CN109133463A - The processing method of foam drainage gas recovery waste water - Google Patents
The processing method of foam drainage gas recovery waste water Download PDFInfo
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- CN109133463A CN109133463A CN201710506010.6A CN201710506010A CN109133463A CN 109133463 A CN109133463 A CN 109133463A CN 201710506010 A CN201710506010 A CN 201710506010A CN 109133463 A CN109133463 A CN 109133463A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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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
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention relates to technical field of waste water processing, disclose a kind of processing method of foam drainage gas recovery waste water, this method comprises: foam drainage gas recovery waste water is carried out coagulating kinetics by (1), obtain supernatant；(2) supernatant is subjected to oxidation processes, to remove the ammonia nitrogen in waste water；(3) waste water for obtaining step (2) carries out thermal precipitation processing, to remove the surfactant in waste water；(4) system that step (3) obtains is evaporated processing.The operating condition of this method is neutral or near neutral (without strong acid condition and basic conditions), simple process, low in cost, applied widely, can substantially purify water after processing, efficiently solve the problems, such as that foam drainage gas recovery waste water is reluctant.
Description
Technical field
The present invention relates to technical field of waste water processing, and in particular to a kind of processing method of foam drainage gas recovery waste water.
Background technique
Gas field development middle and later periods drop in formation pressure, side, bottom water promote and implement the operations such as pressure break, acidification, make shaft bottom
With generate hydrops in pit shaft, gas production reduces even water logging and stops production.People eliminate shaft bottom hydrops using a variety of methods,
Middle foaming water discharge method is widely used due at low cost, fast, construction of producing effects is easy, does not influence gas well liquid loading.Foam helps mining gas
Method is by injecting a certain amount of foam cleanup additive in gas well, after shaft bottom hydrops is contacted with foam cleanup additive, by natural gas
The agitation of stream, generates a large amount of low-density resistance aqueous foams, is carried to ground from shaft bottom with air-flow, to reach stable yields, increase production and prolong
The purpose of its long flush stage.
A large amount of waste water can be discharged with bubble during foam helps mining gas, referred to as (i.e. foam drainage gas recovery is useless for bubble draining
Water).Due to joined some surfactants and macromolecule with specific function into well during foam helps mining gas
Polymer contains more surface reactive material, soluble solid etc., COD so the water quality of the bubble draining of discharge is complex in composition
It is higher.It is at normal temperature in milkiness liquid status, emulsification degree is high, and there is the oil that floats on surface, and has peculiar smell, easily blisters, and foam volume
Greatly, antifoaming speed is slow.
Due to the addition of exhibiting high surface activating agent, bubble draining is easily blistered, and its high salinity determines that its biochemical is poor,
It is difficult to enter common sewage-treatment plant.
Bubble draining is different from routine and contains surface active agent wastewater, and gas production foaming agent uses amphoteric surfactant, such as beet
Bases surfactant, it is difficult targetedly to implement processing means.Therefore, bubble drainage sunk well is difficult, patent application
CN104773893A discloses the bubble draining of use " Fenton oxidation+coagulation+stripping+reduction vaporization " flow processing, processing stream
A variety of oxidants, catalyst, flocculant and flocculation aid need to be added in journey, and needs repeatedly to adjust pH value in entire treatment process, operate
It is complicated.In addition, Fenton oxidation reaction need to carry out under strong acid environment, equipment and maintenance cost are higher, and there are security risks.
It is there is no under the conditions of neutral or near neutral at present, the technique that bubble draining is effectively treated easy to operate.
Summary of the invention
The purpose of the invention is to overcome the above-mentioned problems in the prior art, it is useless to provide a kind of foam drainage gas recovery
The processing method of water, the operating condition of this method are neutral or near neutral (without strong acid condition and basic conditions), technique letter
It is single, low in cost, applied widely, it can substantially purify water after processing, efficiently solve foam drainage gas recovery waste water and be difficult to locate
The problem of reason.
To achieve the goals above, the present invention provides a kind of processing method of foam drainage gas recovery waste water, this method packets
It includes:
(1) foam drainage gas recovery waste water is subjected to coagulating kinetics, obtains supernatant；
(2) supernatant is subjected to oxidation processes, to remove the ammonia nitrogen in waste water；
(3) waste water for obtaining step (2) carries out thermal precipitation processing, to remove the surfactant in waste water；
(4) system that step (3) obtains is evaporated processing.
Method of the invention takes full advantage of the property and the surfactant (both sexes such as glycine betaine of bubble draining itself
Ionic surface active agent) the characteristics of, the type and dosage of medicament are considerably reduced compared with prior art, and are not needed repeatedly
PH value is adjusted, stripping is not needed, no stripping bring foam takes the reluctant problem of foam of water greatly, after collection.And
And whole process all carries out under neutral or near neutral condition (without strong acid condition and basic conditions), avoids Fenton
The corrosion of equipment brought by highly acid and safety problem are aoxidized, it is simple process, low in cost, applied widely, it can be big after processing
Width purifies water.Wherein, this method uses the process of " coagulating sedimentation+oxidation+thermal precipitation+evaporation ", and passes through thermal precipitation
Method removal waste water in surfactant (thermal precipitation processing in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid
Precipitated with being generated under heating conditions with the betaines surfactant in foam drainage gas recovery waste water), realization was evaporated
Cheng Wending solves the problems, such as that foam drainage gas recovery waste water is reluctant.
A preferred embodiment of the invention, using aluminium chloride or aluminum sulfate as coagulant, using less
Dosage is 6-8 in pH value, carries out coagulating kinetics under conditions of preferably 7-7.5, and can to evaporate water can satisfy
(according to " integrated wastewater discharge standard " (GB8978-1996) standard, discharge water outlet need to meet COD < 100mg/ for qualified discharge requirement
L, ammonia nitrogen < 15mg/L), when selecting aluminium chloride as additional impurity will not be introduced when coagulant.In addition, using other kinds of mixed
Solidifying agent, increasing dosage also may make evaporation water outlet to meet qualified discharge requirement.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of processing methods of foam drainage gas recovery waste water, this method comprises:
(1) foam drainage gas recovery waste water is subjected to coagulating kinetics, obtains supernatant；
(2) supernatant is subjected to oxidation processes, to remove the ammonia nitrogen in waste water；
(3) waste water for obtaining step (2) carries out thermal precipitation processing, to remove the surfactant in waste water；
(4) system that step (3) obtains is evaporated processing.
In the case of process of the present invention it is preferred, in step (1), the method for coagulating kinetics includes: to foaming water discharge
Coagulant and optional flocculation aid are added in gas production waste water, and the pH value of control system is 6-8.Further, control system
PH value is 7-7.5.
Under preferable case, coagulant is aluminium chloride, aluminium polychloride, iron chloride, poly-ferric chloride, ferric sulfate, polymerised sulphur
At least one of sour iron, aluminum sulfate and polyaluminium sulfate.The present inventor has found under study for action, specific for the present invention
Foam drainage gas recovery waste water (such as the aftermentioned foam drainage gas recovery waste water of the present invention), in selective chlorination aluminium or aluminum sulfate as mixed
Under solidifying agent, the specified conditions that pH value is the preferred 7-7.5 of 6-8, using less dosage, there can be more excellent coagulating sedimentation
Effect (is marked so that evaporating water and can satisfy qualified discharge requirement according to " integrated wastewater discharge standard " (GB8978-1996)
Standard, discharge water outlet need to meet COD < 100mg/L, ammonia nitrogen < 15mg/L), it is additional for that will not be introduced when coagulant when selecting aluminium chloride
Impurity.It will be understood by those skilled in the art that when selecting other kinds of flocculant, if improving the flocculant
Dosage also can get preferable coagulating sedimentation effect, so that evaporating water can satisfy qualified discharge requirement.
Flocculation aid is not selected particularly, can be various flocculation aids commonly used in the art, it is heavy in order to improve coagulation
Shallow lake effect shortens the coagulating sedimentation time, and under preferable case, flocculation aid is polyacrylamide.When flocculation aid and coagulant make together
Used time can be improved coagulating sedimentation effect, the time for shortening coagulating sedimentation, improve treatment effeciency.Wherein, polyacrylamide can be with
For the various cationic-type polyacrylamides for Coagulation aiding commonly used in the art, number-average molecular weight can be 1,500,000-
20000000, it can be commercially available.
In order to improve coagulating sedimentation effect, under preferable case, the dosage of coagulant is 300-1500ppm, further preferably
For 500-1000ppm；The dosage of flocculation aid is 0-20ppm, further preferably 3-10ppm.
In the present invention, it will be understood by those skilled in the art that coagulation is cohesion and flocculated general name.The present invention will mix
Solidifying agent (such as aluminium chloride) and optional flocculation aid (such as polyacrylamide) are added in bubble draining, can make suspension tiny in waste water
Particulate matter, jelly and oil particles mutually adsorb and are combined into biggish particle, to make suspended matter or jelly from waste water
It precipitates, keeps water quality after processing limpid.This step is prepared for post precipitation surfactant.
Compare existing bubble drainage sunk well technique (referring to patent application CN104773893A), and the mode used is first
By advanced oxidation, then carry out coagulation again, the present invention has the advantages that Fenton oxidation is at high cost, under strong acid environment into
Row, equipment and maintenance cost are higher, and there are security risks, and need repeatedly to adjust pH value；And the present invention passes through a coagulation
Precipitation process can significantly remove particulate matter, colloid and oil particles, and easy to operate, cost is greatly lowered.
In the case of process of the present invention it is preferred, in step (2), the method for oxidation processes includes: to be added into supernatant
Hypochlorite.
Under preferable case, chlorate is at least one of sodium hypochlorite, postassium hypochlorite and calcium hypochlorite, further preferably
For sodium hypochlorite.
In order to effectively remove ammonia nitrogen and some simple organic matters, under preferable case, the dosage of hypochlorite is 500-
2500ppm, further preferably 800-1500ppm.Wherein, after the hypochlorite of aforementioned dosage is added, the pH value of system can be with
Control is 6-9, preferably 7-9 (for weak basic condition).
In the present invention, it will be understood by those skilled in the art that the process of oxidation processes be by hypochlorite (as follows
Sodium chlorate) it is reacted with ammonia nitrogen and simple organic, the process of nitrogen, chlorate (such as sodium chloride) and water is generated, can effectively be dropped
Low ammonia nitrogen concentration and COD realize the qualified discharge of ammonia nitrogen and COD in evaporation water outlet.
Fenton oxidation used in the prior art that compares (referring to patent application CN104773893A), hypochlorite oxidation
Cost can be greatly lowered, and do not have to adjust pH value repeatedly, the effect that Fenton oxidation removes ammonia nitrogen is poor, and hypochlorite oxygen
Change is good to ammonia nitrogen removal effect, and can remove simple organic, keeps evaporation water outlet water-quality COD up to standard.
In the case of process of the present invention it is preferred, in step (3), the method for the thermal precipitation processing includes: to step
(2) phosphate and/or silicate and tungstates and/or molybdate, phosphotungstic acid, silico-tungstic acid, phosphorus molybdenum are added in the waste water obtained
The pH value of at least one of acid and silicomolybdic acid, regulation system is 5-7, further preferably 6-7, and system is carried out at heating
Reason.It will be understood by those skilled in the art that " phosphate and/or silicate and tungstates and/or molybdenum are added into waste water
At least one of hydrochlorate, phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid " is directed to be added in waste water: (a) phosphate and silicon
At least one of hydrochlorate and at least one of tungstates and molybdate, (b) phosphotungstic acid, (c) silico-tungstic acid, (d) phosphomolybdic acid
(e) at least one of the substance of this five kinds of situations of silicomolybdic acid, wherein at least one of phosphate and silicate and wolframic acid
At least one of salt and molybdate can generate during heating one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, silicomolybdic acid or
It is several.And phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid can under heating conditions with betaines surfactant (such as
Contain R-N+-CH2-COO-) complex compound is generated, and then form precipitating.
Under preferable case, the condition of heat treatment includes: that temperature is 80-100 DEG C.
Wherein, for phosphate, silicate, tungstates and molybdate, there is no particular limitation, can be respectively this field
Common various phosphate, silicate, tungstates and molybdate, under preferable case, phosphate is sodium dihydrogen phosphate, biphosphate
At least one of potassium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium phosphate and potassium phosphate, silicate are sodium metasilicate and/or silicic acid
Potassium, tungstates are sodium tungstate and/or potassium tungstate, and molybdate is sodium molybdate and/or potassium molybdate.
In order to effectively remove surfactant, under preferable case, phosphatic dosage is 0-45ppm, the silicate
Dosage is 0-110ppm, and the dosage of the tungstates is 0-1500ppm, and the dosage of the molybdate is 0-1100ppm, the phosphorus
The dosage of wolframic acid is 0-1200ppm, and the dosage of the silico-tungstic acid is 0-1200ppm, and the dosage of the phosphomolybdic acid is 0-700ppm,
The dosage of the silicomolybdic acid is 0-700ppm.It will be understood by those skilled in the art that the dosage of aforementioned each substance should not be same
When be zero, need to guarantee at least one of this five kinds of situations of aforementioned during heating (a)-(e) corresponding substance exist, i.e.,
Guarantee to be ultimately present at least one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid (in heating process in step (3)
It is middle to generate or directly as in reactant addition system) it reacts with surfactant, and aforementioned each respective substance is preceding
Stating the dosage in range can be determined according to the content of surfactant, and it is ripe to be selected specifically to those skilled in the art institute
Know, details are not described herein.
In the present invention, it will be understood by those skilled in the art that thermal precipitation is mainly the spy according to surfactant
Sign (contains R-N the invention is particularly suited to glycine betaine is this kind of+-CH2-COO-The removal of the surfactant of group), in fire-bar
Under part, in acidic environment and neutral environment, in phosphotungstic acid present in system, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid at least
It is a kind of to generate the characteristics of precipitating with surfactant, the surfactant that foam helps in mining gas waste water is completely removed, steaming is reached
Bubble-tight purpose during hair.Entire reaction process avoids many and diverse operating procedure and Fenton oxidation highly acid institute band
The equipment corrosion come and safety problem.
And the processing method (referring to patent application CN104773893A) of prior art Surfactant is mainly advanced
Oxidation plus stripping.Advanced oxidation brings higher cost, and complicated operating procedure, and experiment has peace under strongly acidic conditions
Full hidden danger；Stripping process further increases cost, and during stripping foam take water is big, collect after foam be difficult to handle
The problem of do not solved at all.The present invention is existed by one or more of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid
It reacts under heating condition with surfactant and generates complex compound, and then precipitate, surfactant and significantly can be completely removed
Cost is reduced, heat provided by being evaporated under reduced pressure below is made full use of.
In the present invention, the adjusting of the pH value of each step realizes that acid is preferably dilute salt by the way that acid or alkali are added into system
Acid, alkali are preferably sodium hydroxide and/or potassium hydroxide, further preferably sodium hydroxide (will not introduce new impurity).
In the case of process of the present invention it is preferred, in step (4), the mode of the evaporation process is to be evaporated under reduced pressure, preferably
For multiple-effect reduction vaporization.
Preferably, it is that economic benefits and social benefits are evaporated under reduced pressure that the multiple-effect, which is evaporated under reduced pressure, and the condition that the economic benefits and social benefits are evaporated under reduced pressure includes: first
The temperature of effect evaporation is 80-100 DEG C, and pressure is -0.04~-0.02MPa；The temperature of second effect evaporation is 60-80 DEG C, pressure
For -0.08~-0.06MPa.
In the present invention, the system that step (3) obtains directly can be subjected to reduction vaporization processing, it can also be first by step
(3) system obtained is separated by solid-liquid separation, then obtained liquid phase is carried out reduction vaporization processing.It, can be with when processing is evaporated under reduced pressure
System is first heated to relevant temperature by selectivity, then enters back into decompressor, in the process using the evaporation pre- thermal wastewater of water, is reached
Thermal cycle, energy saving purpose.Evaporation process of the invention can be carried out steadily, and good in nitrate nitrogen removal effect after evaporation, can be steamed with reuse
A large amount of sodium chloride crystal is generated after hair.
Method of the invention is particularly suitable for being added during foam helps mining gas after having betaines surfactant
The bubble of generation drains, it is therefore preferable that in the case of, the content of glycine betaine is 0.1-10mmol/ in the foam drainage gas recovery waste water
L, further preferably 0.2-1.5mmol/L.
Preferably, the COD of the foam drainage gas recovery waste water is 4000-22000mg/L, pH value 5.7-7.5, suspended matter
Content is 85000-120000mg/L, ammonia-nitrogen content 190-360mg/L, chloride ion content 12000-14000mg/L.
Embodiment
The present invention will be described in detail by way of examples below, but the range being not intended to limit the present invention.Below
In embodiment, unless otherwise instructed, used method is method commonly used in the art, and material used can be by commercially available
It obtains, pH is adjusted by hydrochloric acid or sodium hydroxide.
COD is measured using the method for GB11914-1989.
Cl is measured using the method for GB/T15453-2008-Content.
Ammonia-nitrogen content is measured using the method for HJ 535-2009.
Suspension content is measured using GB11901-89 method.
According to the method in document (" content that direct titrimetric method measures active matter and free uncle amine in glycine betaine product ")
The content of (1.2.3 diphasic titration measures glycine betaine active matter content) measurement glycine betaine.
Embodiment 1
The present embodiment is used to illustrate the processing method of foam drainage gas recovery waste water of the invention.
Waste water basic condition to be processed: waste water is that (addition has dodecyl two to southwest gas field foam gas production process
Methyl betaine) the bubble draining that generates, COD 13521mg/L, pH value 6.7, suspension content 91287mg/L, ammonia nitrogen contains
Amount is 210mg/L, and the content of chloride ion content 13089mg/L, glycine betaine are 0.3mmol/L, and color is yellow, has hydro carbons
Smell.
(1) be added into bubble draining 800ppm aluminium chloride and 5ppm polyacrylamide (purchased from German BASF BASF,
Model Zetag 8165, similarly hereinafter), adjusting pH value is 7.2, stirring, and bubble draining quickly generates a large amount of yellow wadding bodies, and wadding body is rapid
Precipitating.Solution layering, upper layer are clear solution, and lower layer is yellow coagulating sedimentation object, obtain supernatant after centrifuge separation.Supernatant
COD is 5001mg/L, and COD is greatly lowered.
(2) sodium hypochlorite of 1000ppm is added into supernatant, reacts 30min.
(3) sodium dihydrogen phosphate of 12ppm and the sodium tungstate of 250ppm are added in the waste water obtained to step (2), by system
PH value is adjusted to 7, and system is then heated to 80 DEG C, generates pale yellow precipitate.
(4) system for obtaining step (3) carries out the processing of economic benefits and social benefits reduction vaporization, wherein the item of processing is evaporated under reduced pressure in economic benefits and social benefits
Part includes: that the temperature of the first effect evaporation is 85 ± 2 DEG C, and pressure is -0.03 ± 0.01MPa；The temperature of second effect evaporation is 65 ± 2
DEG C, pressure is -0.07 ± 0.01MPa.Evaporation can be carried out steadily, and good in nitrate nitrogen removal effect after evaporation, and top steam carries out former
It is collected after liquid heat exchange, bottom is Nacl.
After whole process processing, it is discharged colorless and odorless, COD 24mg/L, suspension content 0mg/L, ammonia-nitrogen content is
5.9mg/L, chloride ion content 73mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 2
The present embodiment is used to illustrate the processing method of foam drainage gas recovery waste water of the invention.
Waste water basic condition to be processed: waste water is that (addition has dodecyl two to southwest gas field foam gas production process
Methyl betaine) the bubble draining that generates, COD 13580mg/L, pH value 6.7, suspension content 92246mg/L, ammonia nitrogen contains
Amount is 200mg/L, and the content of chloride ion content 13103mg/L, glycine betaine are 0.33mmol/L, and color is yellow, has hydrocarbon
Class smell.
(1) aluminium chloride of 500ppm and the polyacrylamide of 10ppm is added into bubble draining, adjusting pH value is 7, stirring,
Bubble draining quickly generates a large amount of yellow wadding bodies, and wadding body precipitates rapidly.Solution layering, upper layer are clear solution, and lower layer is mixed for yellow
Retrogradation starch obtains supernatant after centrifuge separation.Supernatant C OD is 5212mg/L, and COD is greatly lowered.
(2) sodium hypochlorite of 1500ppm is added into supernatant, reacts 25min.
(3) tungsten of the sodium dihydrogen phosphate of 5ppm, the sodium metasilicate of 12ppm, 180ppm are added in the waste water obtained to step (2)
System pH is adjusted to 6 by the sodium molybdate of sour sodium and 110ppm, and system is then heated to 90 DEG C, generates pale yellow precipitate.
(4) system for obtaining step (3) carries out the processing of economic benefits and social benefits reduction vaporization, wherein the item of processing is evaporated under reduced pressure in economic benefits and social benefits
Part includes: that the temperature of the first effect evaporation is 82 ± 2 DEG C, and pressure is -0.03 ± 0.01MPa；The temperature of second effect evaporation is 62 ± 2
DEG C, pressure is -0.07 ± 0.01MPa.Evaporation can be carried out steadily, and good in nitrate nitrogen removal effect after evaporation, and top steam carries out former
It is collected after liquid heat exchange, bottom is Nacl.
After whole process processing, it is discharged colorless and odorless, COD 34mg/L, suspension content 0mg/L, ammonia-nitrogen content is
5mg/L, chloride ion content 69mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 3
The present embodiment is used to illustrate the processing method of foam drainage gas recovery waste water of the invention.
Waste water basic condition to be processed: waste water is that (addition has dodecyl two to southwest gas field foam gas production process
Methyl betaine) generate bubble draining, COD 13542mg/L, pH value 6.7, suspension content 102182mg/L, ammonia nitrogen
Content is 200mg/L, and the content of chloride ion content 13129mg/L, glycine betaine are 0.31mmol/L, and color is yellow, is had
Hydro carbons smell.
(1) aluminium chloride of 1000ppm and the polyacrylamide of 3ppm is added into bubble draining, adjusting pH value is 7.5, is stirred
It mixes, bubble draining quickly generates a large amount of yellow wadding bodies, and wadding body precipitates rapidly.Solution layering, upper layer is clear solution, and lower layer is yellow
Coagulating sedimentation object obtains supernatant after centrifuge separation.Supernatant C OD is 5002mg/L, and COD is greatly lowered.
(2) sodium hypochlorite of 800ppm is added into supernatant, reacts 35min.
(3) sodium dihydrogen phosphate of 4.5ppm, the sodium metasilicate and 230ppm of 12ppm are added in the waste water obtained to step (2)
Sodium molybdate, system pH is adjusted to 7, system is then heated to 85 DEG C, pale yellow precipitate is generated, is filtered, obtains
Filtrate.
(4) filtrate is subjected to the processing of economic benefits and social benefits reduction vaporization, wherein the condition that processing is evaporated under reduced pressure in economic benefits and social benefits includes: the first effect
The temperature of evaporation is 82 ± 2 DEG C, and pressure is -0.03 ± 0.01MPa；Second effect evaporation temperature be 65 ± 2 DEG C, pressure be-
0.07±0.01MPa.Evaporation can be carried out steadily, and good in nitrate nitrogen removal effect after evaporation, and top steam is received after carrying out stoste heat exchange
Collection, bottom is Nacl.
After whole process processing, it is discharged colorless and odorless, COD 29mg/L, suspension content 0mg/L, ammonia-nitrogen content is
5mg/L, chloride ion content 83mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 4
The present embodiment is used to illustrate the processing method of foam drainage gas recovery waste water of the invention.
Waste water basic condition to be processed: waste water is that (addition has dodecyl two to southwest gas field foam gas production process
Methyl betaine) the bubble draining that generates, COD 14728mg/L, pH value 6.7, suspension content 89564mg/L, ammonia nitrogen contains
Amount is 210mg/L, and the content of chloride ion content 12489mg/L, glycine betaine are 1.4mmol/L, and color is yellow, has hydro carbons
Smell.
(1) aluminium chloride of 400ppm and the polyacrylamide of 15ppm is added into bubble draining, adjusting pH value is 6.5, is stirred
It mixes, bubble draining quickly generates a large amount of yellow wadding bodies, and wadding body precipitates rapidly.Solution layering, upper layer is clear solution, and lower layer is yellow
Coagulating sedimentation object obtains supernatant after centrifuge separation.Supernatant C OD is 7019mg/L, and COD is greatly lowered.
(2) calcium hypochlorite of 1800ppm is added into supernatant, reacts 35min.
(3) phosphotungstic acid of 1100ppm is added in the waste water obtained to step (2), system pH is adjusted to 7, then will
System is heated to 90 DEG C, generates pale yellow precipitate.
(4) filtrate is subjected to the processing of economic benefits and social benefits reduction vaporization, wherein the condition that processing is evaporated under reduced pressure in economic benefits and social benefits includes: the first effect
The temperature of evaporation is 82 ± 2 DEG C, and pressure is -0.03 ± 0.01MPa；Second effect evaporation temperature be 65 ± 2 DEG C, pressure be-
0.07±0.01MPa.Evaporation can be carried out steadily, and good in nitrate nitrogen removal effect after evaporation, and top steam is received after carrying out stoste heat exchange
Collection, bottom is Nacl.
After whole process processing, it is discharged colorless and odorless, COD 62mg/L, suspension content 0mg/L, ammonia-nitrogen content is
9mg/L, chloride ion content 60mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 5
According to the method for embodiment 1, unlike, in step (1), with aluminium polychloride (purchased from Tianjin recovery fining
Work research institute) replace aluminium chloride.Supernatant C OD is 9030mg/L after coagulation, and COD is substantially reduced.
After whole process processing, it is discharged colorless and odorless, COD 92mg/L, suspension content 0mg/L, ammonia-nitrogen content is
8mg/L, chloride ion content 72mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 6
According to the method for embodiment 1, unlike, in step (1), aluminium chloride is replaced with iron chloride.Supernatant after coagulation
COD is 10030mg/L, and COD decreases.
After whole process processing, it is discharged colorless and odorless, COD 108mg/L, suspension content 0mg/L, ammonia-nitrogen content is
9.3mg/L, chloride ion content 78mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 7
According to the method for embodiment 1, unlike, in step (1), with poly-ferric chloride (purchased from Tianjin recovery fining
Work research institute) replace aluminium chloride.Supernatant C OD is 11030mg/L after coagulation, and COD decreases.
After whole process processing, it is discharged colorless and odorless, COD 117mg/L, suspension content 0mg/L, ammonia-nitrogen content is
10.5mg/L, chloride ion content 77mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 8
According to the method for embodiment 1, unlike, in step (1), aluminium chloride is replaced with ferric sulfate.Supernatant after coagulation
COD is 9053mg/L, and COD is substantially reduced.
After whole process processing, it is discharged colorless and odorless, COD 98mg/L, suspension content 0mg/L, ammonia-nitrogen content is
9.8mg/L, chloride ion content 80mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 9
According to the method for embodiment 1, unlike, in step (1), aluminium chloride is replaced with aluminum sulfate.Supernatant after coagulation
COD is 6529mg/L, and COD is greatly lowered.
After whole process processing, it is discharged colorless and odorless, COD 42mg/L, suspension content 0mg/L, ammonia-nitrogen content is
7mg/L, chloride ion content 69mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 10
According to the method for embodiment 1, (magnificent (Beijing) purchased from Divine Land with polyaluminium sulfate in step (1) unlike
Science and Technology Ltd.) replace aluminium chloride.Supernatant C OD is 9928mg/L after coagulation, and COD decreases.
After whole process processing, it is discharged colorless and odorless, COD 102mg/L, suspension content 0mg/L, ammonia-nitrogen content is
9.9mg/L, chloride ion content 78mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 11
According to the method for embodiment 1, unlike, in step (1), it is added without polyacrylamide, that is, add into bubble draining
Enter the aluminium chloride of 800ppm, adjusting pH value is 7.2, stirring, and bubble draining quickly forms tiny wadding body, and wadding body is in faint yellow, wadding body
It is difficult to settle, be dispersed in bubble draining, just will appear obvious layering, and point of wadding body and water by (10h or so) for a long time
It is bad from effect, by being centrifugally separating to obtain supernatant.Supernatant C OD is 5229mg/L, and COD is greatly lowered.
After whole process processing, it is discharged colorless and odorless, COD 35mg/L, suspension content 0mg/L, ammonia-nitrogen content is
6mg/L, chloride ion content 70mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 12
According to the method for embodiment 1, unlike, in step (1), adjusting pH value is 6.Supernatant C OD is after coagulation
6921mg/L, COD are substantially reduced.
After whole process processing, it is discharged colorless and odorless, COD 57mg/L, suspension content 0mg/L, ammonia-nitrogen content is
8.1mg/L, chloride ion content 72mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 13
According to the method for embodiment 1, unlike, in step (1), adjusting pH value is 8.Supernatant C OD is after coagulation
7525mg/L, COD are substantially reduced.
After whole process processing, it is discharged colorless and odorless, COD 75mg/L, suspension content 0mg/L, ammonia-nitrogen content is
8.3mg/L, chloride ion content 77mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 14
According to the method for embodiment 1, unlike, in step (1), adjusting pH value is 4.Supernatant C OD is after coagulation
11026mg/L, COD decrease.
After whole process processing, it is discharged colorless and odorless, COD 114mg/L, suspension content 0mg/L, ammonia-nitrogen content is
10.2mg/L, chloride ion content 82mg/L, the content of glycine betaine are 0mmol/L.
Embodiment 15
According to the method for embodiment 1, unlike, in step (1), adjusting pH value is 10.Supernatant C OD is after coagulation
10217mg/L, COD decrease.
After whole process processing, it is discharged colorless and odorless, COD 109mg/L, suspension content 0mg/L, ammonia-nitrogen content is
10mg/L, chloride ion content 78mg/L, the content of glycine betaine are 0mmol/L.
Comparative example 1
According to the method for embodiment 1, unlike, in step (2), Fenton reagent is added into supernatant, wherein every
It rises in bubble draining and 1g FeSO is added4With the H of 2ml2O2, adjusting pH value is 3.5, reacts 30min.
After whole process processing, it is discharged colorless and odorless, COD 30mg/L, suspension content 0mg/L, ammonia-nitrogen content is
102mg/L, chloride ion content 80mg/L, the content of glycine betaine are 0mmol/L.
The operating condition of the method for the present invention is neutral or near neutral (without strong acid condition and basic conditions), technique letter
It is single, low in cost, applied widely, it can substantially purify water after processing, efficiently solve foam drainage gas recovery waste water and be difficult to locate
The problem of reason.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of processing method of foam drainage gas recovery waste water, which is characterized in that this method comprises:
(1) foam drainage gas recovery waste water is subjected to coagulating kinetics, obtains supernatant；
(2) supernatant is subjected to oxidation processes, to remove the ammonia nitrogen in waste water；
(3) waste water for obtaining step (2) carries out thermal precipitation processing, to remove the surfactant in waste water；
(4) system that step (3) obtains is evaporated processing.
2. according to the method described in claim 1, wherein, in step (1), the method for the coagulating kinetics includes: to bubble
Coagulant and optional flocculation aid are added in foam water pumping gas production waste water, and the pH value of control system is 6-8, preferably 7-7.5.
3. according to the method described in claim 2, wherein, the coagulant is aluminium chloride, aluminium polychloride, iron chloride, polymerization
At least one of iron chloride, ferric sulfate, bodied ferric sulfate, aluminum sulfate and polyaluminium sulfate, preferably aluminium chloride；And/or
The flocculation aid is polyacrylamide；
Preferably, the dosage of the coagulant is 300-1500ppm, further preferably 500-1000ppm；The flocculation aid
Dosage is 0-20ppm, further preferably 3-10ppm.
4. method described in any one of -3 according to claim 1, wherein in step (2), the method packet of the oxidation processes
It includes: hypochlorite being added into supernatant.
5. according to the method described in claim 4, wherein, the hypochlorite is sodium hypochlorite, postassium hypochlorite and calcium hypochlorite
At least one of；
Preferably, the dosage of the hypochlorite is 500-2500ppm, further preferably 800-1500ppm.
6. method described in any one of -5 according to claim 1, wherein in step (3), the side of the thermal precipitation processing
Method includes: that phosphate and/or silicate and tungstates and/or molybdate, phosphorus tungsten are added into the waste water that step (2) obtains
At least one of acid, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid, the pH value of regulation system are 5-7, preferably 6-7, and by system into
Row heat treatment；
Preferably, it is 80-100 DEG C that the condition of the heat treatment, which includes: temperature,.
7. according to the method described in claim 6, wherein, the phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate, phosphoric acid hydrogen two
At least one of sodium, dipotassium hydrogen phosphate, sodium phosphate and potassium phosphate；And/or
Silicate is sodium metasilicate and/or potassium silicate；And/or
Tungstates is sodium tungstate and/or potassium tungstate；And/or
Molybdate is sodium molybdate and/or potassium molybdate.
8. method according to any one of claims 1-7, wherein in step (4), the mode of the evaporation process is
Multiple-effect is evaporated under reduced pressure, and it is preferably that economic benefits and social benefits are evaporated under reduced pressure that the multiple-effect, which is evaporated under reduced pressure, and the condition that the economic benefits and social benefits are evaporated under reduced pressure includes: the
The temperature of one effect evaporation is 80-100 DEG C, and pressure is -0.04~-0.02MPa；The temperature of second effect evaporation is 60-80 DEG C, pressure
For -0.08~-0.06MPa.
9. method described in any one of -8 according to claim 1, wherein glycine betaine in the foam drainage gas recovery waste water
Content is 0.1-10mmol/L, preferably 0.2-1.5mmol/L.
10. according to the method described in claim 9, wherein, the COD of the foam drainage gas recovery waste water is 4000-22000mg/
L, pH value 5.7-7.5, suspension content 85000-120000mg/L, ammonia-nitrogen content 190-360mg/L, chloride ion content
For 12000-14000mg/L.
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