CN102478511A - Method for testing influence of salinity on flocculation effect of hydrophobic polymeric flocculant - Google Patents
Method for testing influence of salinity on flocculation effect of hydrophobic polymeric flocculant Download PDFInfo
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- CN102478511A CN102478511A CN2010105676173A CN201010567617A CN102478511A CN 102478511 A CN102478511 A CN 102478511A CN 2010105676173 A CN2010105676173 A CN 2010105676173A CN 201010567617 A CN201010567617 A CN 201010567617A CN 102478511 A CN102478511 A CN 102478511A
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Abstract
The invention discloses a method for testing influence of salinity on flocculation effect of a hydrophobic polymeric flocculant. The method comprises steps of: preparing a polymeric flocculant and clay suspending liquids with different salinities; adding the clay suspending liquids with different salinities in a same volume respectively into different test containers and adjusting to a same pH value; adding hydrophobic polymeric flocculant of a same volume into the clay suspending liquids; standing for a while and comparing light transmittances through observation, so as to obtain influence of salinity on flocculation effect of the hydrophobic polymeric flocculant. The invention can rapidly test influence of salinity on flocculation effect of a hydrophobic polymeric flocculant, has high test accuracy, simple operation steps and low test cost, so as to select hydrophobic polymeric flocculants according to different sewage and enhance treatment effect of hydrophobic polymeric flocculants.
Description
Technical field
The present invention relates to a kind of method of testing salinity to the flocculating effect influence of hydrophobic polymer flocculating agent.
Background technology
Along with the continuous increase of rapid economy development and population, energy production is on the rise with the environmental problem that consumption produces, and particularly water pollution problems has become the hot issue of various circles of society's common concern.In many municipal effluents and industrial waste water, the petroleum industry oily waste water is the most representative.Developed and produced multiple sewage-treating agent in order to improve the oily waste water treatment effeciency, comprised coagulant, flocculating agent, flotation agent etc.Wherein the hydrophobic polymer flocculating agent can be accelerated water purification speed as efficient water treatment agent, removes suspension and noxious material in the water.
Oil content in the oily waste water exists with oil slick, dispersed oil, oil emulsion and four kinds of forms of dissolving wet goods usually.Because the difference of existence form, the method for handling oily waste water is also just different.At present external oil-contaminated water of oil field is handled the facility that adopts and is mainly contained settling pit, oil interceptor, inclined plate grease pond, removes oil tank, coarse jar, pressure slurry tank, flotation cell (post), pressure filter, single valve filter tank, combined type treating apparatus, hydrocyclone and fine filter etc. except that oil tank, coagulation naturally.The affiliated facility that adopts has various buffering system jars (pond), reclaims water pot (pond), backwash tank (pond), slop oil tank, medicament establishing system, various water pump and oil-water metering facility etc.
In recent years, some new equipment have been developed in the processing of oily sewage (mainly being oil extraction-generated waste water) abroad, like novel closed float tank, hydrocyclone, various combined type oil-water separators etc.The successful exploitation of these devices is all of great advantage to integrated and the reduction equipment volume and the construction costs etc. of the treatment effect that improves oily sewage, the treatment efficiency that improves equipment, realization treatment facility function.
Yet be not that single method is handled oily waste water and just can be reached the effluent quality requirement, several kinds of disposal routes of actual waste water treatment project needs are combined into various treatment process system and handle oily waste water.Along with science and technology development, the improvement technology of oil-contaminated water of oil field is strengthened when constantly exploring and is improved both at home and abroad in recent years.According to the data from abroad introduction, the characteristics and the important symbol of new oilfield produced water treatment process are that hydrocyclone is introduced flow process, substitute traditional oil removal and flotation cells.In the U.S. North Sea oil field re-injection oil-containing sewage treatment technique flow process, adopted 3 oil-water separators and 6 hydrocyclone series connection, the water quality after the processing can reach the requirement of re-injection water.Wherein oil content is reduced to below 20～30mg/L by 200～500mg/L (mainly existing with O/W type form of emulsion).In addition, the many oil removal by air bubbling technology that adopted of the U.S.'s its treatment process in newly-built oily water treatment station.U.S.'s Gulf oilfield produced water processing technological flow is made up of unit such as oil-water separator, flocculation, air supporting, GAC-FBR (activated charcoal biological fluidized-bed reactor), electrodialysis; Handle back day maximum oil content and be no more than 10mg/L, reached very strict emission control standards.Many scholars' research shows, handles the condensed oil sewage that contains some hardly degraded organic substances and generally adopts the biochemical oxidation method, and its technological process mainly comprises unit operationss such as oil-water separator, air supporting, chemical oxidation, biological membrane hydrolysis acidification, filtration.
Developed and produced multiple sewage-treating agent in order to improve the oily waste water treatment effeciency, comprised coagulant, flocculating agent, flotation agent etc.Wherein the hydrophobic polymer flocculating agent can be accelerated water purification speed as efficient water treatment agent, removes suspension and noxious material in the water.The disposal route of oily waste water is also a lot, and particularly handle oily waste water and have the treatment effeciency height, the residence time is short, energy consumption is low, occupation of land is little by the turbine air flotation method for wherein air supporting method, control and characteristics easy to maintenance.Add flotation agent during air supporting and can not only obtain better air flotation effect, and can shorten the flocculation reaction time, this is to reducing capital expenditure, cutting down the consumption of energy and operating cost has great importance in the actual engineering.
Can roughly the flocculating agent of studying at present and using be divided into inorganic flocculating agent, organic flocculant, composite flocculation agent and microbial flocculant four big classes according to the composition of flocculating agent and preparation method's difference.
(1) inorganic flocculating agent
The applicating history of inorganic flocculating agent is long, and traditional inorganic flocculating agent has low molecular inorganic salts such as aluminium sulphate, aluminum chloride, ferrous sulphate, ferric trichloride, and its advantage is a less expensive, but there is bigger problem in they in water treatment procedure.Its consumption is big, and aggregation velocity is slow, and the floccus of formation is little, and corrosivity is strong, and in wastewater treatment, usually causes the sludge dewatering difficulty, and sludge quantity is big, and is undesirable at some occasion purifying water effect, and replaced by inorganic polymer flocculant gradually.Inorganic polymer flocculant is after the sixties in 20th century, just to grow up in the world.In recent years, development and application polymeric aluminum, iron, silicon and various composite flocculant became focus.The kind of inorganic polymer flocculant is cationic in the series that China progressively forms to have aluminium polychloride (PAC), polyaluminium sulfate (PAS), polymer phosphate aluminium (PAP), bodied ferric sulfate (PFC), a polymer phosphate iron (PFP) etc.; Anionic activated silicic acid (AS), polymeric silicicacid (PS) arranged; Inorganic composite type PAFC (PAFC), poly-silicic acid iron sulfate (PFSS), polysilicate sulfuric acid aluminium (PASS), polymeric silicicacid iron chloride (PFSC), polymerization sulfuric chlorohydrin iron (PFCS), polymer aluminium silicate (PASI), polymeric silicicacid iron (PFSI), polymer phosphate ferro-aluminum (PSFP), silico-calcium composite polymeric iron chloride (SCPAFC) etc. are arranged.They and traditional flocculating agent relatively usefulness are more excellent, and more cheap than organic polymer coargulator, and be widely used in feeding water, the various flow processs of industrial waste water and municipal effluent.
(2) organic polymer coargulator
The organic polymer coargulator molecular weight is big, of a great variety, have very strong adsorption bridging ability; Compare with inorganic polymer flocculant; Have that consumption is few, the flocculation dewatering ability is strong, settling velocity is fast, it is few to generate sludge quantity; And advantages such as the salt that coexisted, pH value and temperature effect are little received extensive attention in recent years, and it has a extensive future.Used at present and mainly contained organic polymer coargulator two major types synthetic and modification.
1. synthetic organic polymer flocculating agent
Press the electrically charged difference of macromolecular chain, that organic polymer coargulator can be divided into is cationic, four big types of anionic, nonionic and amphoteric ion types.Polyacrylamide (PAM) is owing to there is a small amount of amide group to be hydrolyzed to carboxyl in polymerization process; Often have the negative ion characteristic; Usually degree of hydrolysis is called non-ionic polyacrylamide, the partially hydrolyzed polyacrylamide that is called greater than 4% less than 4% polyacrylamide.In anionic synthetic organic polymer flocculating agent, high, the good water solubility of the partially hydrolyzed polyacrylamide molecular weight that contains shuttle sodium base anionic group is the broad-spectrum polymeric flocculant of excellent performance.Generally obtain, perhaps add the hydrolytic reagent heating hydrolysis and make amide group partly change carboxylic sodium base into and obtain by polyacrylamide by acrylic amide and PAA copolymerization.Because it contains equally distributed carboxyl anion, can combine to form corresponding gel with polyvalent metal ion, therefore effect is remarkable in containing heavy metal-polluted water treatment.In addition, sodium polyacrylate since higher, the good water solubility of its molecular weight, avirulence, strong flocculation also be used widely.Because how electronegative colloid and suspended particle be, use cationic flocculant can in particle electrically charged, reach the purpose of flocculation.Therefore, cationic high-molecular flocculant has become the focus of synthetic organic polymer flocculating agent.Consumption at state's cationic flocculants such as Japan and the United States accounts for 60% of synthetic flocculant total amount, and is annual also with the speed increment more than 10%.Cationic flocculant mainly is quaternary ammonium salts and polyamine class, and wherein cation-modified polyacrylamide occupies larger proportion.Cation-modified polyacrylamide generally obtains through copolymerization or mannich reaction, and major product has quaternary ammoniated PAMC, acrylic amide and N, N-dimethyl amido acrylamide copolymer.
Amphiphatic high polymer coagulant generally by the vinyl monomer that contains the yin, yang ionic group through free radicals copolymerization reaction and macromolecule modified obtaining, wherein anionic group is carboxyl, sulfonic group, sulfate, cation group is the quaternary amine alkali.Amphiphatic high polymer coagulant is owing to have the characteristics of yin, yang ionic group concurrently; Charged situation maybe be different under the different medium condition, are suitable for handling the pollutant with different electric charges, and its pH value scope of application is wide; Salt-resistance is good; Particularly when being directed against the pollution system of yin, yang ion coexist, Amphiphatic high polymer coagulant not only has electrical neutralization, adsorption bridging, and intermolecular " winding " package action is arranged.
2. natural modified polymeric flocculant
Natural modified family macromolecule organic flocculant is one type of ecological safety type flocculating agent, compares with synthetic organic polymer coargulator, has good " environmental acceptability ", and being one type has applications well prospect, cheap and good-quality novel flocculant.Because natural macromolecule flocculating agent electric density is less, molecular weight is on the low side, and molecular structure is difficult to regulation and control and is prone to biodegradation takes place and loses flocculation activity, so research direction mainly concentrates on they are carried out modification both at home and abroad.Can be divided into natural modified polymeric flocculant starch based, cellulose family, vegetable gum class and gather polysaccharide by raw material sources.Wherein the most noticeable to the modification of starch.Modification mainly contains the cationic starch of tertiary amine or quaternary amines through the etherification reaction preparation; Perhaps with monomer-grafted copolymerization, crosslinked such as acrylic amide, acrylic acid; Make multipolymer also have the high molecular character of synthetic simultaneously; Make multipolymer be the cladodification structure, disperse the flocculation group, making it has stronger absorption, bridge formation, volume to sweep effect to the particle in the suspension system.Present domestic development and use mainly contain the starch-grafted polymkeric substance of hydroxyl (ISC), cationic starch CS-1 type etc.In addition, in development and appliable plant glue class, gather and also obtain remarkable progress aspect the natural modified polymeric flocculant of polysaccharide.Like Xiao Yao etc., be raw material with the larch bark, not only flocculating effect is obvious with the quaternary ammoniated kation tannin JHF that obtains of benzyl chloride again after amine-methylated to tannin wherein, can also play inhibition, sterilization.Contain amide group, hydroxyl in the shitosan quasi-molecule; Can form stable huge legendary turtle compound with heavy metal ion; Through introducing methylol with the chloroacetic acid reaction, can make amphoteric chitosan after the hydrolysis, amido also capable of using and aldehyde radical reaction generate SChiff alkali; Select to contain in the molecular structure aldehyde of carboxyl, process amphoteric chitosan.Wu Gen etc. utilize the schiff base reaction between shitosan and the vanillic aldehyde, increase its side chain number and length, prepare flocculating agent VCG more efficiently, and its COD clearance is higher, and dosage is lower.
(3) composite flocculation agent
For the complicated water body of composition, single flocculating agent can not satisfy the requirement of water treatment usually.The development of composite flocculation agent is just arisen at the historic moment.Composite flocculation agent roughly is divided into inorganic composite flocculant, organic composite coagulator and inorganic organic composite coagulator three major types.Domestic and international research is primarily aimed at inorganic organic composite coagulator at present.The mechanism of action of such flocculating agent is: behind the sewage impurity absorption inorganic flocculating agent, the adsorption bridging effect through organic polymer coargulator precipitates.Because cooperative effect, composite flocculation agent has not only comprised the advantage of original single flocculating agent, has also remedied deficiency separately.Many reports are arranged recently both at home and abroad, as: usefulness PAC-PAM composite flocculation agents such as Chen Lifeng, Li Mingjun are respectively applied for ferrous salt, PAM composite flocculation agent and handle different turbidity sewages and contain the electroplating wastewater that C produces.Flocculating property, mechanism and optimal coagulant dose etc. to them have been done a series of deep researchs, be illustrated in soon the stage of stirring and be with compression double electric layer,
The absorption charge neutrality is main, and the stage of stirring is to be adsorbed as the master with bridging slowly, and incorgruous flocculation and difference fleece hocket with fixed attention in the quiet heavy stage, reach the purpose of rapid sedimentation.Usefulness PAMC and the composite efficient flocculatings of having realized the living rhzomorph fermentation liquor of centering of zeyssatite such as Li Shaojie have improved its liquid-solid separating property greatly.
(4) microbial flocculant
Microbial flocculant is meant and utilizes microbial technique, through the fermentation of microorganism, and extracting, refining and one type of flocculating agent obtaining has efficient, nontoxic, advantages such as the flocculation object is extensive, decolorizing effect uniqueness.In 70 generations of 20th century, Japanese scholar has found to have the microbial culture medium of flocculation in research phthalandione vinegar biodegradation process.In the later stage eighties, processed first kind of biological flocculant of called after NOC-1 and drop into suitability for industrialized production and be used for wastewater treatment.
The hydrophobic polymer flocculating agent can be accelerated water purification speed as efficient water treatment agent, removes suspension and noxious material in the water.But; The instant capacity and the bin stability of the existing many hydrophobic polymer solution that synthesize are not fine, and the hydrophobic polymer flocculating agent dissolves the thinning or formation microgel of solution postpone of a specified duration of back preparation owing to the introducing of hydrophobic monomer is difficult to dissolving; Even occur being separated, produce white precipitate.
In the synthesis technique of hydrophobic polymer flocculating agent, initiating agent dosage major decision the size of polymer molecular weight, there is an optimum value scope in molecular weight to the influence of flocculating property.The too little or too high effect that does not all have efficient flocculating of molecular weight is because the flocculation process of organic polymer coargulator relates generally to the charge neutrality and absorption two aspects of building bridge.When molecular weight is too low,, is difficult to produce the crane span structure effect and forms flco, play protecting colloid on the contrary, cause that the part colloidal particles can't go down by flocculating setting in the supernatant though polymkeric substance can be adsorbed on the surface of particle.Along with polymer molecular weight increases, the big size of molecule in solution is just big more, and the crane span structure ability is strong more, and flocculating effect strengthens.But the molecular weight that is not polymkeric substance is just good more to flocculating effect more greatly, and molecular weight is too big, and flocculation rate is too fast, can cause the suspension of fine particle to remain in the supernatant liquor.Molecular weight is too big in addition, and polymer water dissolubility variation is difficult for disperseing and dissolving in water body, is unfavorable for flocculation.
When the hydrophobic polymer flocculating agent was applied to wastewater treatment, the salinity in the sewage can produce very big influence to its flocculating effect.Therefore; Test out the different flocculating effect of hydrophobic polymer flocculating agent in the sewage of different salt concentration; And then, the hydrophobic polymer flocculating agent is applied to wastewater treatment seems most important according to the different different hydrophobic polymer flocculating agents of sewage selection.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art; A kind of method of testing salinity to the flocculating effect influence of hydrophobic polymer flocculating agent is provided, and this method of testing can test out the influence of salinity to hydrophobic polymer flocculating agent flocculating effect fast, and measuring accuracy is high; Operation steps is simple; Testing cost is low, and then can select different hydrophobic polymer flocculating agents according to different sewage, improves the wastewater treatment efficiency of hydrophobic polymer flocculating agent.
The object of the invention is realized through following technical proposals: the test salinity may further comprise the steps the method for the flocculating effect influence of hydrophobic polymer flocculating agent:
(a) preparation hydrophobic polymer flocculating agent sample;
(b) the clay suspension of preparation different salt concentration;
(c) the clay suspension with the different salt concentration of equivalent adds respectively in the different test chambers, and is adjusted to identical pH value;
(d) the hydrophobic polymer flocculating agent of adding equivalent in the clay suspension;
(e) leave standstill a period of time, compare transmittance through observing, thereby obtain the influence of salinity hydrophobic polymer flocculating agent flocculating effect.
In the said step (c), test chamber is a beaker.
In the said step (c), the value of pH value is 7.
In the said step (c), regulate the pH value of clay suspension through HCl solution and NaOH solution.
The concentration of said HCl solution and NaOH solution is 0.1mol/L.
In the said step (b), salt is NaCl.
In sum; The invention has the beneficial effects as follows: can test out the influence of salinity fast hydrophobic polymer flocculating agent flocculating effect; Measuring accuracy is high, and operation steps is simple, and testing cost is low; And then can select different hydrophobic polymer flocculating agents according to different sewage, improve the wastewater treatment efficiency of hydrophobic polymer flocculating agent.
Description of drawings
Fig. 1 is the curve map of salinity to the transmittance influence.
Embodiment
Below in conjunction with embodiment, the present invention is done further detailed description, but embodiment of the present invention is not limited only to this.
Embodiment:
The test salinity that the present invention relates to is to the method for the flocculating effect influence of hydrophobic polymer flocculating agent, and its concrete steps are following:
(a) preparation hydrophobic polymer flocculating agent sample;
(b) the clay suspension of preparation different salt concentration;
(c) the clay suspension with the different salt concentration of equivalent adds respectively in the different test chambers, and is adjusted to identical pH value;
(d) the hydrophobic polymer flocculating agent of adding equivalent in the clay suspension;
(e) leave standstill a period of time, compare transmittance through observing, thereby obtain the influence of salinity hydrophobic polymer flocculating agent flocculating effect.
In the said step (c), test chamber is a beaker.
In the said step (c), the value of pH value is 7.
In the said step (c), regulate the pH value of clay suspension through HCl solution and NaOH solution.
The concentration of said HCl solution and NaOH solution is 0.1mol/L.
In the said step (b), salt is NaCl.
When the hydrophobic polymer flocculating agent was applied to wastewater treatment, the salinity in the sewage can produce very big influence to its flocculating effect.Therefore; Test out the different flocculating effect of hydrophobic polymer flocculating agent in the sewage of different salt concentration; And then, the hydrophobic polymer flocculating agent is applied to wastewater treatment seems most important according to the different different hydrophobic polymer flocculating agents of sewage selection.
Because the flocculating effect of hydrophobic polymer flocculating agent directly can draw through its transmittance, so the present invention has recorded the influence of different dosages to transmittance, can draw its flocculating effect through transmittance; The present invention has selected on the market modal NaCl as the salt in the sewage; Result through said method records is as shown in Figure 1, and as can beappreciated from fig. 1: along with NaCl concentration increases, transmittance obviously rose before this; When NaCl concentration was 0.06%, transmittance was up to 97.1%.Yet along with the continuation of NaCl concentration increases, printing opacity takes the lead in descending a little to some extent, and it is mild to descend.Along with the rising of NaCl concentration, Na
+Constantly push the surface of clay diffuse electric double layer; The current potential of colloidal particle diminishes, and electrostatic double layer constantly is compressed, and the clay micelle collides more easily and forms more closely knit aggregation; More easily and interpolymer interaction and flocculate, so transmittance obviously rises through bridging action.Yet the affiliation that adds of NaCl causes the contraction of big molecular coil, is unfavorable for bridging action, and under the acting in conjunction of this effect and the effect of NaCl promotion particle coagulation, transmittance amplitude of variation under higher salt concentrations is very little, and settling of floccus speed descends to some extent.
Above-mentioned method of testing can test out the influence of salinity to hydrophobic polymer flocculating agent flocculating effect fast; Measuring accuracy is high; Operation steps is simple; Testing cost is low, and then can select different hydrophobic polymer flocculating agents according to different sewage, improves the wastewater treatment efficiency of hydrophobic polymer flocculating agent.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction, and every foundation technical spirit of the present invention, any simple modification, equivalent variations to above embodiment did all fall within protection scope of the present invention.
Claims (6)
1. the test salinity is characterized in that the method for the flocculating effect influence of hydrophobic polymer flocculating agent, may further comprise the steps:
(a) preparation hydrophobic polymer flocculating agent sample;
(b) the clay suspension of preparation different salt concentration;
(c) the clay suspension with the different salt concentration of equivalent adds respectively in the different test chambers, and is adjusted to identical pH value;
(d) the hydrophobic polymer flocculating agent of adding equivalent in the clay suspension;
(e) leave standstill a period of time, compare transmittance through observing, thereby obtain the influence of salinity hydrophobic polymer flocculating agent flocculating effect.
2. test salinity according to claim 1 is characterized in that to the method for the flocculating effect influence of hydrophobic polymer flocculating agent in the said step (c), test chamber is a beaker.
3. test salinity according to claim 1 is characterized in that to the method for the flocculating effect influence of hydrophobic polymer flocculating agent in the said step (c), the value of pH value is 7.
4. test salinity according to claim 1 is characterized in that the method for the flocculating effect influence of hydrophobic polymer flocculating agent, in the said step (c), regulates the pH value of clay suspension through HCl solution and NaOH solution.
5. test salinity according to claim 4 is characterized in that to the method for the flocculating effect influence of hydrophobic polymer flocculating agent the concentration of said HCl solution and NaOH solution is 0.1mol/L.
6. test salinity according to claim 1 is characterized in that to the method for the flocculating effect influence of hydrophobic polymer flocculating agent in the said step (b), salt is NaCl.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103245623A (en) * | 2013-05-11 | 2013-08-14 | 北京工业大学 | Method for measuring relative hydrophobicity of granule sludge cells |
| CN103524016A (en) * | 2013-10-22 | 2014-01-22 | 山东省环境保护科学研究设计院 | Stable settling agent and stable settling method of heavy-metal bottom mud |
| CN108728365A (en) * | 2018-04-18 | 2018-11-02 | 中国科学院生态环境研究中心 | A method of being suitable for efficient flocculating harvesting microalgae under wide Variation of Salinity Condition |
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2010
- 2010-11-22 CN CN2010105676173A patent/CN102478511A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103245623A (en) * | 2013-05-11 | 2013-08-14 | 北京工业大学 | Method for measuring relative hydrophobicity of granule sludge cells |
| CN103524016A (en) * | 2013-10-22 | 2014-01-22 | 山东省环境保护科学研究设计院 | Stable settling agent and stable settling method of heavy-metal bottom mud |
| CN108728365A (en) * | 2018-04-18 | 2018-11-02 | 中国科学院生态环境研究中心 | A method of being suitable for efficient flocculating harvesting microalgae under wide Variation of Salinity Condition |
| CN108728365B (en) * | 2018-04-18 | 2022-07-01 | 中国科学院生态环境研究中心 | Method for efficiently flocculating and harvesting microalgae under wide salinity condition |
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Application publication date: 20120530 |