CN102229618A - Hexamethylenediamine tetramethylene phosphonic acid disodium salt and its production process - Google Patents
Hexamethylenediamine tetramethylene phosphonic acid disodium salt and its production process Download PDFInfo
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- CN102229618A CN102229618A CN2011101053337A CN201110105333A CN102229618A CN 102229618 A CN102229618 A CN 102229618A CN 2011101053337 A CN2011101053337 A CN 2011101053337A CN 201110105333 A CN201110105333 A CN 201110105333A CN 102229618 A CN102229618 A CN 102229618A
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- disodium salt
- water
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- phosphonic acid
- tetramethylene phosphonic
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 49
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 20
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 9
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 30
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 23
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000002826 coolant Substances 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 6
- 241000370738 Chlorion Species 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000005764 inhibitory process Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000002455 scale inhibitor Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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Abstract
The invention provides a hexamethylenediamine tetramethylene phosphonic acid disodium salt and its production process, which belongs to the chemical technical field. Hexylenediamine, phosphorous acid, formaldehyde and sodium hydroxide are taken as the raw materials, hydrochloric acid is taken as a catalyst. The process comprises the following steps: (1) metering hexylenediamine and water negative pressure for drawing into a kettle, drawing hydrochloric acid into a hydrochloric acid dropping pot, dropping hydrochloric acid off under temperature controlling; (2) drawing phosphorous acid into the kettle, strictly controlling the temperature range of 95 - 105 DEG C in the process, adding formaldehyde; (3) controlling temperature range of 95 - 110 DEG C for 1 hour, concentrating materials for increasing viscosity, wherein chloride ions of the product is lower than 5%; (4) adding water for regulating output, adding sodium hydroxide at the temperature below 80 DEG C, regulating the pH value of the product of the kettle to 4.0-4.5; (5) cooling to a temperature below 65 DEG to feed for obtaining the product. The invention has good scale inhibition effect, the active ingredient content of the product is greater than or equal to 25.0 calculated according to the weight of disodium salt; and is used for circulating water and effectively reducing phosphor content of circulating water in blow-off water.
Description
Technical field:
The present invention relates to a kind of anti-incrustation corrosion inhibitor that is applied to the processing of boiler water processing, reverse osmosis membrane, also can be used for uniform dose of peroxide stabiliser, noble metal extraction agent and electroplating industry metal ion etc., particularly a kind of hexanediamine tetramethylene phosphonic acid disodium salt and production technique thereof belong to chemical technology field.
Background technology:
Water conditioner hydroxy ethylene diphosphonic acid in the market, Amino Trimethylene Phosphonic Acid total phosphorous are then up to 48%, and molecular weight is low, cause water conditioner under abominable water quality and wide pH value value condition of water quality, easily to decompose, reduce even lose scale inhibitor effect under the standard state, too much add and to cause the water systems'phosphorus constituent content to increase, water eutrophication is unfavorable for the circulating water system maintenance.In view of this, it is low that marginal period is looked forward to total phosphorus acid content, and scale inhibitor efficient height, scale inhibition dirt are planted many hexanediamine tetramethylene phosphonic acid disodium salts and come out.
Summary of the invention:
The objective of the invention is at above deficiency, and a kind of hexanediamine tetramethylene phosphonic acid disodium salt and the production technique thereof of development, to satisfy the needs of current socio-economic development.The present invention is a kind of organic phosphine acids anti-incrustation corrosion inhibitor that is applied to many water treatment systems such as industrial circulating cooling water system, it has scale inhibition effect preferably, be used for recirculated water, can effectively improve the recirculated water concentration rate, reduce the water consumption rate of recirculated water, and can effectively reduce the content of phosphorus in the recirculated water sewer, help environmental protection, simultaneously, can alleviate phosphorus and be that Scale inhibitors causes microbial reproduction and the corrosion that causes, the waste gas that generates is made technology salt acid product, has not only stopped " three-waste pollution ", but also has increased economic benefit.The low molecule amine of the general employing of water conditioner, formaldehyde, phosphorus trichloride are that raw material synthesizes, the present invention is a raw material with hexanediamine, phosphorous acid, formaldehyde, sodium hydroxide, synthetic a kind of total phosphorus acid content is low, scale inhibitor efficient height, and the scale inhibition dirt is planted many hexanediamine tetramethylene phosphonic acid disodium salts.
Technical scheme of the present invention is achieved in that
A kind of hexanediamine tetramethylene phosphonic acid disodium salt is to be raw material with hexanediamine, phosphorous acid, formaldehyde, sodium hydroxide, is that catalyzer processes with the concentrated hydrochloric acid, and its reaction equation is:
Obtain hexanediamine tetramethylene phosphonic acid disodium salt, molecular formula is C
10H
26N
2O
12P
4Na
2, its structural formula is:
Technical scheme of the present invention can be achieved in that
A kind of production technique of hexanediamine tetramethylene phosphonic acid disodium salt is to be that 37% formaldehyde, sodium hydroxide are raw material with hexanediamine, phosphorous acid, content, is catalyzer with the concentrated hydrochloric acid, and the add-on of various materials is carried out according to following steps by weight successively:
The first step, accurately measure in 684 parts of hexanediamines and the 90 parts of water suction stills, extract 1200 parts of concentrated hydrochloric acids in hydrochloric acid drips jar, open and stir, under the logical water coolant condition of chuck, hydrochloric acid is dripped off;
Second step, emptying chuck water coolant in 2010 parts of phosphorous acid suction stills, are opened jacket steam and are warming up to 95 ℃, drip 2400 parts in formaldehyde;
The 3rd step, the insulation of 95 ~ 110 ℃ of temperature controls 1 hour are concentrated into the material retrogradation, after adding entry and continuing to be concentrated into the material retrogradation, add entry again and continue to be concentrated into the material retrogradation;
The 4th goes on foot, adds water transfers about 10000 parts of output, 500 parts in hydro-oxidation sodium below 80 ℃;
The 5th goes on foot, is cooled to blowing below 65 ℃.
Further, in the mode suction still of the water in the described the first step with negative pressure.
Further, the hydrochloric acid in the described the first step drips and drips under 70 ℃ of following conditions of temperature control.
Further, the formaldehyde dropping temperature in described second step is 95 ~ 105 ℃.
Further, the material in described the 3rd step is concentrated to the product chlorion and is lower than 5%.
Further, the actual add-on of the sodium hydroxide in described the 4th step is 4.0 ~ 4.5 to be as the criterion to transfer still product 1% pH value of water solution.
Its product quality indicator of hexanediamine tetramethylene phosphonic acid disodium salt that obtains is:
In the active component content of disodium salt, % 〉=25.0
With PO
3 3-The phosphorous acid content of meter, %≤3.0
The pH of 1% aqueous solution, 4.0 ~ 4.5
Density in the time of 20 ℃, g/cm
-3〉=1.20
With Cl
-The chloride content of meter, %≤5.0
With Fe
2+The iron level of meter, μ g/g≤20
The outward appearance light yellow transparent liquid.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Positively effect of the present invention is:
1, the hexanediamine tetramethylene phosphonic acid disodium salt that obtains of technical scheme of the present invention has very high solubleness, can stop that the scaling salt class forms incrustation scale in the water, is good calcium sulfate Scale inhibitors, especially is suitable for high-alkali high pH condition.
2, the present invention has scale inhibition effect preferably, be used for recirculated water, can effectively improve the recirculated water concentration rate, reduce the water consumption rate of recirculated water, and can effectively reduce the content of phosphorus in the recirculated water sewer, help environmental protection, simultaneously, can alleviate phosphorus and be that Scale inhibitors causes microbial reproduction and the corrosion that causes, the waste gas of generation is made technology salt acid product, not only stopped " three wastes " and polluted, but also increased economic benefit.
Embodiment:
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1:
The present invention is that 37% formaldehyde and sodium hydroxide are raw material with hexanediamine, phosphorous acid, content, is catalyzer with the concentrated hydrochloric acid, carries out according to following steps successively:
The first step, accurately measure in 684 kg hexanediamines and the 90 kg water negative pressure suction stills, extract 1200 kg concentrated hydrochloric acids in hydrochloric acid drips jar, open and stir, under the logical water coolant condition of chuck, temperature control below 70 ℃ drips off hydrochloric acid;
Second step, emptying chuck water coolant in 2010 kg phosphorous acid suction stills, are opened jacket steam and are warming up to 95 ℃, drip formaldehyde 2400kg;
The 3rd step, the insulation of 100 ℃ of temperature controls 1 hour are concentrated into the material retrogradation, after adding entry and continuing to be concentrated into the material retrogradation, add entry again and continue to be concentrated into the material retrogradation, make the product chlorion be lower than 5%;
The 4th goes on foot, adds water transfers the about 10000kg of output, 500 kg of hydro-oxidation sodium below 80 ℃, and actual add-on is 4.0 to transfer still product 1% pH value of water solution;
The 5th goes on foot, is cooled to blowing below 65 ℃.
The quality index of the product that obtains:
In the active component content of disodium salt, % 25.3
With PO
3 3-The phosphorous acid content of meter, % 2.1
The pH of 1% aqueous solution, 4.0
Density in the time of 20 ℃, g/cm
-31.253
With Cl
-The chloride content of meter, % 3.9
With Fe
2+The iron level of meter, μ g/g 3.7
The outward appearance light yellow transparent liquid.
Embodiment 2:
The present invention is that 37% formaldehyde and sodium hydroxide are raw material with hexanediamine, phosphorous acid, content, is catalyzer with the concentrated hydrochloric acid, carries out according to following steps successively:
The first step, accurately measure in 684 kg hexanediamines and the 90 kg water negative pressure suction stills, extract 1200 kg concentrated hydrochloric acids in hydrochloric acid drips jar, open and stir, under the logical water coolant condition of chuck, temperature control below 70 ℃ drips off hydrochloric acid;
Second step, emptying chuck water coolant in 2010 kg phosphorous acid suction stills, are opened jacket steam and are warming up to 100 ℃, drip formaldehyde 2400kg;
The 3rd step, the insulation of 95 ℃ of temperature controls 1 hour are concentrated into the material retrogradation, after adding entry and continuing to be concentrated into the material retrogradation, add entry again and continue to be concentrated into the material retrogradation, make the product chlorion be lower than 5%;
The 4th goes on foot, adds water transfers the about 10000kg of output, 500 kg of hydro-oxidation sodium below 80 ℃, and actual add-on is 4.3 to transfer still product 1% pH value of water solution;
The 5th goes on foot, is cooled to blowing below 65 ℃.
The quality index of the product that obtains:
In the active component content of disodium salt, % 26.0
With PO
3 3-The phosphorous acid content of meter, % 2.5
The pH of 1% aqueous solution, 4.3
Density in the time of 20 ℃, g/cm
-31.256
With Cl
-The chloride content of meter, % 4.1
With Fe
2+The iron level of meter, μ g/g 3.5
The outward appearance light yellow transparent liquid.
Embodiment 3:
The present invention is that 37% formaldehyde and sodium hydroxide are raw material with hexanediamine, phosphorous acid, content, is catalyzer with the concentrated hydrochloric acid, carries out according to following steps successively:
The first step, accurately measure in 684 kg hexanediamines and the 90 kg water negative pressure suction stills, extract 1200 kg concentrated hydrochloric acids in hydrochloric acid drips jar, open and stir, under the logical water coolant condition of chuck, temperature control below 70 ℃ drips off hydrochloric acid;
Second step, emptying chuck water coolant in 2010 kg phosphorous acid suction stills, are opened jacket steam and are warming up to 105 ℃, drip formaldehyde 2400kg;
The 3rd step, the insulation of 110 ℃ of temperature controls 1 hour are concentrated into the material retrogradation, after adding entry and continuing to be concentrated into the material retrogradation, add entry again and continue to be concentrated into the material retrogradation, make the product chlorion be lower than 5%;
The 4th goes on foot, adds water transfers the about 10000kg of output, 500 kg of hydro-oxidation sodium below 80 ℃, and actual add-on is 4.5 to transfer still product 1% pH value of water solution;
The 5th goes on foot, is cooled to blowing below 65 ℃.
The quality index of the product that obtains:
In the active component content of disodium salt, % 25.7
With PO
3 3-The phosphorous acid content of meter, % 1.9
The pH of 1% aqueous solution, 4.5
Density in the time of 20 ℃, g/cm
-31.254
With Cl
-The chloride content of meter, % 3.6
With Fe
2+The iron level of meter, μ g/g 3.8
The outward appearance light yellow transparent liquid.
Claims (8)
1. hexanediamine tetramethylene phosphonic acid disodium salt is characterized in that the structural formula of this compound is:
。
2. product that contains the described hexanediamine tetramethylene phosphonic acid of claim 1 disodium salt is characterized in that the quality index of this product is:
In the active component content of disodium salt, % 〉=25.0
With PO
3 3-The phosphorous acid content of meter, %≤3.0
The pH of 1% aqueous solution, 4.0 ~ 4.5
Density in the time of 20 ℃, g/cm
-3〉=1.20
With Cl
-The chloride content of meter, %≤5.0
With Fe
2+The iron level of meter, μ g/g≤20.
3. the production technique of the product of an a kind of hexanediamine tetramethylene phosphonic acid disodium salt as claimed in claim 2, it is characterized in that: with hexanediamine, phosphorous acid, content is that 37% formaldehyde, sodium hydroxide are raw material, with the concentrated hydrochloric acid is catalyzer, the add-on of each material is carried out according to following steps by weight successively:
The first step, accurately measure in 684 parts of hexanediamines and the 90 parts of water suction stills, extract 1200 parts of concentrated hydrochloric acids in hydrochloric acid drips jar, open and stir, under the logical water coolant condition of chuck, hydrochloric acid is dripped off;
Second step, emptying chuck water coolant in 2010 parts of phosphorous acid suction stills, are opened jacket steam and are warming up to 95 ℃, drip 2400 parts in formaldehyde;
The 3rd step, the insulation of 95 ~ 110 ℃ of temperature controls 1 hour are concentrated into the material retrogradation, after adding entry and continuing to be concentrated into the material retrogradation, add entry again and continue to be concentrated into the material retrogradation;
The 4th goes on foot, adds water transfers about 10000 parts of output, 500 parts in hydro-oxidation sodium below 80 ℃;
The 5th goes on foot, is cooled to blowing below 65 ℃.
4. the production technique of a kind of hexanediamine tetramethylene phosphonic acid disodium salt according to claim 3 is characterized in that: in the mode suction still of the water in the first step with negative pressure.
5. the production technique of a kind of hexanediamine tetramethylene phosphonic acid disodium salt according to claim 3 is characterized in that: the hydrochloric acid in the first step drips and drips under 70 ℃ of following conditions of temperature control.
6. the production technique of a kind of hexanediamine tetramethylene phosphonic acid disodium salt according to claim 3 is characterized in that: the formaldehyde dropping temperature in second step is 95 ~ 105 ℃.
7. the production technique of a kind of hexanediamine tetramethylene phosphonic acid disodium salt according to claim 3 is characterized in that: the material in the 3rd step is concentrated to the product chlorion and is lower than 5%.
8. the production technique of a kind of hexanediamine tetramethylene phosphonic acid disodium salt according to claim 3 is characterized in that: the actual add-on of the sodium hydroxide in the 4th step is 4.0 ~ 4.5 to be as the criterion to transfer still product 1% pH value of water solution.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103819506A (en) * | 2014-03-12 | 2014-05-28 | 山东省泰和水处理有限公司 | Preparation method of scale and corrosion inhibitor for circulating cooling water in oil refinery |
| CN104844649A (en) * | 2015-05-26 | 2015-08-19 | 周峰 | Preparation method of bis(hexamethylene triamine penta (methylene phosphonic acid)) |
| CN106146553A (en) * | 2015-04-09 | 2016-11-23 | 山东鑫泰水处理技术有限公司 | A kind of preparation method of hexapotassium potassium salt |
| CN112094293A (en) * | 2019-06-17 | 2020-12-18 | 山东鑫泰水处理技术股份有限公司 | Production process of high-purity solid zinc hydroxyethylidene diphosphonate |
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| CN112094293A (en) * | 2019-06-17 | 2020-12-18 | 山东鑫泰水处理技术股份有限公司 | Production process of high-purity solid zinc hydroxyethylidene diphosphonate |
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Application publication date: 20111102 |