CN107265675A - A kind of solid slow-release type antisludging agent and preparation method thereof - Google Patents
A kind of solid slow-release type antisludging agent and preparation method thereof Download PDFInfo
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- CN107265675A CN107265675A CN201710509466.8A CN201710509466A CN107265675A CN 107265675 A CN107265675 A CN 107265675A CN 201710509466 A CN201710509466 A CN 201710509466A CN 107265675 A CN107265675 A CN 107265675A
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
- C02F5/125—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
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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
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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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
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Organic Chemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to oilfield additive technical field, and in particular to a kind of solid slow-release type antisludging agent and preparation method thereof.The antisludging agent is by organic acid, bio-matrix, water, adhesive, dispersant and auxiliary agent composition, its preparation method is to handle with briquetting in press is put into after being stirred in mixer raw material, then collect extrudate and natural air drying, air dry matter is crushed again, sieving, collect sieving particle, solid slow-release type antisludging agent can be obtained, gained solid slow-release type antisludging agent of the invention has slow release, dosing is convenient, the good advantage of scale inhibition effect, can be to oil well casing after use, the equipment such as oil pipe and pull bar plays a good protection, reduce oilfield servicing cost payout, it is a kind of easy to use, the oilfield additive of economy and durability.
Description
Technical field
The invention belongs to oilfield additive technical field, and in particular to a kind of solid slow-release type antisludging agent and preparation method thereof.
Background technology
In oilfield, the essence of fouling is that oil field water turns into supersaturation.The scale formation of oil field water is often caused
It is stuck such as oil well pump, annular space is blocked, the internal diameter of gathering line falls sharply between well casing and sucker rod, or even by Severe blockage etc.
Problem, has severely impacted being normally carried out for oil field production.
At present, the method for control oil field water fouling can be largely classified into chemical method and physical method.Chemical scale-inhibiting method
Including ion exchange softening method, lime softening method, acid adding method, it is passed through CO2Method plus antisludging agent method, physical scale inhibition method then include
Embrane method, Electrostatic water treatment, electronics water process, coat heat exchanger anti-corrosion, scale-inhibiting coating with anti-corrosion, scale-inhibiting coating and suppress fouling, use
Plastic heat exchanger.Compared with physical method, chemical method is particularly plus the method for antisludging agent has small investment, is fed intake simple, effect
Really good the advantages of, thus oilfield scales preventing and treating frequently with this method.
Presently used corrosion inhibiting and descaling agent is usually the liquid of organic phosphoric acid, polymerization of carboxylic acid and polymeric phosphate compound system
Antisludging agent.This system has good limit effect and synergistic, has the advantages that cost is low, consumption is few, easy to use, but
It is that, there is also some shortcomings, generally for scale problems are solved, the antisludging agent of liquid is directly injected into underground by people from well head, but
These antisludging agents soon as Produced Liquid flows away or stick to shaft bottom can not be all arrived on tube wall, therefore addition compared with
Greatly, action period and effect are also not ideal enough, waste substantial amounts of medicine, return production and management brings many troubles.It is based on
How this, overcome the shortcomings of existing liquid antisludging agent, develops that a kind of addition is small, scale inhibition effect is good, and action period length is consolidated
The problem of build antisludging agent is oilfield additive field urgent need to resolve.
The content of the invention
The technical problems to be solved by the invention：It is big for current liquid antisludging agent addition, action period and scale inhibition effect
There is provided a kind of solid slow-release type antisludging agent and preparation method thereof for really undesirable defect.
In order to solve the above technical problems, the present invention is using technical scheme as described below：
A kind of solid slow-release type antisludging agent, it is characterised in that include the raw material of following parts by weight：60~65 parts of organic acids, 40
~45 parts of bio-matrixes, 20~25 parts of water, 15~20 parts of adhesives, 6~9 parts of dispersants, 1~3 part of auxiliary agent.
2. solid slow-release type antisludging agent according to claim 1, it is characterised in that the preparation method of the organic acid
Comprise the following steps：
（1）In mass ratio 1:3, maleic anhydride and lysine are put into reactor, the four of 2~3 times of lysine quality are added
The titanium dioxide of hydrogen furans and lysine quality 1~2%, is heated to reflux；
（2）After backflow terminates, filtered, collect filter residue, rinsed filter residue using water, the filter residue after flushing is air-dried, collected
Air dry matter, in mass ratio 3~6:1, air dry matter is well mixed with sodium citrate, you can obtain organic acid.
The preparation of the bio-matrix comprises the following steps：
A. in mass ratio 1:3, the dirt in oil field pipe is well mixed with rural area soil, mixture is collected, water use regulation is mixed
The water content of compound is then layed in culture pond to 60~65%, and laying depth is 6~10cm, by 80~90 every square metre
If the earthworm of earthworm phase, cultivated if the earthworm of earthworm phase is put into culture pond；B. culture pond internal memory is collected after culture terminates
Earthworm living, by the earthworm of collection and 1.2mol/L hydrochloric acid in mass ratio 1:3 are put into bruisher and smash to pieces, and mixing is smashed in collection to pieces
Thing, is centrifuged, and collects centrifugate, centrifugate is freeze-dried, and collects dried object, you can obtain bio-matrix.
Described adhesive is polyvinylpyrrolidone and polyvinyl alcohol in mass ratio 1:4 mix.
The dispersant is any one in sodium tripolyphosphate, lauryl sodium sulfate or stearic acid.
The auxiliary agent is triethanolamine and titanium dioxide in mass ratio 6:1 mixes.
A kind of preparation method of solid slow-release type antisludging agent, comprises the following steps：Proportioning progress by weight takes raw material,
It is put into mixer and stirs, collect stirring mixture, be placed in press carrying out briquetting, collects extrudate, and natural wind
It is dry, air dry matter is crushed, sieved, sieving particle is collected, you can obtain solid slow-release type antisludging agent.The present invention and other method phase
Than advantageous effects are：
（1）The present invention in tetrahydrofuran environment and under Titanium Dioxide effect, forms acyl by maleic anhydride and lysine
Amine substance, and compounded with sodium citrate, organic acid is formed, the metal ions such as organic acid and calcium ion, magnesium ion are utilized
Water miscible complex compound is formed, the formation of dirt is prevented, while by the specific culture to earthworm, making it form grease decomposition in vivo
Enzyme, and coordinated with organic acid, the formation of dirt is on the one hand prevented, on the other hand grease is decomposed, resistance is preferably reached
The effect of dirt cleaning；
（2）The present invention is using polyvinylpyrrolidone and polyvinyl alcohol as adhesive, and wherein polyvinylpyrrolidone has good
Water solubility, reuse polyvinyl alcohol reduction solubility property, to reach the effect of sustained release, at the same polyvinylpyrrolidone dissolving after
Water-soluble electrolytes are formed, steric hindrance is produced, contacting with each other between dirty nucleus is prevented into, prevents dirt from agglomeration, then make
Increase holdup time of the solid slow-release type antisludging agent in oil field pipe with triethanolamine, extend the scale inhibition cycle, utilize titanium dioxide
Titanium is catalyzed, enhancing snaking and scale inhibition effect, while improving enzymatic activity using titanium dioxide, increases the effect of enzyme, further
Strengthen scale inhibition effect.
Embodiment
The preparation method of organic acid comprises the following steps：
（1）In mass ratio 1:3, maleic anhydride and lysine are put into reactor, the four of 2~3 times of lysine quality are added
The titanium dioxide of hydrogen furans and lysine quality 1~2%, is heated to reflux；
（2）After backflow terminates, filtered, collect filter residue, rinsed filter residue using water, the filter residue after flushing is air-dried, collected
Air dry matter, in mass ratio 3~6:1, air dry matter is well mixed with sodium citrate, you can obtain organic acid.
The preparation of bio-matrix comprises the following steps：
A. in mass ratio 1:3, the dirt in oil field pipe is well mixed with rural area soil, mixture is collected, water use regulation is mixed
The water content of compound is then layed in culture pond to 60~65%, and laying depth is 6~10cm, by 80~90 every square metre
The earthworm of young earthworm, the earthworm of young earthworm is put into culture pond and carries out culture 10~15 days, and cultivation temperature is 18~26 DEG C, is cultivated
Every 15~20h in journey, the dirt added into culture pond in the oil field pipe of rural area soil quality 10~12%；
B. the earthworm survived in culture pond is collected after culture terminates, by the earthworm of collection and 1.2mol/L hydrochloric acid in mass ratio 1:
3 are put into bruisher and smash 10~15min to pieces with 11000r/min, and mixture is smashed in collection to pieces, is centrifuged, and collects centrifugation
Liquid, is freeze-dried to centrifugate, collects dried object, you can obtain bio-matrix.The preparation of adhesive：By polyvinylpyrrolidine
Ketone and polyvinyl alcohol in mass ratio 1:4 mix.
The selection of dispersant：Any one in sodium tripolyphosphate, lauryl sodium sulfate or stearic acid.
The preparation of auxiliary agent：By triethanolamine and titanium dioxide in mass ratio 6:1 mixes.
Solid slow-release type antisludging agent of the present invention, includes the raw material of following parts by weight：60~65 parts of organic acids, 40~45 parts
Bio-matrix, 20~25 parts of water, 15~20 parts of adhesives, 6~9 parts of dispersants, 1~3 part of auxiliary agent.Solid slow-release type resistance of the present invention
The preparation method of dirty agent, comprises the following steps：Raw material is taken by proportioning progress by weight, is put into mixer and stirs,
Stirring mixture is collected, is placed in press carrying out briquetting with 20MPa, extrudate, and natural air drying is collected, by air dry matter powder
It is broken, 200 mesh sieves are crossed, sieving particle are collected, you can obtain solid slow-release type antisludging agent.
Example 1
The preparation method of organic acid comprises the following steps：
（1）In mass ratio 1:3, maleic anhydride and lysine are put into reactor, the tetrahydrochysene furan of 2 times of lysine quality is added
Mutter and lysine quality 1% titanium dioxide, be heated to reflux；
（2）After backflow terminates, filtered, collect filter residue, rinsed filter residue using water, the filter residue after flushing is air-dried, collected
Air dry matter, in mass ratio 3:1, air dry matter is well mixed with sodium citrate, you can obtain organic acid.
The preparation of bio-matrix comprises the following steps：
B. in mass ratio 1:3, the dirt in oil field pipe is well mixed with rural area soil, mixture is collected, water use regulation is mixed
The water content of compound is then layed in culture pond to 60%, and laying depth is 6cm, by the earthworm of 80 every square metre young earthworms,
The earthworm of young earthworm is put into culture pond and carries out culture 10 days, cultivation temperature is 18 DEG C, per 15h in incubation, to culture pond
Dirt in the interior oil field pipe for adding rural area soil quality 10%；
B. the earthworm survived in culture pond is collected after culture terminates, by the earthworm of collection and 1.2mol/L hydrochloric acid in mass ratio 1:
3 are put into bruisher and smash 10min to pieces with 11000r/min, and mixture is smashed in collection to pieces, is centrifuged, and collects centrifugate, right
Centrifugate is freeze-dried, and collects dried object, you can obtain bio-matrix.
The preparation of adhesive：By polyvinylpyrrolidone and polyvinyl alcohol in mass ratio 1:4 mix.
The preparation of auxiliary agent：By triethanolamine and titanium dioxide in mass ratio 6:1 mixes.
Solid slow-release type antisludging agent of the present invention, includes the raw material of following parts by weight：60 parts of organic acids, 40 parts of bio-baseds
Matter, 20 parts of water, 15 parts of adhesives, 6 parts of sodium tripolyphosphates, 1 part of auxiliary agent.
The preparation method of solid slow-release type antisludging agent of the present invention, comprises the following steps：Taken by proportioning by weight
Raw material, is put into mixer and stirs, and collects stirring mixture, is placed in press carrying out briquetting with 20MPa, collects extruding
Thing, and natural air drying, air dry matter is crushed, and crosses 200 mesh sieves, collects sieving particle, you can obtain solid slow-release type antisludging agent.
Example 2
The preparation method of organic acid comprises the following steps：
（1）In mass ratio 1:3, maleic anhydride and lysine are put into reactor, the tetrahydrochysene furan of 2 times of lysine quality is added
Mutter and lysine quality 1% titanium dioxide, be heated to reflux；
（2）After backflow terminates, filtered, collect filter residue, rinsed filter residue using water, the filter residue after flushing is air-dried, collected
Air dry matter, in mass ratio 5:1, air dry matter is well mixed with sodium citrate, you can obtain organic acid.
The preparation of bio-matrix comprises the following steps：
C. in mass ratio 1:3, the dirt in oil field pipe is well mixed with rural area soil, mixture is collected, water use regulation is mixed
The water content of compound is then layed in culture pond to 63%, and laying depth is 8cm, by the earthworm of 85 every square metre young earthworms,
The earthworm of young earthworm is put into culture pond and carries out culture 13 days, cultivation temperature is 22 DEG C, per 18h in incubation, to culture pond
Dirt in the interior oil field pipe for adding rural area soil quality 11%；
B. the earthworm survived in culture pond is collected after culture terminates, by the earthworm of collection and 1.2mol/L hydrochloric acid in mass ratio 1:
3 are put into bruisher and smash 13min to pieces with 11000r/min, and mixture is smashed in collection to pieces, is centrifuged, and collects centrifugate, right
Centrifugate is freeze-dried, and collects dried object, you can obtain bio-matrix.
The preparation of adhesive：By polyvinylpyrrolidone and polyvinyl alcohol in mass ratio 1:4 mix.
The preparation of auxiliary agent：By triethanolamine and titanium dioxide in mass ratio 6:1 mixes.
Solid slow-release type antisludging agent of the present invention, includes the raw material of following parts by weight：63 parts of organic acids, 43 parts of bio-baseds
Matter, 23 parts of water, 18 parts of adhesives, 8 parts of lauryl sodium sulfate, 2 parts of auxiliary agents.
The preparation method of solid slow-release type antisludging agent of the present invention, comprises the following steps：Taken by proportioning by weight
Raw material, is put into mixer and stirs, and collects stirring mixture, is placed in press carrying out briquetting with 20MPa, collects extruding
Thing, and natural air drying, air dry matter is crushed, and crosses 200 mesh sieves, collects sieving particle, you can obtain solid slow-release type antisludging agent.
Example 3
The preparation method of organic acid comprises the following steps：
（1）In mass ratio 1:3, maleic anhydride and lysine are put into reactor, the tetrahydrochysene furan of 3 times of lysine quality is added
Mutter and lysine quality 2% titanium dioxide, be heated to reflux；
（2）After backflow terminates, filtered, collect filter residue, rinsed filter residue using water, the filter residue after flushing is air-dried, collected
Air dry matter, in mass ratio 6:1, air dry matter is well mixed with sodium citrate, you can obtain organic acid.
The preparation of bio-matrix comprises the following steps：
In mass ratio 1:3, the dirt in oil field pipe is well mixed with rural area soil, mixture is collected, mixes water use regulation
The water content of thing is then layed in culture pond to 65%, and laying depth is 10cm, by the earthworm of 90 every square metre young earthworms, will
The earthworm of young earthworm, which is put into culture pond, carries out culture 15 days, and cultivation temperature is 26 DEG C, per 20h in incubation, into culture pond
The dirt added in the oil field pipe of rural area soil quality 12%；B. the earthworm survived in culture pond is collected after culture terminates, will be received
The earthworm of collection and 1.2mol/L hydrochloric acid in mass ratio 1:3 are put into bruisher and smash 15min to pieces with 11000r/min, and collection smashs mixed to pieces
Compound, is centrifuged, and collects centrifugate, centrifugate is freeze-dried, and collects dried object, you can obtain bio-matrix.
The preparation of adhesive：By polyvinylpyrrolidone and polyvinyl alcohol in mass ratio 1:4 mix.
The preparation of auxiliary agent：By triethanolamine and titanium dioxide in mass ratio 6:1 mixes.
Solid slow-release type antisludging agent of the present invention, includes the raw material of following parts by weight：65 parts of organic acids, 45 parts of bio-baseds
Matter, 25 parts of water, 20 parts of adhesives, 9 parts of stearic acid, 3 parts of auxiliary agents.
The preparation method of solid slow-release type antisludging agent of the present invention, comprises the following steps：Taken by proportioning by weight
Raw material, is put into mixer and stirs, and collects stirring mixture, is placed in press carrying out briquetting with 20MPa, collects extruding
Thing, and natural air drying, air dry matter is crushed, and crosses 200 mesh sieves, collects sieving particle, you can obtain solid slow-release type antisludging agent.
Comparative example：The oil field special solid antisludging agent of Suzhou green technology Co., Ltd production.
Application method：Antisludging agent is placed in a length of 4m, external diameter and oil well pump external diameter identical screen casing, oil well pump is connected to
Lower end, the solid slow-release antisludging agent slow mechanism dissolved when liquid flow crosses screen casing, active ingredient therein discharges therewith.
According to above-mentioned application method, by the oil field of solid slow-release type antisludging agent and comparative example made from present example 1~3
Special solid antisludging agent is used, and is used for effect and is detected, its testing result is as shown in table 1：Table 1
| Detection project | Example 1 | Example 2 | Example 3 | Comparative example |
| Antisludging agent usage amount mg/L | 10 | 10 | 10 | 50~60 |
| Scale inhibition performance/% | 93.2 | 94.6 | 95.7 | 82.9 |
| Corrosion rate mm/a | 0.076 | 0.071 | 0.068 | 0.137 |
| Action period/day | 152 | 163 | 175 | 128 |
Note：Antisludging agent usage amount is on the basis of the water quality of oil field.
In summary, solid slow-release type antisludging agent produced by the present invention has slow release, dosing convenience, scale inhibition effect good
Advantage, the equipment such as oil well casing, oil pipe and pull bar can be played a good protection after use, reduce oilfield servicing cost
Expenditure, is a kind of oilfield additive easy to use, economy and durability.
Claims (7)
1. a kind of solid slow-release type antisludging agent, it is characterised in that include the raw material of following parts by weight：60~65 parts of organic acids,
40~45 parts of bio-matrixes, 20~25 parts of water, 15~20 parts of adhesives, 6~9 parts of dispersants, 1~3 part of auxiliary agent.
2. solid slow-release type antisludging agent according to claim 1, it is characterised in that the preparation method of the organic acid includes
Following steps：
（1）In mass ratio 1:3, maleic anhydride and lysine are put into reactor, the four of 2~3 times of lysine quality are added
The titanium dioxide of hydrogen furans and lysine quality 1~2%, is heated to reflux；
（2）After backflow terminates, filtered, collect filter residue, rinsed filter residue using water, the filter residue after flushing is air-dried, collected
Air dry matter, in mass ratio 3~6:1, air dry matter is well mixed with sodium citrate, you can obtain organic acid.
3. solid slow-release type antisludging agent according to claim 1, it is characterised in that the preparation of the bio-matrix is included such as
Lower step：
A. in mass ratio 1:3, the dirt in oil field pipe is well mixed with rural area soil, mixture is collected, water use regulation is mixed
The water content of compound is then layed in culture pond to 60~65%, and laying depth is 6~10cm, by 80~90 every square metre
If the earthworm of earthworm phase, cultivated if the earthworm of earthworm phase is put into culture pond；B. culture pond internal memory is collected after culture terminates
Earthworm living, by the earthworm of collection and 1.2mol/L hydrochloric acid in mass ratio 1:3 are put into bruisher and smash to pieces, and mixing is smashed in collection to pieces
Thing, is centrifuged, and collects centrifugate, centrifugate is freeze-dried, and collects dried object, you can obtain bio-matrix.
4. solid slow-release type antisludging agent according to claim 1, it is characterised in that described adhesive is polyvinylpyrrolidine
Ketone and polyvinyl alcohol in mass ratio 1:4 mix.
5. solid slow-release type antisludging agent according to claim 1, it is characterised in that the dispersant be sodium tripolyphosphate,
Any one in lauryl sodium sulfate or stearic acid.
6. solid slow-release type antisludging agent according to claim 1, it is characterised in that the auxiliary agent is triethanolamine and dioxy
Change titanium in mass ratio 6:1 mixes.
7. the preparation method of the solid slow-release type antisludging agent according to claim 1~6 any one, it is characterised in that bag
Include following steps：Proportioning progress by weight takes raw material, is put into mixer and stirs, and collects stirring mixture, juxtaposition
Briquetting is carried out in press, extrudate, and natural air drying is collected, air dry matter is crushed, sieve, sieving particle is collected, you can
Solid slow-release type antisludging agent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919653A (en) * | 2021-01-22 | 2021-06-08 | 广东巴沃夫环保科技有限公司 | Solid water treatment agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613599A (en) * | 2009-06-25 | 2009-12-30 | 天津开广工业水处理有限公司 | A kind of solid corrosion and scale inhibitor and preparation method thereof |
| CN101805597A (en) * | 2010-03-11 | 2010-08-18 | 中国石油集团川庆钻探工程有限公司 | Solid corrosion and scale inhibitor for oil field |
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2017
- 2017-06-28 CN CN201710509466.8A patent/CN107265675B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613599A (en) * | 2009-06-25 | 2009-12-30 | 天津开广工业水处理有限公司 | A kind of solid corrosion and scale inhibitor and preparation method thereof |
| CN101805597A (en) * | 2010-03-11 | 2010-08-18 | 中国石油集团川庆钻探工程有限公司 | Solid corrosion and scale inhibitor for oil field |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919653A (en) * | 2021-01-22 | 2021-06-08 | 广东巴沃夫环保科技有限公司 | Solid water treatment agent |
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