CN107055729A - The chitosan flocculant that a kind of dopamine is modified - Google Patents
The chitosan flocculant that a kind of dopamine is modified Download PDFInfo
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- CN107055729A CN107055729A CN201710389155.2A CN201710389155A CN107055729A CN 107055729 A CN107055729 A CN 107055729A CN 201710389155 A CN201710389155 A CN 201710389155A CN 107055729 A CN107055729 A CN 107055729A
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention provides a kind of chitosan flocculant for handling the sewage containing polyacrylamide, is to prepare the dopamine that chitosan has o-dihydroxy structure by glutaraldehyde scion grafting in acid condition.The material green non-pollution used of the flocculant of the present invention, the harm to environment is smaller；The novel flocculant synthesized through dopamine grafted chitosan substantially increases the adsorption capacity and dissolubility of chitosan, good to polymer-bearing waste-water flocculating effect；Can be with secondary flocculation dye wastewater containing the precipitation after polyacrylamide sewage water using flocculant process, and have more satisfactory flocculating effect；The flocculant is realized reclaims secondary recycling to polyacrylamide, has relatively good flocculating effect to polymer-bearing waste-water and dyeing and printing sewage, substantially increases flocculation efficiency, has saved flocculation cost.
Description
Technical field
The invention belongs to technical field of sewage, and in particular to a kind of preparation method of new modified chitosan flocculant
And with handling process of the flocculant to petroleum waste water and dyeing and printing sewage.
Background technology
The current most of oil field of China is widely used deposits in polyacrylamide (PAM) displacement of reservoir oil, but oil well produced liquid
PAM make oilfield sewage turn into a kind of complicated profit system.This polymer-bearing waste-water is compared with common sewage：Viscosity is bigger,
Emulsion system is more stablized, interfacial film strength increase, demulsification difficulty increase, and sewage takes husky amount and takes oil mass increase.Therefore due to
PAM presence adds sewage disposal in difficulty.Some simple processing have only been done in most domestic oil field, and this processing is often
It is extremely difficult to the discharge standard of country.If this sewage not up to standard is discharged into underground, formation pore can be caused to block, reduction note
Outlet capacity and oil well output；If serious wound will can be caused to the health and ecological environment of human and animal on the ground by being discharged into
Evil.Therefore the processing of polymer-bearing waste-water is an important content of disposing polluted water in oil.
The method of current polymer-contained sewage mainly has physicomechanical processes, microorganism treatment, method of chemical treatment.Physical machine
Tool method handling process is fairly simple, but needs large-scale processing equipment and treatment effeciency is than relatively low.Microorganism treatment is excellent
Point is treatment effeciency height and cleanliness without any pollution, but investigative technique is immature, microbe-derived relatively simple, environmental suitability
Difference, is extremely difficult to the requirement of extensive polymer-contained sewage.Method of chemical treatment mainly includes some inorganic flocculants, such as gathers
Ferric sulfate and aluminium polychloride are closed, its advantage is that processing method is simple, economical and practical；Disadvantage is often to cause secondary dirt
Dye.But there is presently no report for the research of organic flocculant polymer-contained sewage.
The method of current polymer-contained sewage still has many deficiencies to need improvement in summary.Used the invention provides one kind
The new organic flocculant of chitosan that dopamine is modified, this will be a new technical field.Chitosan is inherently a kind of
Flocculant, environmental protection is cheap, and can be biodegradable；Dopamine is from the viscous of marine organisms mussel bio secretion
Found in attached albumen, with preferable biocompatibility, adhesiveness and water imbibition.Dopamine is introduced on chitosan skeleton to carry
The high adsorptivity of chitosan, is realized to PAM flocculation treatments；And the sedimentation compound two of PAM and flocculant can be reclaimed
Secondary utilize handles dyeing and printing sewage.
The content of the invention
To solve the above problems, the present invention provides a kind of chitosan flocculant of polymer-contained sewage, and preparation method thereof
With corresponding sewage treatment process, so as to solve the green process problem of wastewater efficient.
Chitosan flocculant provided by the present invention, its structural formula is as follows：
Wherein n scope is 1500-2500.
Chitosan flocculant provided by the present invention is that chitosan is had into neighbour by glutaraldehyde scion grafting in acid condition
Prepared by the dopamine of dihydroxy based structures.
A kind of described flocculant, its preparation method is as follows
1) dissolve chitosan in acid solution, add glutaraldehyde, the stirring reaction at 30-50 DEG C；Will be reacted molten
Liquid, which is fitted into the bag filter that molecular cut off is 14000, is dialysed；
2) by step 1) obtain dialyzate in add stirring reaction at excessive dopamine, 20-30 DEG C；Solution after reaction
It is fitted into the bag filter of molecular cut off 14000 and is dialysed；
3) in step 2) dialyzate in add stirring reaction at sodium borohydride, 20-30 DEG C；Reaction solution centrifugation is sunk
Form sediment, precipitation is dried；
4) 5 parts of weight percent methyl iodides, 2 parts of weight sodium hydroxides and 3.6 parts of weight sodium iodides are dissolved in 120 parts of weight respectively
In METHYLPYRROLIDONE, stir；
5) precipitation obtained in 3) is added in the solution described in (4), stirring reaction at 30-60 DEG C；After reaction terminates,
Acetone precipitation product is added, solution is filtered or centrifugation obtains product, flocculant is dried to obtain.
Be used as the preferred of embodiment, step 1) described in acid solution be hydrochloric acid or acetic acid.
Step 2) described in dopamine and chitosan mass ratio be 1:1-5:1.Step 4) described in methyl iodide quality
Mass ratio with chitosan is 1:1-3:1.
Flocculant provided by the present invention is used to handle sewage and dyeing and printing sewage containing polyacrylamide.
A kind of its application method, is first to handle after the sewage containing polyacrylamide, reclaims flocculant and polyacrylamide
Compound, be used further to handle dyeing and printing sewage.
The material green non-pollution used of the flocculant of the present invention, biocompatibility is preferably, cheap；Effectively through many
The novel flocculant of bar amine grafted chitosan synthesis substantially increases the adsorption capacity and dissolubility of chitosan, and polymer-bearing waste-water is wadded a quilt with cotton
Solidifying effect significantly, has filled up the blank of organic flocculant polymer-contained sewage.Because PAM is also a kind of flocculant in itself, commonly use
In sewage disposal；Therefore we utilize flocculant process polymer-bearing waste-water after sediment composite can with secondary flocculation dye wastewater,
Realize and secondary recycling is reclaimed to flocculant and PAM, substantially increase flocculation efficiency, saved flocculation cost.
Brief description of the drawings
Fig. 1：The syntheti c route figure of the flocculant of the present invention；Wherein (i) Chi is that chitosan raw material (ii) GDC is glutaraldehyde
The intermediate product that scion grafting with chitosan is generated, (iii) GDC-g-DA is the final product that GDC is synthesized with the scion grafting of dopamine.
Fig. 2:Flocculant III and PAM the flocculation dye methyl violet sewage design sketch of the present invention.
Fig. 3:Comparison diagram before and after flocculant III of the present invention and PAM flocculation BG dye wastewater flocculations.
Fig. 4：Clearances and PH graph of a relation of the flocculant III of the present invention to PAM.
Fig. 5：The flocculant III of present invention quality and the graph of a relation of PAM clearances.
Embodiment
The present invention is described in detail with reference to specific embodiment.
Embodiment 1：
(1) by 1 gram of chitosan, (deacetylation is 80%, and ten thousand) relative molecular mass, is dissolved in 50ml acetic acid for 35
In (0.1mol/L) solution, adjusted with 0.1mol/L sodium hydroxide solution to PH and be equal to 5,120 grams of glutaraldehydes are added, at 48 DEG C
Lower high-speed stirred reacts 24h.Reacted solution is fitted into molecular cut off in 14000 bag filters and bag filter is placed in into 1L
Dialyse 12h in water, is repeated 7 times.
(2) in (1) described dialyzate, high-speed stirred reaction 12h at 1 gram of dopamine, 25 DEG C is added.Solution after reaction
It is fitted into the bag filter of molecular cut off 14000 and bag filter is placed in 1L water the 12h that dialyses, is repeated 7 times.
(3) in (2) described dialyzate, add at 0.5 gram of sodium borohydride, 25 DEG C and stir 12h.By solution in 2000rpm
Centrifuged under rotating speed, take and 12h is dried at 100 DEG C of lower sediment thing.
(4) 5 grams of methyl iodides, sodium hydroxide and 1 gram of sodium iodide are dissolved in 120 grams of METHYLPYRROLIDONEs respectively.
(5) material described in (3) is added in the solution described in (4), high-speed stirred reacts 12h at 50 DEG C.Reaction knot
Shu Hou, the acetone precipitation product of 100 grams of addition, 2000rpm centrifugations obtain drying 24h at product, 100 DEG C, obtain grafting rate
52% flocculant I.
Embodiment 2：
(1) by 1 gram of chitosan, (deacetylation is 80%, and ten thousand) relative molecular mass, is dissolved in 50ml acetic acid for 35
In (0.1mol/L) solution, adjusted with 0.1mol/L sodium hydroxide solution to PH and be equal to 5,120 grams of glutaraldehydes are added, at 48 DEG C
Lower high-speed stirred reacts 24h.Reacted solution is fitted into molecular cut off in 14000 bag filters and bag filter is placed in into 1L
Dialyse 12h in water, is repeated 7 times.
(2) in (1) described dialyzate, high-speed stirred reaction 12h at 3 grams of dopamine, 25 DEG C is added.Solution after reaction
It is fitted into the bag filter of molecular cut off 14000 and bag filter is placed in 1L water the 12h that dialyses, is repeated 7 times.
(3) in (2) described dialyzate, add at 0.5 gram of sodium borohydride, 25 DEG C and stir 12h.By solution in 2000rpm
Centrifuged under rotating speed, take and 12h is dried at 100 DEG C of lower sediment thing.
(4) 5 grams of methyl iodides, sodium hydroxide and 3 grams of sodium iodides are dissolved in 120 grams of METHYLPYRROLIDONEs respectively
In.
(5) material described in (3) is added in the solution described in (4), high-speed stirred reacts 12h at 50 DEG C.Reaction knot
Shu Hou, the acetone precipitation product of 100 grams of addition, 2000rpm centrifugations obtain drying 24h at product, 100 DEG C, obtain grafting rate
60% flocculant II.
Embodiment 3：
(1) by 1 gram of chitosan, (deacetylation is 90%, and ten thousand) relative molecular mass, is dissolved in 50ml hydrochloric acid for 25
In (0.1mol/L) solution, adjusted with the sodium hydroxide solution of mass fraction 0.1% to PH and be equal to 5, add 120 grams of glutaraldehydes,
High-speed stirred reacts 24h at 48 DEG C.Reacted solution is fitted into molecular cut off in 14000 bag filters and by bag filter
The 12h that dialyses is placed in 1L water, is repeated 7 times.
(2) in (1) described dialyzate, high-speed stirred reaction 12h at 5 grams of dopamine, 25 DEG C is added.Solution after reaction
It is fitted into the bag filter of molecular cut off 14000 and bag filter is placed in 1L water the 12h that dialyses, is repeated 7 times.
(3) in (2) described dialyzate, add at 0.5 gram of sodium borohydride, 25 DEG C and stir 12h.By solution in 2000rpm
Centrifuged under rotating speed, take and 12h is dried at 100 DEG C of lower sediment thing.
(4) 5 grams of methyl iodides, sodium hydroxide and 1 gram of sodium iodide are added in 120 grams of METHYLPYRROLIDONEs respectively.
(5) material described in (3) is added in the solution described in (4), high-speed stirred reacts 12h at 50 DEG C.Reaction knot
Shu Hou, the acetone precipitation product of 100 grams of addition, 2000rpm centrifugations obtain drying 24h at product, 100 DEG C, obtain grafting rate
75% flocculant III.
The polymer-contained sewage of embodiment 4 and secondary flocculation dye methyl violet sewage
It is 500mg/L to prepare PAM concentration respectively, and PH is 7 polymer-bearing waste-water, and crystal violet concentration is dirty for 100mg/L printing and dyeing
Water.Take 5 parts of 20ml polymer-bearing waste-water, be separately added into the chitosans of phase homogenous quantities, aluminium polychloride, flocculant I, flocculant II,
Flocculant III, each 20mg, 200rpm quickly stir 5min, and then 50rpm stirs 15min slowly, to precipitation generation, take within static 2 hours
The supernatant of solution carries out detecting its viscosity before and after flocculation, and according to formula Q=(No-Ne)/No*100%, (wherein Q represents to remove
Rate, No and Ne represent respectively flocculation before and after solution viscosity, unit is Pa.S) calculate PAM clearance.Secondary flocculation takes 5
Part 20ml dyeing and printing sewage is separately added into above-mentioned each 20mL of flocculation sediment compound of same volume, and 200rpm is quickly stirred
5min, then 50rpm stir 15min, static 2 hours slowly.Its supernatant is taken to determine the ultraviolet absorption value of crystal violet according to formula Q=
(Ao-Ae) (wherein Q represents clearance rate to/Ao*100%, and Ao and Ae represent the ultraviolet absorption value of the solution before and after flocculation respectively, single
Position is L/ (gcm)) so as to calculate clearance rate.
The different flocculants of table 1 are to PAM and the removal effect of crystal violet
| Flocculant | Polyacrylamide clearance | Crystal violet clearance |
| Chitosan | 25% | 20% |
| Aluminium polychloride | 43% | 58% |
| Flocculant I | 53% | 71% |
| Flocculant II | 57% | 76% |
| Flocculant III | 62% | 81% |
Major pollutants PAM decides the viscosity of sewage in polymer-bearing waste-water；Therefore in polymer-contained sewage, viscosity is to comment
One key factor of valency sewage flocculation effect.Therefore we calculate PAM clearance rate by the viscosity of sewage before and after flocculation.
The chitosan being modified as can be seen from Table 1 through dopamine is significantly larger than poly-aluminium and unmodified shell to polyacrylamide clearance
Glycan；Thus adhesion and bridge formation ability that dopamine improves chitosan are also demonstrated.It can be seen that two from table 1 and Fig. 2
Secondary flocculation crystal violet sewage also achieves preferable flocculating effect, realizes the recycling to flocculant and PAM, greatly improves
Flocculation efficiency, has saved flocculation cost.
The polymer-contained sewage of embodiment 5 and secondary flocculation BG dye wastewater
It is 500mg/L to prepare PAM concentration respectively, and PH is 9 polymer-bearing waste-water, and BG concentration is 150mg/L dyeing and printing sewage.
5 parts of 20ml polymer-bearing waste-water is taken, the chitosans of phase homogenous quantities, aluminium polychloride, flocculant I, flocculant II, flocculation is separately added into
Agent III, each 20mg, 200rpm quickly stir 5min, and then 50rpm stirs 15min slowly, generate within static 2 hours to precipitation, according to public affairs
(wherein Q represents clearance rate to formula Q=(No-Ne)/No*100%, and No and Ne represent the viscosity of the solution before and after flocculation, unit respectively
Pa.S) calculate PAM clearance.Secondary flocculation takes 5 parts of 20ml dyeing and printing sewage to be separately added into the above-mentioned flocculation of same volume
Sediment composite each 20mL, 200rpm quickly stir 5min, and then 50rpm stirs 15min, static 2 hours slowly.Its supernatant is taken to survey
Determining the ultraviolet absorption value of BG, (wherein Q represents clearance rate, and Ao and Ae are represented respectively according to formula Q=(Ao-Ae)/Ao*100%
The ultraviolet absorption value of solution before and after flocculation, unit is L/ (gcm)) so as to calculate BG clearance rate.
Removal effect of the flocculant of table 2 to PAM and BG
| Flocculant | PAM clearances | BG clearance |
| Chitosan | 25% | 16% |
| Aluminium polychloride | 43% | 67% |
| Flocculant I | 58% | 85% |
| Flocculant II | 61% | 90% |
| Flocculant III | 67% | 94% |
The flocculating effect of the novel chitosan flocculant synthesized as can be seen from Table 2 will far better than traditional flocculant,
Wherein flocculant C flocculating effect is best.It can be found that in alkalescence condition in PAM result of once being flocculated in comparative example 4
Lower flocculation PAM effect is more preferable.Secondary flocculation BG dye wastewater, the color hair of BG before and after as can be seen from Figure 3 flocculating
BG dye wastewater is given birth to after obvious change, flocculation close to colourless, clearance has reached 94%.
Influences of the embodiment 6PH to the PAM that flocculates
It is 500mg/L to prepare PAM concentration respectively, and PH is 3,5,7,9,11,13 polymer-bearing waste-water, respectively takes 20ml, adds matter
Amount identical flocculant III20mg, 200rpm quickly stir 5min, and then 50rpm stirs 15min, static 2 hours to precipitation life slowly
Into, take flocculation before and after solution supernatant carry out detect its viscosity according to formula Q=(No-Ne)/No*100%, (wherein Q is represented
Clearance rate, No and Ne represent respectively flocculation before and after solution viscosity, unit is Pa.S) calculate PAM clearance rate.Draw PAM
The graph of a relation of clearance rate and PH, as shown in figure 4, gradually increasing with PH rise PAM clearance rates, compares in the environment of alkalescence
Flocculating effect in acid environment is more preferable, the clearance highest when PH is 11.
Influence of the different flocculant additions of embodiment 7 to the PAM that flocculates
It is 500mg/L to prepare PAM concentration, and PH is 11 polymer-bearing waste-water.The polymer-bearing waste-water 20mL of 6 parts of same volumes is taken, point
Not Jia Ru flocculant III 5mg 10mg 15mg 20mg 25mg 30mg35mg, 200rpm quickly stir 5min, then 50rpm
It is slow to stir 15min, static 2 hours to precipitation generation, take the supernatant of solution before and after flocculating to carry out detecting its viscosity according to formula Q=
(No-Ne) (wherein Q represents clearance rate to/No*100%, and No and Ne represent the viscosity of the solution before and after flocculation respectively, and unit is
Pa.S PAM clearance rate) is calculated.Draw the graph of a relation of PAM clearance rates and flocculant III mass, as can be seen from Figure 5 with
The increase of flocculant addition, removal takes the lead in increasing and then tended towards stability, and when adding 25mg, clearance reaches maximum, backward base
This holding is stable.Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned technological means, also
Including being combined constituted technical scheme by above technical characteristic.Described above is the embodiment of the present invention, should
When pointing out, for those skilled in the art, under the premise without departing from the principles of the invention, it can also make
Some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (9)
1. a kind of chitosan flocculant, its structural formula is as follows：
Wherein n is 1500-2500.
2. the preparation method of the chitosan flocculant described in claim 1, is in acid condition by glutaraldehyde by chitosan
Scion grafting has prepared by the dopamine of o-dihydroxy structure.
3. preparation method as claimed in claim 2, it is characterised in that the preparation process of described method is as follows：
1) by the molten acid solution of chitosan, glutaraldehyde, the stirring reaction at 30-50 DEG C are added；Reacted solution is loaded and cut
Stay and dialysed in the bag filter that molecular weight is 14000；
2) by step 1) obtain dialyzate in add stirring reaction at excessive dopamine, 20-30 DEG C；Solution loads after reaction
Dialysed in the bag filter of molecular cut off 14000；
3) in step 2) dialyzate in add stirring reaction at sodium borohydride, 20-30 DEG C；Reaction solution centrifugation is precipitated, and is sunk
Shallow lake is dried；
4) 5 parts of weight percent methyl iodides, 2 parts of weight sodium hydroxides and 3.6 parts of weight sodium iodides are added to 120 parts of weight N- first respectively
Solution is made in base -2-Pyrrolidone；
5) by step 3) in obtained precipitation be added in the solution described in (4), stirring reaction at 30-60 DEG C；After reaction terminates,
Acetone precipitation product is added, solution is filtered or centrifugation obtains product, flocculant is dried to obtain.
4. method as claimed in claim 4, it is characterised in that described step 1) in acid solution be hydrochloric acid or acetic acid.
5. method as claimed in claim 4, it is characterised in that described step 2) in dopamine and chitosan mass ratio
For 1-5:1.
6. method as claimed in claim 4, it is characterised in that described step 4) described in methyl iodide and chitosan quality
Than for 1-3:1.
7. application of the chitosan flocculant in sewage of the processing containing polyacrylamide described in claim 1.
8. application of the chitosan flocculant in processing dyeing and printing sewage described in claim 1.
9. a kind of method for handling sewage, it is characterised in that described method, is that first the chitosan described in claim 1 is wadded a quilt with cotton
Solidifying agent is added to adsorbed after the sewage containing polyacrylamide after, reclaim flocculant, be then added in dyeing and printing sewage carry out
Absorption.
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| CN109402193A (en) * | 2018-11-08 | 2019-03-01 | 浙江海洋大学 | A method of flocculant is prepared using ocean cock Salmonella |
| CN110327896A (en) * | 2019-06-21 | 2019-10-15 | 中科广化（重庆）新材料研究院有限公司 | A kind of magnetism poly-dopamine/carboxymethyl chitosan adsorbent and the preparation method and application thereof |
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| CN110952326B (en) * | 2019-12-20 | 2022-05-03 | 晋江亿兴隆纺织实业有限公司 | Size for full cotton yarn slashing and slashing process |
| CN114622411A (en) * | 2019-12-20 | 2022-06-14 | 晋江亿兴隆纺织实业有限公司 | Environment-friendly sizing process for all-cotton yarn |
| CN114622411B (en) * | 2019-12-20 | 2023-10-20 | 晋江亿兴隆纺织实业有限公司 | Environment-friendly sizing process of all-cotton yarn |
| CN112520934A (en) * | 2020-12-18 | 2021-03-19 | 华自科技股份有限公司 | Method for producing tap water by utilizing magnetic weighting agent coagulation magnetic separation technology |
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