CN106565003A - Production process of high-efficiency and high-concentration polyaluminum ferric chloride sulfate - Google Patents
Production process of high-efficiency and high-concentration polyaluminum ferric chloride sulfate Download PDFInfo
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- CN106565003A CN106565003A CN201611225283.5A CN201611225283A CN106565003A CN 106565003 A CN106565003 A CN 106565003A CN 201611225283 A CN201611225283 A CN 201611225283A CN 106565003 A CN106565003 A CN 106565003A
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- aluminum
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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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
Abstract
The invention discloses a production process of high-efficiency and high-concentration polyaluminum ferric chloride sulfate. The production process comprises the following steps: under a condition of not adding a large amount of technological equipment and other raw materials, extracting aluminum and ferric ions from ferric trihydrate alumina mineral powder are extracted by a sulfuric acid and hydrochloric acid di-acid dissolving mode, performing polymerization reaction with calcium aluminate powder, and generating the high-efficiency and high-concentration liquid polymerized di-acid ferro-aluminum through a negative pressure synergic concentration process to replace a conventional solid product. The process is simple, practical and easy to operate; the water purification effect of the prepared high-efficiency and high-concentration liquid polymerized di-acid ferro-aluminum and the water purification effect of the conventional solid product is about 1 to 1; and the equipment investment is low, the cost performance of the raw materials is high, the production cost is greatly reduced, and the production process is suitable for industrial production.
Description
Technical field
The invention belongs to poly-aluminum ferric chloride sulfate production technical field, and in particular to a kind of efficiently highly concentrated poly-aluminum ferric chloride sulfate
Production technology.
Background technology
Poly-aluminum ferric chloride sulfate is a kind of new and effective water purification agent, collects the advantage of aluminium salt system and molysite system efficient water-purifying agent in one
Body, has the advantages that active ingredient is high, basicity is high, the degree of polymerization is big, molecule link network gathers, huge structure, in purification of water quality mistake
There is higher adsorption-condensation ability and more preferable purifying water effect in journey, be a kind of efficient, quick, low consumption, nontoxic, safe nothing
Machine efficient water-purifying agent.
At present, poly-aluminum ferric chloride sulfate mainly has liquid (aluminium and total active ingredient >=10.5% of iron) and solid (aluminium and iron is total
Active ingredient >=30%) two kinds.Solid product is on the basis of fluid product, to produce liquid through techniques such as drying, drying
Product are converted into solid product, and this process increased the costs such as substantial amounts of artificial, fuel, equipment, packaging, carrying.Solid product
Advantage be that long distance transportation cost performance is high.But, using front and solid product must be diluted preparation, solid
Product adds water to come back to by a certain percentage and come into operation after liquid condition.And change into the process of solid product in fluid product
In, limited by technique, it is general to be difficult for 100% effective ingredient to be completely converted into solid.Simultaneously in high-temperature drying procedures
In, the degree of polymerization of product is destroyed.Therefore, the liquid after the viscosity of fluid product can again dilute than the solid of Jing high temperature drying
The viscosity of product, purity are higher.But because the active ingredient of poly-aluminum ferric chloride sulfate solid product is still high compared with fluid product, cause
Water treatment efficiency solid product is about 1 with fluid product:3.The cost performance of solid product long distance transportation is higher, therefore liquid is produced
Product market still cannot effectively promote.If efficiently highly concentrated fluid product can be selected, reach in water process and solid
The same water treatment efficiency of product, then can solve caused various problems in dry run, while the country or state can also be reached
Find a good sale in outward, the advantage of solid product will not exist, can more realize economic benefit.Therefore, efficiently highly concentrated liquid polymeric is produced
It is the revolutionary technical barrier for being currently badly in need of capturing that double-acid ferro-aluminum directly substitutes solid product.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art part, there is provided a kind of efficiently highly concentrated poly-aluminum ferric chloride sulfate
Production technology, in the case where a large amount of process equipments and other raw material are not increased, dissolved using sulfuric acid and hydrochloric acid bisgallic acid
Mode extracts aluminium, the iron ion in iron content bauxite trihydrate powder, while carrying out polymerisation with calcium aluminate powder, and is increased by negative pressure
The efficiently highly concentrated liquid polymeric double-acid ferro-aluminum of effect concentration technology production, to substitute Conventional solid product.The features simple and practical process is easy
Operation, obtained efficiently highly concentrated liquid polymeric double-acid ferro-aluminum is about 1 with Conventional solid product purifying water effect:1, equipment investment is low,
Raw material cost performance is high, and production cost is reduced in a large number, is adapted to industrialized production.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of production technology of poly-aluminum ferric chloride sulfate, including：
Step one：Under agitation by the hydrochloric acid of suitable quantity of water and 127～168 parts of total acidities 30～32% and 8～14 part 97～
99% sulfuric acid mixing, is added thereto to 35～58 parts of alumina contents for 40～45%, iron oxide content under normal pressure and temperature
For 20～25% iron content bauxite trihydrate powder, stir to dissolving；Then it is persistently overheating to temperature of reaction system control 105～
125 DEG C, 3.5～5.0h is reacted under normal pressure；
Step 2：The feed liquid that step one is obtained supplements under agitation suitable quantity of water, adds 46～63 parts of calcium aluminate powder, adds
During using reaction self-heating lifted feed temperature, add and finish rear water use regulation feed liquid density >=1.25g/ml, then add
4～7 parts of synergist tertiary sodium phosphate, is warming up to temperature of reaction system and controls at 100～115 DEG C, and 3～4h is reacted under normal pressure；
Step 3：The feed liquid that step 2 is obtained carries out separation of solid and liquid, obtains mother liquor；
Step 4：The mother liquor concentrations that step 3 is obtained to density is 1.45～1.50g/ml, then is cured 3～5 days, is obtained final product
Efficient highly concentrated liquid polymeric double-acid ferro-aluminum, its relative density is 1.45～1.50g/ml, alumina weight percentage composition >=19%,
Iron oxide weight percentage is 2.0～3.0%, basicity ＞ 85.0%, pH value 3.5～5.0, water insoluble matter content ＜
0.1%.
In one embodiment：In the calcium aluminate powder, acid-soluble aluminum content 48～54%, calcium oxide content 26～34%.
In one embodiment：In the step 3, separation of solid and liquid adopts plate compression device.
In one embodiment：In the step 4, concentrated using negative pressure synergy enrichment facility.
Among the present invention, unless otherwise stated, according to the mass fraction, content is mass fraction to number.
The present invention be on the basis of using existing process equipment and raw material, do not increase a large amount of process equipments and other
In the case of raw material, innovation and creation are carried out, product economy benefit is higher, while overcoming a following production technology difficult problem：
1. in the technique of the present invention, two not good liquors after calcium aluminate powder and synergist polymerisation are passed through into plate compression device
Press filtration, obtains mother liquor, on the one hand ensures the purity of mother liquor, and despumation is to polymerization effect in mother liquor negative pressure synergy concentration process
Affect, on the other hand, the impurity contained in mother liquor impurity blocking device in negative pressure synergy enrichment facility, damage can be avoided to set
It is standby, cause synergy concentration process smoothly to realize.And in existing production technology, in order to exclude waste residue impurity to existing process
The impact of former synergist waterglass or sodium aluminosilicate enhanced reaction of modification, is that plate compression point must be carried out before calcium aluminate powder is added
Separate out mother liquor.If according to the traditional handicraft, it is impossible to obtain the efficient highly concentrated liquid polymeric double-acid ferro-aluminum of the present invention.
2. in order to realize the production of efficient highly concentrated poly-aluminum ferric chloride sulfate, invention introduces new synergist tertiary sodium phosphate, newly
Synergist can be engaged with follow-up negative pressure synergy enrichment facility and maturing process, promote and reach the increasing of poly-aluminum ferric chloride sulfate
Effect polymerization enrichment purification, has been significantly greatly increased hydroxyl overseas Chinese federation and has improved the product degree of polymerization, makes the total active ingredient of aluminium and iron, the molecule of product
The product quality indicators such as the quantity of electric charge, coagulability, bin stability and basicity improve level.If using other synergy
Agent, then cannot obtain the efficient highly concentrated liquid polymeric double-acid ferro-aluminum of the present invention.
3. efficiently highly concentrated polymeric bisgallic acid alumnium iron process is all linked with one another for whole production, and indispensable, this is present invention applicant
Through a large amount of, prolonged development test, the final technology for summarizing invention.By the concrete response parameter of modulation process, each raw material
Add parts by weight and each raw material order of adding, these be all present invention production efficiently highly concentrated poly-aluminum ferric chloride sulfate key because
Element.If each raw material is added, ratio of weight and number is improper, each raw material order of adding is incorrect, the concrete response parameter of each technique does not regulate and control
It is good, then cannot smoothly complete the production of efficient highly concentrated poly-aluminum ferric chloride sulfate.
The efficient highly concentrated liquid polymeric double-acid ferro-aluminum that the present invention is obtained, the relative density at 20 DEG C is 1.45～1.50g/
Ml, alumina weight percentage composition >=19%, iron oxide weight percentage is 2.0～3.0%, basicity ＞ 85.0%, pH
Value 3.5～5.0, water insoluble matter content ＜ 0.1%.And the liquid polymeric double-acid ferro-aluminum that produces according to existing process is at 20 DEG C
Relative density be 1.20～1.25g/ml, alumina weight percentage composition >=10%, iron oxide weight percent content 1.5～
3.0%, basicity ＞ 85.0%, pH value 3.5～5.0, water insoluble matter content ＜ 0.1%, the two is compared has larger gap, says
The bright efficient highly concentrated liquid polymeric double-acid ferro-aluminum product that the present invention cannot be produced according to existing process.
By the present invention prepare efficient highly concentrated poly-aluminum ferric chloride sulfate (liquid) 1#, typical polymerization double-acid ferro-aluminum (solid) 2#,
Typical polymerization double-acid ferro-aluminum (liquid) 3#, tradition water purification agent polyaluminium chloride (liquid) 4# and traditional water purification agent polyaluminium chloride (solid)
5#, in Xiamen, water factory carries out coagulation contrast test and (takes each medicament optimum dosage detection water outlet water by six stirring instruments
Matter), as a result such as following table：
As can be seen from the above table, each comprehensive physical and chemical index of product of the present invention is superior to traditional water purification agent polyaluminium chloride product
Product, traditional liquid product water treatment efficiency is about 3 with Conventional solid product:1, and the product of the present invention and conventional solid polymerization
Double-acid ferro-aluminum water treatment efficiency is about 1:1.This is that existing process cannot be realized.
Compared with background technology, it has the advantage that the technical program：
1. the present invention carries out extracting aluminium, the iron in iron content bauxite trihydrate powder by the way of sulfuric acid and the dissolving of hydrochloric acid bisgallic acid
Ion, while polymerisation is carried out with calcium aluminate powder, and by the efficiently highly concentrated liquid polymeric of negative pressure synergy concentration technology production
Double-acid ferro-aluminum product.Not only each cost of material is relatively low but also technical matters is also relatively simple, and adds synergy in polymerisation
Agent, while by negative pressure synergy concentration technology, hydroxyl overseas Chinese federation being significantly greatly increased and having improved the product degree of polymerization, makes the aluminium and iron of product total
The product quality indicators such as active ingredient, molecule charge amount, coagulability, bin stability and basicity improve level.The present invention
Obtained product integrates aluminium salt water purification agent and molysite water clarifier advantage effectively by aluminium, iron ion organic synthesis, formed it is main into
Divide content complementary, effectively reduce the residual aluminum ions of products application water outlet when drinking water treatment, preferably ensure health.
Efficiently highly concentrated liquid polymeric double-acid ferro-aluminum properties of product are suitable with solid polymerization double-acid ferro-aluminum.
2. the aluminium and total active ingredient >=21% of iron of the obtained efficiently highly concentrated liquid polymeric double-acid ferro-aluminum product of the present invention, only
Water effect is about 1 with Conventional solid product:1, complete alternative solid product.Fluid product is effectively saved through being dried, drying
The technique such as dry is converted into the costs such as solid product, produced substantial amounts of artificial, fuel, equipment, packaging, carrying, while avoiding
In high-temperature drying procedures, the loss of polymeric bisgallic acid alumnium iron product active ingredient and the destruction of the product degree of polymerization are solved solid
The wasting of resources, dust, the caking that makes moist, employee's occupational disease, high labor intensive, package waste that body product occurs in use
The problems such as thing process, environmental pollution.Efficiently highly concentrated liquid polymeric double-acid ferro-aluminum facilitates long distance transportation, is adapted to home or overseas remote
Pin, is greatly enlarged the market of liquid polymeric double-acid ferro-aluminum, makes fluid product substitute solid product and is possibly realized.
3. in the case where a large amount of process equipments and other raw material are not increased, the side dissolved using sulfuric acid and hydrochloric acid bisgallic acid
Formula extracts aluminium, the iron ion in iron content bauxite trihydrate powder, while polymerisation is carried out with calcium aluminate powder, and by negative pressure synergy
The efficiently highly concentrated liquid polymeric double-acid ferro-aluminum of concentration technology production.Weight is added by the concrete response parameter of modulation process, each raw material
Amount number and each raw material order of adding, these are all the key factors of the efficient highly concentrated poly-aluminum ferric chloride sulfate of present invention production.If each
Raw material adds that ratio of weight and number is improper, each raw material order of adding is incorrect, the concrete response parameter of each technique does not regulate and control, then without
Method smoothly completes the production of efficient highly concentrated poly-aluminum ferric chloride sulfate.This is present invention applicant through a large amount of, prolonged research examination
Test, it is final to summarize what is determined.
Description of the drawings
With reference to the accompanying drawings and examples the invention will be further described.
Fig. 1 is the technological process of production schematic diagram of the efficient highly concentrated poly-aluminum ferric chloride sulfate of the present invention.
Specific embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1
Step one：, using suitable quantity of water is added in steam-heated acidproof primary first-order equation kettle, constantly stir with agitating device
Mix down and add 155 parts of technical hydrochloric acids and 13 part of 98% sulfuric acid by proportioning, 56 parts of the addition in the hydrochloric acid solution under normal pressure and temperature
Iron content bauxite trihydrate powder, stirs to dissolving；Then it is persistently overheating to temperature of reaction system control at 105～125 DEG C, under normal pressure
Insulation reaction 5h；Sampling detection；
Step 2：The feed liquid that step one is obtained utilizes steam-heated acidproof by pumping to agitating device
In polymerization secondary response kettle, lower appropriate supplementary water is stirred continuously, and adds 60 parts of calcium aluminate powder, during adding using reaction certainly
Heat lifts feed temperature, adds and finishes rear water use regulation feed liquid density 1.29g/ml, then adds 6 parts of synergist tertiary sodium phosphate,
It is warming up to temperature of reaction system to control at 100～115 DEG C, under normal pressure 4h is reacted；Sampling detection；
Step 3：The secondary feed liquid that step 2 is obtained carries out separation of solid and liquid by plate and frame filter press press filtration, obtains mother
320 parts of liquid；Sampling detection；
Step 4：The mother liquor that step 3 is obtained enters negative pressure synergy enrichment facility by pumping carries out synergy concentration, concentration
It is 1.48g/ml to density, then pumps it to aerobic fermentation tank, aeration is cured 5 days under normal temperature and pressure, obtains final product efficient highly concentrated liquid polymeric
187 parts of double-acid ferro-aluminum product, detection warehouse-in.Finished product meets existing product standard.
Wherein, the technical hydrochloric acid is that (in terms of HCl, i.e., HCl contents are Nacl 31%) to total acidity to total acidity 31%
Acid.Alumina content is that 40～45%, iron oxide content is 20～25% in the iron content bauxite trihydrate powder.The calcium aluminate
In powder, acid-soluble aluminum content 50%, calcium oxide content 28～31%.
Embodiment 2
Step one：, using suitable quantity of water is added in steam-heated acidproof primary first-order equation kettle, constantly stir with agitating device
Mix down and add 129 parts of technical hydrochloric acids and 9 part of 98% sulfuric acid by proportioning, add 40 parts in the hydrochloric acid solution under normal pressure and temperature and contain
Iron bauxite trihydrate powder, stirs to dissolving；Then it is persistently overheating to control at 105～125 DEG C to temperature of reaction system, protect under normal pressure
Temperature reaction 4h；Sampling detection；
Step 2：The feed liquid that step one is obtained utilizes steam-heated acidproof by pumping to agitating device
In polymerization secondary response kettle, lower appropriate supplementary water is stirred continuously, and adds 49 parts of calcium aluminate powder, during adding using reaction certainly
Heat lifts feed temperature, adds and finishes rear water use regulation feed liquid density 1.26g/ml, then adds 4 parts of synergist tertiary sodium phosphate,
It is warming up to temperature of reaction system to control at 100～115 DEG C, under normal pressure 3.5h is reacted；Sampling detection；
Step 3：The secondary feed liquid that step 2 is obtained carries out separation of solid and liquid by plate and frame filter press press filtration, obtains mother
281 parts of liquid；Sampling detection；
Step 4：The mother liquor that step 3 is obtained enters negative pressure synergy enrichment facility by pumping carries out synergy concentration, concentration
It is 1.47g/ml to density, then pumps it to aerobic fermentation tank, aeration is cured 3 days under normal temperature and pressure, obtains final product efficient highly concentrated liquid polymeric
174 parts of double-acid ferro-aluminum product, detection warehouse-in.Finished product meets existing product standard.
Wherein, the technical hydrochloric acid is that (in terms of HCl, i.e., HCl contents are Nacl 31%) to total acidity to total acidity 31%
Acid.Alumina content is that 40～45%, iron oxide content is 20～25% in the iron content bauxite trihydrate powder.The calcium aluminate
In powder, acid-soluble aluminum content 50%, calcium oxide content 28～31%.
Embodiment 3
Step one：, using suitable quantity of water is added in steam-heated acidproof primary first-order equation kettle, constantly stir with agitating device
Mix down and add 141 parts of technical hydrochloric acids and 12 part of 98% sulfuric acid by proportioning, 47 parts of the addition in the hydrochloric acid solution under normal pressure and temperature
Iron content bauxite trihydrate powder, stirs to dissolving；Then it is persistently overheating to temperature of reaction system control at 105～125 DEG C, under normal pressure
Insulation reaction 4.5h；Sampling detection；
Step 2：The feed liquid that step one is obtained utilizes steam-heated acidproof by pumping to agitating device
In polymerization secondary response kettle, lower appropriate supplementary water is stirred continuously, and adds 56 parts of calcium aluminate powder, during adding using reaction certainly
Heat lifts feed temperature, adds and finishes rear water use regulation feed liquid density 1.28g/ml, then adds 5 parts of synergist tertiary sodium phosphate,
It is warming up to temperature of reaction system to control at 100～115 DEG C, under normal pressure 4h is reacted；Sampling detection；
Step 3：The secondary feed liquid that step 2 is obtained carries out separation of solid and liquid by plate and frame filter press press filtration, obtains mother
306 parts of liquid；Sampling detection；
Step 4：The mother liquor that step 3 is obtained enters negative pressure synergy enrichment facility by pumping carries out synergy concentration, concentration
It is 1.46g/ml to density, then pumps it to aerobic fermentation tank, aeration is cured 4 days under normal temperature and pressure, obtains final product efficient highly concentrated liquid polymeric
183 parts of double-acid ferro-aluminum product, detection warehouse-in.Finished product meets existing product standard.
Wherein, the technical hydrochloric acid is that (in terms of HCl, i.e., HCl contents are Nacl 31%) to total acidity to total acidity 31%
Acid.Alumina content is that 40～45%, iron oxide content is 20～25% in the iron content bauxite trihydrate powder.The calcium aluminate
In powder, acid-soluble aluminum content 50%, calcium oxide content 28～31%.
The above, only present pre-ferred embodiments, therefore can not according to this limit the scope of present invention enforcement, i.e., according to
Equivalence changes that the scope of the claims of the present invention and description are made and modification, all should still belong in the range of the present invention covers.
Claims (4)
1. a kind of production technology of poly-aluminum ferric chloride sulfate, it is characterised in that：Including：
Step one：Under agitation by the hydrochloric acid of suitable quantity of water and 127～168 parts of total acidities 30～32% and 8～14 part 97～99%
Sulfuric acid mixing, be added thereto under normal pressure and temperature 35～58 parts of alumina contents for 40～45%, iron oxide content be 20
～25% iron content bauxite trihydrate powder, stirs to dissolving；Then it is persistently overheating to temperature of reaction system control 105～125
DEG C, 3.5～5.0h is reacted under normal pressure；
Step 2：The feed liquid that step one is obtained supplements under agitation suitable quantity of water, adds 46～63 parts of calcium aluminate powder, adds process
Middle utilization reaction self-heating lifts feed temperature, adds and finishes rear water use regulation feed liquid density >=1.25g/ml, then adds synergy
4～7 parts of agent tertiary sodium phosphate, is warming up to temperature of reaction system and controls at 100～115 DEG C, and 3～4h is reacted under normal pressure；
Step 3：The feed liquid that step 2 is obtained carries out separation of solid and liquid, obtains mother liquor；
Step 4：The mother liquor concentrations that step 3 is obtained to density is 1.45～1.50g/ml, then is cured 3～5 days, obtains final product liquid
Poly-aluminum ferric chloride sulfate, its relative density be 1.45～1.50g/ml, alumina weight percentage composition >=19%, iron oxide weight hundred
Content is divided to be 2.0～3.0%, basicity ＞ 85.0%, pH value 3.5～5.0, water insoluble matter content ＜ 0.1%.
2. the production technology of poly-aluminum ferric chloride sulfate according to claim 1, it is characterised in that：In the calcium aluminate powder, acid
Molten aluminium content 48～54%, calcium oxide content 26～34%.
3. the production technology of poly-aluminum ferric chloride sulfate according to claim 1, it is characterised in that：In the step 3, solid-liquid
Separate and adopt plate compression device.
4. the production technology of poly-aluminum ferric chloride sulfate according to claim 1, it is characterised in that：In the step 4, adopt
Negative pressure synergy enrichment facility is concentrated.
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Cited By (4)
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| CN111003772A (en) * | 2019-12-13 | 2020-04-14 | 杭州萧山三江净水剂有限公司 | Preparation method of dephosphorization polymeric aluminum iron and closed reaction kettle for preparation |
| CN111514840A (en) * | 2020-05-14 | 2020-08-11 | 绍兴上虞联谊化工有限公司 | Production process of polymeric aluminum ferric sulfate for water treatment |
| CN112142177A (en) * | 2020-09-25 | 2020-12-29 | 北京环球中科水务科技有限公司 | Inorganic polymer phosphorus removal agent and preparation method and application thereof |
| CN112159070A (en) * | 2020-09-25 | 2021-01-01 | 北京环球中科水务科技有限公司 | Inorganic polymer sludge conditioner and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111003772A (en) * | 2019-12-13 | 2020-04-14 | 杭州萧山三江净水剂有限公司 | Preparation method of dephosphorization polymeric aluminum iron and closed reaction kettle for preparation |
| CN111003772B (en) * | 2019-12-13 | 2022-08-23 | 杭州萧山三江净水剂有限公司 | Preparation method of dephosphorization polymeric aluminum iron and closed reaction kettle for preparation |
| CN111514840A (en) * | 2020-05-14 | 2020-08-11 | 绍兴上虞联谊化工有限公司 | Production process of polymeric aluminum ferric sulfate for water treatment |
| CN111514840B (en) * | 2020-05-14 | 2021-10-22 | 绍兴上虞联谊化工有限公司 | Production process of polymeric aluminum ferric sulfate for water treatment |
| CN112142177A (en) * | 2020-09-25 | 2020-12-29 | 北京环球中科水务科技有限公司 | Inorganic polymer phosphorus removal agent and preparation method and application thereof |
| CN112159070A (en) * | 2020-09-25 | 2021-01-01 | 北京环球中科水务科技有限公司 | Inorganic polymer sludge conditioner and preparation method and application thereof |
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| CN106565003B (en) | 2019-07-02 |
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