidine glue laminated is split the row of returning Liquid waste water, which is pumped, to be promoted in storage pool to aoxidizing in broken glue pond, and tune pH value is 8.0-9.0, strong oxidizer is added, with circulation Pump is uniformly mixed, and stops 6-10h at normal temperature, is completed to the remaining crosslinking agent and the broken glue of frozen glue oxidation in fracturing outlet liquid waste water Processing；Then, guanidine glue fracturing outlet liquid waste water is pumped from the broken Jiao Chi of oxidation and is pumped into 1# dosing pond, Na is added2CO3PH value is adjusted, It is sufficiently stirred, control pH value is completed to carry out guanidine glue fracturing outlet liquid waste water the processing of quenched and hard-off in 8.5-9.0, then, will Dedicated gel breaker is added from 1# dosing pond from flowing in 2# dosing pond, in 3 ‰ -5 ‰ ratio in guanidine glue fracturing outlet liquid waste water, stirs It mixes, is sufficiently mixed dedicated gel breaker with fracturing fluid waste water, then the row of returning is split to guanidine glue laminated from flowing to brokenly glue and taking off steady hard-off processing pond The broken glue that liquid waste water carries out colloidal suspended substance takes off steady hard-off processing, stops 15min-20min, completes broken glue and takes off steady hard-off processing, The supernatant obtained after the sedimentation of 1# horizontal sedimentation tank is that broken glue takes off steady hard-off supernatant；
Step 3, solid-liquid separation treatment first sink the 1# horizontal sedimentation tank in step 2 in solid-liquid separation treatment unit The sludge obtained after drop is pumped into sludge concentration tank and is concentrated, and concentration pre-separation is completed, then by the sludge after concentration using special Plunger pump is promoted to diaphragm plate frame filter press and carries out solid-liquid separation dehydration processing, completes the dehydration separation of plate and frame filter press；
Water after the separation of solid and liquid all returns to fracturing fluid storage pool, and the solid formation after the separation of solid and liquid is wait ferment Sludge.
Step 4 is removing boron processing unit except boron is handled, and takes off steady hard-off supernatant to broken glue obtained in step 2 first In 3# dosing pond, it is 9.0-10.0 that NaOH, which is added, and adjusts pH value, after mixing is sufficiently stirred, is then flowed into water to be processed certainly 4# dosing pond is added by 3 ‰ -5 ‰ and removes boron agent 1, and after mixing is sufficiently stirred, water to be processed is then flowed into 5# dosing pond certainly, It is added by the o of 3 ‰ o~5 ‰ and removes boron agent 2, mixing is sufficiently stirred, water to be processed is removed in boron reaction tank from inflow then, is passed through Micro- aeration is stirred, and stops 6-8h；It finally flow to 2# horizontal sedimentation tank certainly to be settled in advance, obtain except boron supernatant；
Sludge after the 2# horizontal sedimentation tank sedimentation is still pumped into sludge concentration tank and is concentrated, and completes concentration pre-separation, Then the sludge after concentration is promoted to diaphragm plate frame filter press using dedicated plunger pump and carries out solid-liquid separation dehydration processing.
Step 5, sedimentation filtration are settled again except boron supernatant is pumped into inclined-tube sedimentation tank by what step 4 obtained, are settled Supernatant afterwards is filtered to obtain by active-carbon finely fine filtrator recycles water.
It is a kind of to remove the device that boron processing cycle recycles for guanidine glue fracturing outlet liquid, it is included in and adjusts quenched pretreatment list Member, broken glue take off steady hard-off processing unit, solid-liquid separation treatment unit, except boron processing unit and sedimentation filtration processing unit, described Modifier treatment unit and broken glue take off steady hard-off processing unit and are both provided with medicine machine, measuring equipment and blender, aoxidize broken glue Pond, broken Jiao Chi and 1# horizontal sedimentation tank, the solid-liquid separation treatment unit includes sludge concentration tank and diaphragm plate frame filter press, institute It states except boron processing unit includes dosing metering mixer, aerator, except boron reaction tank and 2# horizontal sedimentation tank, it is described to settle Filter processing unit inclined-tube sedimentation tank and active-carbon finely fine filtrator.
Compared with the conventional method, beneficial effects of the present invention:
This method uses strong oxidizer agent to carry out remaining crosslinking agent and frozen glue first, and glue processing is broken in chain rupture and fracturing fluid is special The broken glue destablizing carried out with gel breaker (YPJJ-1) to colloidal substance, the suspended matter etc. in waste water, i.e., dual broken glue are located in advance Reason, releases the crosslinking boron in remaining crosslinking agent or frozen glue all with borate ion B [OH]4 –Form be present in water In；Then the dual boron that removes is taken to handle, first is that B [OH]4 –It is acted on the adsorption bridging of hydroxide colloid；Second is that B [OH]4 –With Adsorption bridging acts on again after the reaction of polyhydroxy ligand in composite flocculation agent, B [OH]4 –It is formed after being acted on by two ways big Micelle removal is separated from the water by sedimentation, finally, total boron content is lower than 5mg/l.It solves guanidine glue fracturing outlet liquid to remove The problem of boron hardly possible makes to can be used as after guanidine glue fracturing outlet liquid wastewater treatment new water resource and is further continued for for secondary (or repeatedly) It configures fracturing fluid and realizes that the zero-emission of waste water and resource follow to solve the problem of environmental pollution of guanidine glue fracturing outlet liquid waste water Ring recycles purpose.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but the present invention can be defined by the claims and The multitude of different ways of covering is implemented.
Embodiment 1
The efficient broken glue of guanidine glue fracturing outlet liquid takes off steady hard-off pre-treatment step:
1. glue processing is broken in the oxidation of oxidant
Fracturing outlet liquid waste water, which is pumped, to be promoted in storage pool to aoxidizing in broken glue pond, and adding alkali (acid) to adjust pH value is 8.0, then It is separately added into a certain amount of strong oxidizer, is allowed to be uniformly mixed with water with circulating pump.It is broken that 6-10h completion oxidation is stopped at normal temperature Glue processing.
2. the aggregation of gel breaker, cohesion, net is caught and the broken glue destablizings such as gantry
It is pumped into dosing pond 1, is added from the broken Jiao Chi of oxidation firstly, aoxidizing guanidine glue fracturing outlet liquid waste water after breaking gel and being pumped Na2CO3PH value is adjusted, stirring is sufficiently mixed medicament with water.PH value controls in 8.5~9.0 ranges.It also carries out at hard-off simultaneously Reason.
Then, the dedicated broken glue of fracturing fluid is added in 3 ‰~5 ‰ ratio through dosing pond 1 from flowing in dosing pond 2 in waste water Agent (YPJJ-1).Stirring, is sufficiently mixed medicament with waste water.It is carried out after mixing from flowing to brokenly glue and take off steady hard-off processing unit Broken glue takes off steady hard-off processing.Residence time controls in 15min~20min.
In guanidine glue fracturing outlet liquid waste water, boron is mainly with borate ion B [OH]4 –Form exist, but there are also one Part is present in remaining crosslinking agent and frozen glue in the form of being crosslinked boron, it is necessary to which the means by breaking glue again make remaining crosslinking agent It all releases with the crosslinking boron in frozen glue with borate ion B [OH]4 –Form be present in water body, so as to the B in water [OH]4 –It is removed with except boron agent is reacted completely；Meanwhile also to suspended matter, colloidal organic matter and a small amount of boron in waste water Acid ion etc. is acted on by Coagulation and Adsorption and being removed, and water quality is improved, to be subsequent except boron processing is prepared.
Broken glue includes two aspects, first is that carrying out oxidative cleavage to remaining crosslinking agent and frozen glue breaks glue, the other is to guanidine Glue fracturing outlet liquid dispersion colloid (charged particles) carries out coagulation and breaks glue.Special attention will be given to a small amount of remaining crosslinking agent and Frozen glue carries out breaking glue processing again, and other techniques such as screen method, some have only carried out simply the fracturing outlet liquid of dispersion Coagulating treatment, do not account at all and a small amount of remaining crosslinking agent and frozen glue carried out to break glue processing again, make the crosslinking of this part Boron could not release, and can not form complex compound, so shielding is not thorough；Some simple coagulations of company just do not have, wildly This small amount of remaining crosslinking agent and frozen glue are reused as resource.
Embodiment 2
Solid-liquid separation treatment step:
1. the concentration pre-separation of sludge concentration tank.Broken glue takes off steady sludge after pre-processing after the sedimentation of horizontal sedimentation tank 1, removes Boron reaction through horizontal sedimentation tank 2 sedimentation after sludge and the sludge after inclined-tube sedimentation tank settles all be pumped into sludge concentration tank into Row concentration pre-separation.Be conducive to improve the efficiency of diaphragm plate frame filter press in this way and lighten the load.
2. the dehydration of diaphragm plate frame filter press separates.
Sludge after concentrated is promoted to diaphragm plate frame filter press using dedicated plunger pump and carries out at solid-liquid separation dehydration Reason.Horizontal sedimentation tank, sludge concentration tank, inclined-tube sedimentation tank, diaphragm plate frame filter press etc. collectively form solid-liquid separation treatment unit.
Embodiment 3
Except boron processing step:
In order to make B [OH]4 –It is effectively removed, this technique takes the dual boron that removes to handle, first is that B [OH]4 –With hydroxide The adsorption bridging of colloid acts on；Second is that B [OH]4 –With adsorption bridging is made again after the reacting of the polyhydroxy ligand in composite flocculation agent With B [OH]4 –Big micelle is formed after being acted on by two ways and removal is separated from the water by sedimentation.
It is handled 1. what the adsorption bridging of hydroxide colloid acted on removes boron: in dosing pond 3, adding NaOH tune pH value, stirred, It is sufficiently mixed medicament with water.PH value controls in 8.5~9.0 ranges；In dosing pond 4, it is added by 3 ‰~5 ‰ and removes boron agent 1, stirring is sufficiently mixed medicament with water.
2. the boron that removes of composite flocculation agent is handled: being pressed in dosing pond 5It is added and removes boron agent 2, stirring makes medicine Agent is sufficiently mixed with water.
In order to keep reaction more thorough, it is stirred in except boron reaction tank by micro- aeration；Meanwhile folding is equipped in reaction tank Flowing plate can increase the residence time, and the residence time controlled at 6-8 hours.
It is above two to be carried out simultaneously except boron mode, cooperate, have effects that it is dual remove boron, obtain boron in water body It effectively removes.
Embodiment 4
Sedimentation filtration step:
By containing a large amount of suspension floccules in water, it is necessary to pass through sedimentation except boron treated fracturing outlet liquid waste water Separation, sedimentation device are horizontal sedimentation tank and inclined-tube sedimentation tank.
To ensure water stabilization, the supernatant after sedimentation also needs to be filtered processing, and filter is dedicated active-carbon finely Fine filtrator.
The filtered total boron content of effluent quality can be lower than 3mg/l or less.
After guanidine glue fracturing outlet liquid is handled using the method for the present invention except boron, water quality reaches and is better than defined water quality control Project processed and limit value fully meet secondary preparing fracturing fluid requirement.
The foregoing is merely the preferred embodiments of invention, are not intended to limit the scope of the invention, all to utilize this It simply modifies or converts made by description of the invention content, be applied directly or indirectly in other relevant method fields, together Reason is included within the scope of the present invention.

Claims (8)

1. a kind of remove the method that boron processing cycle recycles for guanidine glue fracturing outlet liquid, which is characterized in that the method passes through The de- steady and hard-off pretreatment of efficiently broken glue, solid-liquid separation treatment are carried out, except boron is handled and is settled to guanidine glue fracturing outlet liquid waste water After filtration treatment, obtain can be used for secondary preparing fracturing fluid recycles water.
2. according to claim 1 remove the method that boron processing cycle recycles for guanidine glue fracturing outlet liquid, feature exists In it includes that the broken glue processing of strong oxidizer oxidative cleavage and dedicated gel breaker are broken that the efficiently broken glue, which takes off the pretreatment of steady and hard-off to include, Glue destablizing, the strong oxidizer oxidative cleavage break glue processing and refer to the remaining crosslinking agent and jelly in guanidine glue fracturing outlet liquid The oxidative cleavage that glue carries out breaks glue processing, and the dedicated gel breaker breaks glue destablizing and refers to the glue in guanidine glue fracturing outlet liquid The aggregation of body suspended matter progress, cohesion, net, which catch and build bridge, breaks glue destablizing.
3. according to claim 2 remove the method that boron processing cycle recycles for guanidine glue fracturing outlet liquid, feature exists In the strong oxidizer includes persulfate, and the dedicated gel breaker is YPJJ-1.
4. according to claim 1 remove the method that boron processing cycle recycles for guanidine glue fracturing outlet liquid, feature exists In the solid-liquid separation treatment includes the concentration pre-separation and the dehydration of diaphragm plate frame filter press separation of sludge concentration tank.
5. according to claim 1 remove the method that boron processing cycle recycles for guanidine glue fracturing outlet liquid, feature exists In described except boron processing includes hydroxide colloid absorption and the complexing of polyhydroxy ligand, the hydroxide colloid absorption is Refer to and forms big micelle after adsorbing using hydroxide colloid to B [OH] 4-and rapid subsidence is separated from the water removal, the hydrogen Oxide colloid, which derives from, removes boron agent 1, and the polyhydroxy ligand complexing refers to is matched using multiple hydroxyls in composite flocculation agent Position body is to forming big micelle and rapid subsidence is separated from the water after adsorption bridging effect again after the complex reaction of B [OH] 4- It removes, the polyhydroxy ligand, which derives from, removes boron agent 2.
6. according to claim 5 remove the method that boron processing cycle recycles for guanidine glue fracturing outlet liquid, feature exists In, it is described except boron agent 1 is multi-functional compound macromolecular polymer, it is described except 1 main component of boron agent is Al2O3, Fe2O3 and C member Element, it is described except 2 main component of boron agent be polyacrylamide and containing be body polyol.
7. according to claim 1 remove the method that boron processing cycle recycles for guanidine glue fracturing outlet liquid, feature exists In, comprising the following steps:
Step 1 is adjusted modifier treatment and guanidine glue fracturing outlet liquid waste water is adjusted using circulating pump quenched in storage pool Processing, it is ensured that influent quality is stablized；
Step 2, the efficiently broken de- steady and hard-off pretreatment of glue, takes off steady hard-off processing unit in broken glue, guanidine glue fracturing outlet liquid is given up Water, which is pumped, to be promoted in storage pool to aoxidizing in broken glue pond, and tune pH value is 8.0-9.0, adds strong oxidizer, mixed with circulating pump It closes uniformly, stops 6-10h at normal temperature, complete to the remaining crosslinking agent and the broken Jiao Chu of frozen glue oxidation in fracturing outlet liquid waste water Reason；Then, guanidine glue fracturing outlet liquid waste water is pumped from the broken Jiao Chi of oxidation and is pumped into 1# dosing pond, Na2CO3 tune pH value is added, It is sufficiently stirred, control pH value is completed to carry out guanidine glue fracturing outlet liquid waste water the processing of quenched and hard-off in 8.5-9.0, then, will Dedicated gel breaker is added from 1# dosing pond from flowing in 2# dosing pond, in 3 ‰ -5 ‰ ratio in guanidine glue fracturing outlet liquid waste water, stirs It mixes, is sufficiently mixed dedicated gel breaker with fracturing fluid waste water, then the row of returning is split to guanidine glue laminated from flowing to brokenly glue and taking off steady hard-off processing pond The broken glue that liquid waste water carries out colloidal suspended substance takes off steady hard-off processing, stops 15min-20min, completes broken glue and takes off steady hard-off processing, The supernatant obtained after the sedimentation of 1# horizontal sedimentation tank is that broken glue takes off steady hard-off supernatant；
Step 3, solid-liquid separation treatment first will be after the 1# horizontal sedimentation tank sedimentations in step 2 in solid-liquid separation treatment unit Obtained sludge is pumped into sludge concentration tank and is concentrated, and concentration pre-separation is completed, then by the sludge after concentration using dedicated Plunger pump is promoted to diaphragm plate frame filter press and carries out solid-liquid separation dehydration processing, completes the dehydration separation of plate and frame filter press；
Water after the separation of solid and liquid all returns to fracturing fluid storage pool, and the solid formation after the separation of solid and liquid is dirt to be fermented Mud；
Step 4 is removing boron processing unit except boron is handled, and takes off steady hard-off supernatant in 3# to broken glue obtained in step 2 first In dosing pond, it is 9.0-10.0, after mixing is sufficiently stirred that NaOH, which is added, and adjusts pH value, and water to be processed is then flowed into 4# certainly Dosing pond is added by 3 ‰ -5 ‰ and removes boron agent 1, after mixing is sufficiently stirred, then presses water to be processed from 5# dosing pond is flowed into 3~5 are added except boron agent 2, and mixing is sufficiently stirred, and then remove in boron reaction tank water to be processed from inflow, pass through micro- exposure Gas is stirred, and stops 6-8h；It finally flow to 2# horizontal sedimentation tank certainly to be settled in advance, obtain except boron supernatant；
Sludge after the 2# horizontal sedimentation tank sedimentation is still pumped into sludge concentration tank and is concentrated, and completes concentration pre-separation, then Sludge after concentration is promoted to diaphragm plate frame filter press using dedicated plunger pump and carries out solid-liquid separation dehydration processing；
Step 5, sedimentation filtration are settled what step 4 obtained except boron supernatant is pumped into inclined-tube sedimentation tank, again after sedimentation Supernatant is filtered to obtain by active-carbon finely fine filtrator recycles water.
8. a kind of utilize described in claim 1-7 any one for guanidine glue fracturing outlet liquid except boron processing cycle reuse method Device, be included in adjust quenched pretreatment unit, broken glue takes off steady hard-off processing unit, solid-liquid separation treatment unit, except at boron Manage unit and sedimentation filtration processing unit, which is characterized in that the modifier treatment unit and broken glue take off steady hard-off processing unit all It is provided with medicine machine, measuring equipment and blender, aoxidizes broken Jiao Chi, broken Jiao Chi and 1# horizontal sedimentation tank, the separation of solid and liquid Processing unit includes sludge concentration tank and diaphragm plate frame filter press, and the boron processing unit that removes includes dosing metering mixer, exposes Device of air removes boron reaction tank and 2# horizontal sedimentation tank, the sedimentation filtration processing unit inclined-tube sedimentation tank and the fine mistake of active carbon Filter.
CN201910529851.8A 2019-06-19 2019-06-19 The method and device thereof that boron processing cycle recycles are removed for guanidine glue fracturing outlet liquid Pending CN110240315A (en)

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CN112679020A (en) * 2020-12-25 2021-04-20 成都硕特环保科技有限公司 Low-cost shale gas fracturing flowback fluid treatment system and treatment method

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CN106315934A (en) * 2016-08-30 2017-01-11 中石化石油工程机械有限公司研究院 Experiment device for treatment of fracturing flow-back fluid
CN108585279A (en) * 2018-05-16 2018-09-28 中国石油天然气集团有限公司 A kind of processing method of guanidine glue fracturing outlet liquid

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CN105540918A (en) * 2015-12-15 2016-05-04 安东环保技术有限公司 Treatment method of fracturing flow-back fluid
CN106315934A (en) * 2016-08-30 2017-01-11 中石化石油工程机械有限公司研究院 Experiment device for treatment of fracturing flow-back fluid
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CN111039508A (en) * 2019-12-30 2020-04-21 河南工程学院 Sewage treatment system for hotel and use method
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CN112679020A (en) * 2020-12-25 2021-04-20 成都硕特环保科技有限公司 Low-cost shale gas fracturing flowback fluid treatment system and treatment method

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