CN101016315A - Preparing process adapted for electronic grade solid hydroxyethylidene diphosphonic acid - Google Patents
Preparing process adapted for electronic grade solid hydroxyethylidene diphosphonic acid Download PDFInfo
- Publication number
- CN101016315A CN101016315A CN 200710013340 CN200710013340A CN101016315A CN 101016315 A CN101016315 A CN 101016315A CN 200710013340 CN200710013340 CN 200710013340 CN 200710013340 A CN200710013340 A CN 200710013340A CN 101016315 A CN101016315 A CN 101016315A
- Authority
- CN
- China
- Prior art keywords
- diphosphonic acid
- preparation technology
- temperature
- hydroxy ethylene
- ethylene diphosphonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a making method of electron-grade solid hydroxy trimethylphosphine, which comprises the following steps: (1) cleaning autoclave, condenser and relative equipment clearly; (2) weighing liquid hydroxy trimethylphosphine into autoclave; stirring; (3) dehydrating in the vacuum under 35-120 deg.c; (4) cooling to 40-90 deg.c naturally; adding seed with quantity at 50-50000ppm; (5) cooling to indoor temperature; stewing; aging 4-20h; (7) centrifuging at high-speed centrifuger to dehydrate with velocity at 500-5000r/min; (8) packing the solid HEDP with activity over 95% and arsenic content less than 7ppm.
Description
Technical field
The present invention relates to the preparation technology of a kind of high-purity solid hydroxy ethylene diphosphonic acid (HEDP), the preparation technology who is applicable to electronic grade solid hydroxyethylidene diphosphonic acid of particularly a kind of clean-out system that can be used as electron trade, metal conditioner etc.
Background technology
Hydroxy ethylene diphosphonic acid (hereinafter to be referred as HEDP) is a kind of organic phosphine acids anti-incrustation corrosion inhibitor, can form stable complex compound with multiple metal ions such as iron, copper, zinc, the oxide compound on energy dissolution of metals surface.HEDP is generally as the scale inhibitor of recirculated cooling water, oil-field flooding and dyeing water, and its resistance to acids and bases, anti-oxychlorination performance are good than other organic phospho acid (salt).Can belong to ion with underwater gold, especially calcium ion forms six annulus inner complexs, thereby tool scale inhibition effect and the tangible molten limit effect of tool preferably.In light and textile industries, can make metal and nonmetallic clean-out system, bleaching and dyeing the peroxide stabiliser and the laking agent of industry, the complexing agent of cyanideless electro-plating industry.In addition, because HEDP scale effect preferably also has certain application at domestic detergent and cosmetic industry.In electron trade, HEDP is owing to have corrosion mitigating effect preferably, antiscaling effect and to the passivation effect of metallic surface, can be used for the cleaning of circuit version and metal finishing etc.
Yet the HEDP that is provided often is liquid product in the market, content is generally 50% and 60%, and purity is not high, wherein the content of arsenic is up to 70ppm after testing, and this is concerning electron trade, because arsenic is an important element of surface-mounted integrated circuit and printed circuit board (PCB) electronic component, as gallium arsenide, arsenic potassium, arsenical iron are monolithic integrated microwave circuit (IC) etc., and the residual of arsenic of trace will be caused short circuit and other harm to unicircuit.And concerning washing composition and cosmetic industry, because arsenic is a harmful element, arsenic content is too high will to cause serious harm to HUMAN HEALTH.Solid HEDP packing is simple and easy, store and transportation all very convenient, and the relative liquid product with trucking costs of storage is low, compound concentration regulated at will as required also in the use satisfies under the different treatment situation requirement to different concns.
Therefore, study a kind of high-purity solid HEDP preparation technology, can satisfy social needs greatly applicable to used in electronic industry.
Patent publication No. is that CN1699381A, application number are that 200510039287.X, denomination of invention are the patent application of " hydroxy ethylene diphosphonic acid of content 〉=90% and reparation technology thereof ", disclosed is the hydroxy ethylene diphosphonic acid (HEDP) and the reparation technology thereof of a kind of content 〉=90%, the composition weight percentage composition of its product is: hydroxy ethylene diphosphonic acid 90～98%, unavoidable impurities 1～2%, water surplus; Its reparation technology is to be that 50%～60% hydroxy ethylene diphosphonic acid is a raw material with liquid weight percentage, carries out according to following steps successively: get the raw materials ready; Add the nucleus sodium acetate; Stir; Add crystallization in motion agent dehydrated alcohol; Dehydration; Dry.Its principal claim be " 1, the hydroxy ethylene diphosphonic acid of a kind of content 〉=90%, contain hydroxy ethylene diphosphonic acid, unavoidable impurities and water, it is characterized in that: its composition weight percentage composition is: hydroxy ethylene diphosphonic acid 90～98%; Unavoidable impurities 1～2%; Water surplus.”
The specific implementation process of this application for a patent for invention is: get the raw materials ready (1), is raw material with the city for 50% hydroxy ethylene diphosphonic acid, gets 1000kg and insert reactor; (2) slowly add nucleus sodium acetate 15g; (3) stir, forward slowly stir by hand, and observe its crystalline condition at any time; (4) slowly add crystallization in motion agent dehydrated alcohol 25g, and slowly stir; (5) static 10～12 hours, use centrifuge dewatering; (6) make reverse convection drying with the solid-state hydroxy ethylene diphosphonic acid after 70 ℃ of hot blasts and the dehydration, promptly make content and be 91% solid-state hydroxy ethylene diphosphonic acid product; (7) the back packing appears on the market after testing.
Which impurity does not indicate inevitable impurity in this patent specification specifically is.
Patent publication No. CN1049351A, the patent No. are 90104982.4, denomination of invention is the patent of " purification process of aminomethy-lenephosphonic acids ", its principal claim for " be used for purifying ethylenediamine tetraacetic (methylene phosphonic acid) or 1; 4; 7; 10-tetraazacyclododecanand-1,4,7; the method for 10-four (methylene phosphonic acid), comprising step: (a) this aminophosphonic acid is dissolved in the alkali aqueous solution; (b) solution of step (a) can be joined in a kind of acid solution that keeps elevated temperature and go out aminophosphonic acid with redeposition; (c) solution can be heated the sufficiently long time to guarantee that aminophosphonic acid has begun to precipitate; (d) crystallization of filtration aminophosphonic acid; (e) wash crystallization with water.”
This patent of invention provides a kind of production high purity ammonia methylene phosphonic crystallization method, and its specific implementation method is: (1) is dissolved in aminophosphonic acid in the buck; (2) then solution is joined in a kind of acid solution that keeps elevated temperature and go out aminophosphonic acid with redeposition; (3) solution is heated the sufficiently long time to guarantee that aminophosphonic acid has begun to precipitate; (4) crystallization of filtration aminophosphonic acid; (5) wash crystallization with water.The first step (1) is dissolved in aminophosphonic acid in the alkali aqueous solution, should use ammonium hydroxide; Then step (2) to pH value from 0 to 4 scope, should be used mineral acid with sour souring soln; Step (3) refluxes acid solution for some time, temperature from 35～105 ℃ better, from 70～105 ℃ better, the time is from 0.5～3 hour better, and is better from 0.5～1 hour.Can keep for some time to take place with solution cooling and under this temperature subsequently to precipitation, described temperature from room temperature to 95 ℃ better, from 25～45 ℃ better, the time is from 1～24 hour better, and is better from 12～24 hours.Step (4) is that filtering-depositing is the crystalline aminophosphonic acid at a lower temperature, the crystallization of the purity that obtains requiring, and the thorough wash crystallization of step (5) water is to remove all solution that may contain undesirable impurity then.If do not obtain meeting the requirements of purity, can repeat this method once, can to obtain foreign matter content be 0.1% or be lower than 0.1% product with aforesaid method.
In this patent specification, do not indicate the high purity that its purity can reach electronic-grade yet, do not indicate especially that arsenic content reaches certain requirement in its product.
Summary of the invention
The purpose of this invention is to provide a kind of highly purified preparation technology who is applicable to electronic grade solid hydroxyethylidene diphosphonic acid, made its purity height, can be used as clean-out system, the metal conditioner of electron trade, also can be used as recirculated water and oil-field water processing etc.
To achieve these goals, a kind of preparation technology who is applicable to electronic grade solid hydroxyethylidene diphosphonic acid of the present invention, it is characterized in that: preparation technology may further comprise the steps:
(1) early-stage preparations clean up reactor, condenser and other relevant device;
(2) get the raw materials ready, take by weighing the liquid hydroxy ethylene diphosphonic acid in reactor, and start stirring;
(3) under 35～120 ℃ of temperature, concentrated a part of moisture content of sloughing heats up by vacuum hydro-extraction or under normal pressure;
(4) be cooled to 40～90 ℃ naturally, add crystal seed; Naturally be cooled to 40～90 ℃, be meant after step (3) vacuum hydro-extraction or under normal pressure, begin after 20～120 minutes after the intensification thickening and lower the temperature, the crystal seed that adds is a kind of and/or several in sodium sulfate, SODIUMNITRATE, sodium-chlor, sodium acetate, Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, hydroxy ethylene diphosphonic acid four sodium, ethylenediamine tetramethylene phosphonic acid, the sodium ethylenediamine tetramethylenephosphonate, and the amount that adds crystal seed is 50～50000ppm;
(5) slowly stir, and slowly cooling; Stirring velocity is 10～80rpm, and slowly cooling is to reduce to room temperature from the temperature of step (4) indication, per hour 2～40 ℃ of rate of temperature fall;
(6) reduce to room temperature after, still aging 4～20 hours;
(7) supercentrifuge centrifuge dehydration; Centrifugation rate is 500～5000r/min;
(8) solids package.
Described preparation technology is characterized in that: in step (1) early-stage preparations, washing is with high purity water related production equipment to be washed repeatedly; Wherein related production equipment comprises reactor, condenser, pipeline, valve, scale tank jar, whizzer, wherein high purity water is meant that it is 15～18M Ω/cm that quality index should reach resistivity, and it is that washing time is more than or equal to 2 times that related production equipment is washed repeatedly.
Described preparation technology is characterized in that: during step (2) was got the raw materials ready, the liquid hydroxy ethylene diphosphonic acid was that weight percentage is 50～60% hydroxy ethylene diphosphonic acid.
Described preparation technology is characterized in that: slough in a part of moisture content, select vacuum hydro-extraction for use.
Described preparation technology is characterized in that: in the step (3), the vacuum hydro-extraction temperature is 50～80 ℃.
Described preparation technology is characterized in that: step (4) is lowered the temperature naturally and is added in the crystal seed, and cooling begins cooling after being meant step (3) vacuum hydro-extraction after 40～60 minutes naturally, is cooled to 50～70 ℃ naturally; Add crystal seed amount be 100～20000ppm.
Described preparation technology is characterized in that: step (5) slowly stirs also in the slowly cooling, and slowly stirring velocity is 30～50rpm; Slowly rate of temperature fall is per hour 10～20 ℃.
Described preparation technology is characterized in that: after step (6) is reduced to room temperature, and still aging 12～14 hours.
Described preparation technology is characterized in that: in step (7) the supercentrifuge centrifuge dehydration, centrifugation rate is 2400r/min
Described preparation technology is characterized in that: the product of preparation is the white granular solid matter, and more than 95%, the content of arsenic is below 7ppm in the active constituent of hydroxy ethylene diphosphonic acid for the content of hydroxy ethylene diphosphonic acid.
The invention provides the preparation technology of a kind of high-purity solid hydroxy ethylene diphosphonic acid (HEDP), more than 95%, the 70ppm of the content of arsenic from liquid product before dropped to below the 7ppm in the solid phase prod solid HEDP that produces in the active quantities of HEDP.Because its purity height, can be used as the clean-out system, metal conditioner of metal chelator, the electron trade of textile printing and dyeing industry etc.Owing to be solid form, be different from the market conventional active constituent and be 50% liquid form, solid HEDP packing is simple and easy, storage and transportation are all very convenient, and the relative liquid product with trucking costs of storage is low, compound concentration regulated at will as required also in the use satisfies under the different treatment situation the requirement of different concns, therefore can greatly satisfy social needs.
Preparation technology of the present invention has very significant advantage, (1) the solid hydroxyethylidene diphosphonic acid product produced of the present invention in the active quantities of HEDP more than 95%, the 70ppm of the content of arsenic from liquid product before dropped to below the 7ppm in the solid phase prod, the content of impurity greatly reduces, and can satisfy the specification of quality of electronic industry to the high purity hydroxyl ethylidene diphosphonic acid; (2) operational condition gentleness of the present invention, production process does not have the corrosion three-waste free discharge, is green production process; (3) the present invention need not add organic solvent, thereby has stopped the pollution to environment that the VOC discharging is brought; (4) grain size number of the present invention is big, helps filter operation, product yield height; (5) solid hydroxyethylidene diphosphonic acid of the present invention's production, solid HEDP packing is simple and easy, storage and transportation are all very convenient, and the relative liquid product with trucking costs of storage is low, compound concentration regulated at will as required also in the use satisfies under the different treatment situation requirement to different concns.
Description of drawings
Figure is a process flow sheet of the present invention.
Embodiment
The present invention is a kind of to be applicable to that the product of preparation technology's preparation of electronic grade solid hydroxyethylidene diphosphonic acid is the white granular solid matter, and more than 95%, the content of arsenic is below 7ppm in the active constituent of HEDP for the content of hydroxy ethylene diphosphonic acid.
The present invention as shown in the figure, its preparation technology may further comprise the steps:
(1) early-stage preparations clean up reactor, condenser and other relevant device.Because the solid HEDP that the present invention institute is provided is a kind of high purity product, before producing, must comprise that reactor, condenser, pipeline, valve, scale tank jar, whizzer etc. carry out meticulous careful washing to associated production unit.The washing of indication of the present invention is with high purity water related production equipment to be washed repeatedly.The high purity water of indication of the present invention is that quality index should reach the known commercially available high purity water that resistivity is 15～18M Ω/cm, and indication of the present invention related production equipment is washed repeatedly is that washing time is more than or equal to 2 times.
(2) get the raw materials ready, the liquid hydroxy ethylene diphosphonic acid that takes by weighing a certain amount of certain specification and starts stirring in reactor.The liquid hydroxy ethylene diphosphonic acid is that weight percentage is 50～60% hydroxy ethylene diphosphonic acid, and its quality index should meet HG/T2841-1997.
(3) at a certain temperature, slough a part of moisture content.Indication slough a part of moisture content at a certain temperature, can be the vacuum hydro-extraction under vacuum condition, also can be to heat up under the normal pressure to concentrate.Certain temperature of indication of the present invention is 35～120 ℃, preferred 50～80 ℃.Indication of the present invention is sloughed the preferred vacuum hydro-extraction of a part of moisture content.
(4) be cooled to certain temperature naturally, add crystal seed.Indication be cooled to certain temperature naturally, be to begin cooling after step (3) vacuum hydro-extraction after 20～120 minutes, begin cooling after preferred 40～60 minutes, temperature is reduced to 40～90 ℃, preferred 50～70 ℃.It is a kind of and/or several in sodium sulfate, SODIUMNITRATE, sodium-chlor, sodium acetate, Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, hydroxy ethylene diphosphonic acid four sodium, ethylenediamine tetramethylene phosphonic acid, the sodium ethylenediamine tetramethylenephosphonate that indication of the present invention adds crystal seed.The amount of the adding crystal seed of indication of the present invention is 50～50000ppm, preferred 100～20000ppm.
(5) slowly stir, and slowly cooling.Slowly stir and be meant that stirring velocity is 10～80rpm, preferred 30～50rpm.Indication of the present invention slowly cooling is to reduce to room temperature from the temperature of step (4) indication, better per hour 2～40 ℃ of rate of temperature fall, better per hour 10～20 ℃.
(6) reduce to room temperature after, still aging for some time.Still aging for some time of indication is 4～20 hours still aging time, preferred 12～14 hours.
(7) supercentrifuge centrifuge dehydration.The centrifugation of indication supercentrifuge is meant that centrifugation rate is 500～5000r/min.
(8) solids package.
The invention provides a kind of highly purified preparation technology who is applicable to electronic grade solid hydroxyethylidene diphosphonic acid (HEDP), more than 95%, the 70ppm of the content of arsenic from liquid product before dropped to below the 7ppm in the solid phase prod solid HEDP that produces in the active quantities of HEDP.Because its purity height, can be used as the clean-out system, metal conditioner of metal chelator, the electron trade of textile printing and dyeing industry etc.Owing to be solid form, be different from the market conventional active constituent and be 50% liquid form, solid HEDP packing is simple and easy, storage and transportation are all very convenient, and the relative liquid product with trucking costs of storage is low, compound concentration regulated at will as required also in the use satisfies under the different treatment situation the requirement of different concns, therefore can greatly satisfy social needs.
Preparation technology of the present invention has very significant advantage: the solid hydroxyethylidene diphosphonic acid product that (1) the present invention produces in the active quantities of HEDP more than 95%, the 70ppm of the content of arsenic from liquid product before dropped to below the 7ppm in the solid phase prod, the content of impurity greatly reduces, and can satisfy the specification of quality of electronic industry to the high purity hydroxyl ethylidene diphosphonic acid; (2) operational condition gentleness of the present invention, production process does not have the corrosion three-waste free discharge, is green production process; (3) the present invention need not add organic solvent, thereby has stopped the pollution to environment that the VOC discharging is brought; (4) grain size number of the present invention is big, helps filter operation, product yield height; (5) solid hydroxyethylidene diphosphonic acid of the present invention's production, solid HEDP packing is simple and easy, storage and transportation are all very convenient, and the relative liquid product with trucking costs of storage is low, compound concentration regulated at will as required also in the use satisfies under the different treatment situation requirement to different concns.
Preparation technology's embodiment of the present invention is as follows:
Embodiment 1:
With high purity water with reactor, condenser, pipeline, valve, each relevant device flushing such as whizzer once, add weight percentage and be 3 tons of 50% liquid hydroxy ethylene diphosphonic acids, start stirring, be warmed up to 70 ℃ and draw negative pressure with vacuum, vacuum hydro-extraction 500kg, temperature should must not keep and was higher than 100 ℃ this moment, naturally cooling, slowly cooling after 2 hours is when temperature is reduced to 55 ℃, add crystal seed Amino Trimethylene Phosphonic Acid and each 150g of hydroxy ethylene diphosphonic acid, transfer slow stirring velocity to 30rpm, keep temperature slowly to reduce this moment, and per hour rate of temperature fall is 15 ℃, when reducing to room temperature, remained under this temperature ageing 12 hours.Open baiting valve at the bottom of the still, feed liquid is put to the centrifuge dehydration of high speed whizzer, the rotating speed of whizzer is controlled at 2000rpm.The solid of centrifugal back gained is satisfactory high purity hydroxy ethylene diphosphonic acid, and after testing, product is 95% in the active quantities of HEDP, and the content of arsenic is 6.4ppm.
Embodiment 2:
With high purity water with reactor, condenser, pipeline, valve, each relevant device flushing such as whizzer once, add to add weight percentage and be 3 tons of 50% liquid hydroxy ethylene diphosphonic acids, start stirring, be warmed up to 60 ℃ and draw negative pressure with vacuum, vacuum hydro-extraction 700kg, temperature should must not keep and was higher than 110 ℃ this moment, naturally cooling, slowly cooling after 1 hour is when temperature is reduced to 75 ℃, add crystal seed sodium acetate and each 200g of Amino Trimethylene Phosphonic Acid, transfer slow stirring velocity to 50rpm, keep temperature slowly to reduce this moment, and per hour rate of temperature fall is 25 ℃, when reducing to room temperature, remained under this temperature ageing 6 hours.Open baiting valve at the bottom of the still, feed liquid is put to the centrifuge dehydration of high speed whizzer, the rotating speed of whizzer is controlled at 1000rpm.The solid of centrifugal back gained is satisfactory high purity hydroxy ethylene diphosphonic acid, and after testing, product is 91% in the active quantities of HEDP, and the content of arsenic is 5.5ppm.
Embodiment 3:
Press the schedule of operation of embodiment 1, vacuum hydro-extraction 900kg.Follow-up after reducing to room temperature, remained under this temperature ageing 10 hours, other is with example 1.After testing, product is 96% in the active quantities of HEDP, and the content of arsenic is 3.4ppm.
Embodiment 4:
With high purity water with reactor, condenser, pipeline, valve, each relevant device flushing such as whizzer once, add to add weight percentage and be 2 tons of 50% liquid hydroxy ethylene diphosphonic acids, start stirring, being warmed up to 80 ℃ draws negative pressure extremely with vacuum, vacuum hydro-extraction 700kg, temperature should must not keep and was higher than 120 ℃ this moment, naturally cooling, slowly cooling after 4 hours is when temperature is reduced to 60 ℃, add crystal seed hydroxy ethylene diphosphonic acid and each 120g of sodium sulfate, transfer slow stirring velocity to 50rpm, keep temperature slowly to reduce this moment, and per hour rate of temperature fall is 12 ℃, when reducing to room temperature, remained under this temperature ageing 4 hours.Open baiting valve at the bottom of the still, feed liquid is put to the centrifuge dehydration of high speed whizzer, the rotating speed of whizzer is controlled at 2000rpm.The solid of centrifugal back gained is satisfactory high purity hydroxy ethylene diphosphonic acid, and after testing, product is 91% in the active quantities of HEDP, and the content of arsenic is 6.5ppm.
Claims (10)
1, a kind of preparation technology who is applicable to electronic grade solid hydroxyethylidene diphosphonic acid, it is characterized in that: preparation technology may further comprise the steps:
(1) early-stage preparations clean up reactor, condenser and other relevant device;
(2) get the raw materials ready, take by weighing the liquid hydroxy ethylene diphosphonic acid in reactor, and start stirring;
(3) under 35～120 ℃ of temperature, concentrated a part of moisture content of sloughing heats up by vacuum hydro-extraction or under normal pressure;
(4) be cooled to 40～90 ℃ naturally, add crystal seed; Naturally be cooled to 40～90 ℃, be meant after step (3) vacuum hydro-extraction or under normal pressure, begin after 20～120 minutes after the intensification thickening and lower the temperature, the crystal seed that adds is a kind of and/or several in sodium sulfate, SODIUMNITRATE, sodium-chlor, sodium acetate, Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, hydroxy ethylene diphosphonic acid four sodium, ethylenediamine tetramethylene phosphonic acid, the sodium ethylenediamine tetramethylenephosphonate, and the amount that adds crystal seed is 50～50000ppm;
(5) slowly stir, and slowly cooling; Stirring velocity is 10～80rpm, and slowly cooling is to reduce to room temperature from the temperature of step (4) indication, per hour 2～40 ℃ of rate of temperature fall;
(6) reduce to room temperature after, still aging 4～20 hours;
(7) supercentrifuge centrifuge dehydration; Centrifugation rate is 500～5000r/min;
(8) solids package.
2. preparation technology as claimed in claim 1 is characterized in that: in step (1) early-stage preparations, washing is with high purity water related production equipment to be washed repeatedly; Wherein related production equipment comprises reactor, condenser, pipeline, valve, scale tank jar, whizzer, wherein high purity water is meant that it is 15～18M Ω/cm that quality index should reach resistivity, and it is that washing time is more than or equal to 2 times that related production equipment is washed repeatedly.
3, preparation technology as claimed in claim 1 is characterized in that: during step (2) was got the raw materials ready, the liquid hydroxy ethylene diphosphonic acid was that weight percentage is 50～60% hydroxy ethylene diphosphonic acid.
4, preparation technology as claimed in claim 1 is characterized in that: slough in a part of moisture content, select vacuum hydro-extraction for use.
5, preparation technology as claimed in claim 4 is characterized in that: in the step (3), the vacuum hydro-extraction temperature is 50～80 ℃.
6, preparation technology as claimed in claim 4 is characterized in that: step (4) is lowered the temperature naturally and is added in the crystal seed, and cooling begins cooling after being meant step (3) vacuum hydro-extraction after 40～60 minutes naturally, is cooled to 50～70 ℃ naturally; Add crystal seed amount be 100～20000ppm.
7, preparation technology as claimed in claim 1 is characterized in that: step (5) slowly stirs also in the slowly cooling, and slowly stirring velocity is 30～50rpm; Slowly rate of temperature fall is per hour 10～20 ℃.
8, preparation technology as claimed in claim 1 is characterized in that: after step (6) is reduced to room temperature, and still aging 12～14 hours.
9, preparation technology as claimed in claim 1 is characterized in that: in step (7) the supercentrifuge centrifuge dehydration, centrifugation rate is 2400r/min.
10, preparation technology as claimed in claim 1 is characterized in that: the product of preparation is the white granular solid matter, and more than 95%, the content of arsenic is below 7ppm in the active constituent of hydroxy ethylene diphosphonic acid for the content of hydroxy ethylene diphosphonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100133408A CN100478347C (en) | 2007-02-13 | 2007-02-13 | Preparing process adapted for electronic grade solid hydroxyethylidene diphosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100133408A CN100478347C (en) | 2007-02-13 | 2007-02-13 | Preparing process adapted for electronic grade solid hydroxyethylidene diphosphonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101016315A true CN101016315A (en) | 2007-08-15 |
| CN100478347C CN100478347C (en) | 2009-04-15 |
Family
ID=38725555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100133408A Active CN100478347C (en) | 2007-02-13 | 2007-02-13 | Preparing process adapted for electronic grade solid hydroxyethylidene diphosphonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100478347C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386628B (en) * | 2008-10-29 | 2010-12-15 | 河南清水源科技股份有限公司 | Hydroxylethylidene diphosphonic acid with arsenic content <=3ppm and preparation technique thereof |
| CN102229620A (en) * | 2011-04-27 | 2011-11-02 | 河南清水源科技股份有限公司 | High-purity solid hydroxyethylidenediphosphonic acid tetrasodium salt (HEDP.Na4) and production process thereof |
| CN102276646A (en) * | 2011-07-01 | 2011-12-14 | 常州市科威精细化工有限公司 | Method for producing hydroxyethylidenediphosphonic acid solid |
| CN102875594A (en) * | 2012-10-20 | 2013-01-16 | 山东省泰和水处理有限公司 | Continuous synthesis technique of hydroxyethylidenediphosphonic acid |
| CN103435645A (en) * | 2013-09-09 | 2013-12-11 | 山东省泰和水处理有限公司 | Preparation method of low iron and low chloride hydroxyethylidene-1,1-diphosphonic acid (HEDP) |
| CN103509051A (en) * | 2012-06-21 | 2014-01-15 | 河南清水源科技股份有限公司 | Preparation process for high-purity low-arsenic hydroxyethylidene diphosphonic acid |
| CN109883146A (en) * | 2019-03-29 | 2019-06-14 | 深圳市华威环保建材有限公司 | A kind of building castoff dehydration system and its dewatering process |
-
2007
- 2007-02-13 CN CNB2007100133408A patent/CN100478347C/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386628B (en) * | 2008-10-29 | 2010-12-15 | 河南清水源科技股份有限公司 | Hydroxylethylidene diphosphonic acid with arsenic content <=3ppm and preparation technique thereof |
| CN102229620A (en) * | 2011-04-27 | 2011-11-02 | 河南清水源科技股份有限公司 | High-purity solid hydroxyethylidenediphosphonic acid tetrasodium salt (HEDP.Na4) and production process thereof |
| CN102229620B (en) * | 2011-04-27 | 2014-05-28 | 河南清水源科技股份有限公司 | High-purity solid hydroxyethylidenediphosphonic acid tetrasodium salt (HEDP.Na4) and production process thereof |
| CN102276646A (en) * | 2011-07-01 | 2011-12-14 | 常州市科威精细化工有限公司 | Method for producing hydroxyethylidenediphosphonic acid solid |
| CN103509051A (en) * | 2012-06-21 | 2014-01-15 | 河南清水源科技股份有限公司 | Preparation process for high-purity low-arsenic hydroxyethylidene diphosphonic acid |
| CN103509051B (en) * | 2012-06-21 | 2016-08-03 | 河南清水源科技股份有限公司 | A kind of preparation technology of the hydroxy ethylene diphosphonic acid of the low arsenic of high-purity |
| CN102875594A (en) * | 2012-10-20 | 2013-01-16 | 山东省泰和水处理有限公司 | Continuous synthesis technique of hydroxyethylidenediphosphonic acid |
| CN102875594B (en) * | 2012-10-20 | 2015-05-06 | 山东省泰和水处理有限公司 | Continuous synthesis technique of hydroxyethylidenediphosphonic acid |
| CN103435645A (en) * | 2013-09-09 | 2013-12-11 | 山东省泰和水处理有限公司 | Preparation method of low iron and low chloride hydroxyethylidene-1,1-diphosphonic acid (HEDP) |
| CN109883146A (en) * | 2019-03-29 | 2019-06-14 | 深圳市华威环保建材有限公司 | A kind of building castoff dehydration system and its dewatering process |
| CN109883146B (en) * | 2019-03-29 | 2020-08-14 | 深圳市华威环保建材有限公司 | Construction waste dehydration treatment system and dehydration process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100478347C (en) | 2009-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100478347C (en) | Preparing process adapted for electronic grade solid hydroxyethylidene diphosphonic acid | |
| CN100471860C (en) | Preparing process adapted for electronic grade solid aminotrimethylene phosphonic acid | |
| CN101514306B (en) | Fabric dirt pretreatment agent containing steady biological enzyme complex and low-activity substance and preparation method thereof | |
| CN101381376B (en) | Preparation technology suitable for electronic grade solid ethylenediamine tetramethylene phosphonic acid | |
| CN105829356A (en) | Process for extraction of calcium sensitive pectin | |
| CN101381377B (en) | Preparation technology suitable for electronic grade solid hexamethylenediamine tetramethylene phosphonic acid | |
| CN104193634A (en) | Method for separating mixed crystals of glycine and ammonium chloride | |
| US20100129282A1 (en) | High-purity calcium compounds | |
| CN108948124A (en) | A kind of preparation method of Tea Saponin | |
| CN101597305B (en) | Preparation process for a solid aminotrimethylenephosphonic acid (ATMP) or 1-hydoxy ethyidene-1.1-diphosphonic acid | |
| CN1312163C (en) | Hydroxy ethylidene diphosphonic acid with content of greater than or equal to 90 percent and process for making same | |
| CN104556205A (en) | Technical method for producing feed-grade zinc sulfate in environment-friendly manner by electrolytic zinc slag | |
| CN102602979A (en) | Preparation method for copper chloride hydroxide | |
| JP5079631B2 (en) | Waste liquid reduction method and waste liquid treatment method | |
| KR20100050256A (en) | Method for recovering potasium chloride in liquid waste | |
| CN101644017B (en) | Peroxide stabilizing agent based on biomass extract and preparation method thereof | |
| CN106044868A (en) | Technological method and device for preparing ferrous sulfate crystals by aid of copper sulfate waste liquor | |
| CN105001075B (en) | A kind of extracting method of citric acid | |
| CN1995015B (en) | Method for preparing feed grade methionine copper chelate using waste etching liquor | |
| CN105481136A (en) | Comprehensive treatment method for recycling waste calcium water and waste acid obtained through algin production | |
| CN114057326B (en) | Water treatment method for steam boiler | |
| CN110937614B (en) | Method for preparing purification additive and purification additive prepared by the method | |
| CN102875366B (en) | Method for purifying crude terephthalic acid by adding inhibitor for high temperature reduction | |
| CN110845324B (en) | Preparation process of sodium acetate trihydrate | |
| AU2018438104B2 (en) | Electromagnetic ionic liquid and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANGDONG TAIHE WATER TREATMENT TECHNOLOGIES CO., Free format text: FORMER NAME: SHANDONG TAIHE WATER TREATMENT CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Patentee after: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. Address before: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Patentee before: SHANDONG TAIHE WATER TREATMENT Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province 277100 Patentee after: Shandong Taihe Technology Co.,Ltd. Address before: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Patentee before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |