CN101381377B - Preparation technology suitable for electronic grade solid hexamethylenediamine tetramethylene phosphonic acid - Google Patents
Preparation technology suitable for electronic grade solid hexamethylenediamine tetramethylene phosphonic acid Download PDFInfo
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Abstract
The invention relates to a process for preparing electronic grade hexamethylenediaminetetra (methylenephosphonic acid) solid. The process comprises the following steps: (1) first-phrase preparation which is to clean related equipment; (2) dissolving orthophosphorous acid crystals in high-purity water for recrystallization, and obtaining high purity orthophosphorous acid for later use; (3) placing the high-purity orthophosphorous acid and 30 percent hydrochloric acid into a reaction kettle with stirring and temperate raising, and dripping ethylene diamine into the reaction kettle; (4) raising temperature, dripping methyl alcohol and then keeping temperature; (5) after slight temperature drop, dripping crystal nucleating agent till crystals are precipitated; (6) raising temperature and continuing to dripping methyl alcohol; (7) decreasing temperature step by step; (8) centrifugation, drying, screening and packaging. The white solid particles of EDTMPA has a content of active EDTMPA of more than 95 percent, a content of arsenic less than 0.5 mg/L. The high-purity solid ethylene diamine tetra (methylene phosphonic acid) can be used as metal-chelator for textile dyeing industry, a washing agent for electronic industry, a metal conditioner, etc., and has the advantages of simple package, convenient storage and transportation as a solid.
Description
Technical field
The present invention relates to the preparation technology of a kind of high-purity solid hexamethylenediaminetetramethylene tetramethylene phosphonic acid (HDTMPA), the highly purified preparation technology who is applicable to electronic grade solid hexamethylenediaminetetramethylene tetramethylene phosphonic acid (HDTMPA) of particularly a kind of clean-out system that can be used as electron trade, metal conditioner etc.
Background technology
HDTMPA has the ability of very strong chelated metal ions, with the complexation constant of cupric ion be comprise in all sequestrants of EDTA maximum.HDTMPA is a high purity reagent and nontoxic, and the clean-out system that can be used as semi-conductor chip in electron trade is used to make unicircuit; Do the agent of carrying of radioelement in pharmaceutical industries, be used for checking and the treatment disease; The sequestering power of HDTMPA far surpasses EDTA and DTPA, almost substitutes at all available HDTMPA in place that use EDTA to make sequestrant.
Yet the HDTMPA that is provided often is the liquid sodium product salt in the market, and content is generally below 50%.And purity is not high, after testing wherein the content of arsenic up to 70mg/L, 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.Concerning washing composition and cosmetic industry, because arsenic is a kind of harmful element, arsenic content is too high will to cause serious harm to HUMAN HEALTH.Solid HDTMPA 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 HDTMPA production technique, 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." 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. is that CN1049351A, application number are 90104982.4, denomination of invention is the patent of " purification process of aminomethy-lenephosphonic acids ", a kind of production high purity ammonia methylene phosphonic crystallization method is provided: 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 acids), 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.
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 high-purity solid hexanediamine tetramethylene phosphonic acid (HDTMPA) production technique, make 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.
For achieving the above object, the invention provides a kind of preparation technology who is applicable to electronic grade solid hexanediamine tetramethylene phosphonic acid (HDTMPA), preparation technology may further comprise the steps:
(1) early-stage preparations, equipment washing such as reactor, condenser, pipeline, valve, scale tank jar, whizzer is clean;
(2) crystal phosphorous acid is dissolved in recrystallization in the high purity water, and it is standby to get high-purity phosphorous acid;
(3) with in 1～50 part in high-purity phosphorous acid (mass fraction, down together), 1～60 part of input reactor of 30% hydrochloric acid, open stirring slowly, be warmed up to-5～60 ℃ and begin to drip 2～16 parts of hexanediamines, the dropping time is 1～24hr;
(4) be warming up to 50～120 ℃ after dropwising, drip 1～60 part in formaldehyde, the dropping time is 1～12hr, dropwises insulation; Soaking time is 1～10hr;
(5) treat that temperature is fallen slightly after, add crystal nucleating agent, until there being crystal to separate out; The crystal nucleating agent that adds is one or more in sodium sulfate, SODIUMNITRATE, sodium-chlor, sodium acetate, Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, sodium acetate+hydroxy ethylene diphosphonic acid (mass ratio is 1:3), hydroxy ethylene diphosphonic acid four sodium, ethylenediamine tetramethylene phosphonic acid (sodium), the hexanediamine tetramethylene phosphonic acid;
(6) the intensification back continues to drip 2～40 parts in formaldehyde, and the dropping time is 0.1～10 hour, dropwises, and is incubated 0～24 hour;
(7), cool to-10～50 ℃ by the rate of temperature fall that per hour falls 1～40 ℃;
(8) centrifuge washing, centrifugation rate are 500～5000r/min, and drying is sieved, and packing obtains white crystal, and purity is more than 95%.
Described preparation technology, it is characterized in that: in step (1) early-stage preparations, washing is with high purity water related production equipment to be washed repeatedly, Xiang Guan production unit wherein, comprise reactor, condenser, pipeline, valve, scale tank jar, whizzer, 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: the high purity water that uses in the step (2) is meant that resistivity is 15～18M Ω/cm in the quality index.
Described preparation technology is characterized in that: the add-on of the high-purity phosphorous acid of step (3) is 10～50 parts, and the add-on of 30% hydrochloric acid is 10～50 parts, is warmed up to-5～60 ℃, and the amount that drips hexanediamine is 2～14 parts, and the dropping time is 2～24hr.
Described preparation technology is characterized in that: in the step (4), the temperature that dropwises intensification is 60～120 ℃, and the amount of the formaldehyde of dropping is 5～50 parts, and the dropping time is 1～12hr, and soaking time is 1～10hr.
Described preparation technology is characterized in that: step (5) is lowered the temperature naturally and is meant that step (4) soaking time after 1～10 hour, is cooled to 50～100 ℃ naturally; Add crystal nucleating agent amount be 0.001～0.5 part, until there being crystal to separate out.
Described preparation technology is characterized in that: the back of heating up in the step (6) continues to drip 2～20 parts in formaldehyde, and the dropping time is 0.1～10 hour, dropwises insulation 0～24 hour.
Described preparation technology is characterized in that: step (7) refers to per hour fall 1～20 ℃ by certain speed cooling, cools to 0～50 ℃.
Described preparation technology is characterized in that: in step (8) the whizzer centrifuge dehydration, centrifugation rate is 1000～5000r/min.
The invention provides the production technique of a kind of high-purity solid hexanediamine tetramethylene phosphonic acid (HDTMPA), more than 95%, the 70mg/L of the content of arsenic from liquid product before dropped to below the 0.5mg/L in the solid phase prod white granular solid HDTMPA that produces in the active quantities of HDTMPA.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 HDTMPA 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.
Method of the present invention has very significant advantage, (1) the solid hexanediamine tetramethylene phosphonic acid product produced of the present invention in the active quantities of HDTMPA more than 95%, the 70mg/L of the content of arsenic from liquid product before dropped to below the 0.5mg/L in the solid phase prod, the content of impurity greatly reduces, and can satisfy the specification of quality of electronic industry to high-purity hexanediamine tetramethylene phosphonic 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) the solid HDTMPA packing of the present invention's production is simple and easy, storage and transportation are all very convenient, and the relative liquid product with trucking costs of storage is low, and 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
A kind of preparation technology who is applicable to electronic grade solid hexamethylenediaminetetramethylene tetramethylene phosphonic acid (HDTMPA) of the present invention, the product of preparation is the white granular solid matter, more than 95%, the content of arsenic is below 0.5mg/L in the active constituent of HDTMPA for the content of hexamethylenediaminetetramethylene tetramethylene phosphonic acid.
The present invention as described in Figure, its production technique may further comprise the steps:
(1) early-stage preparations: equipment washing such as reactor, condenser, pipeline, valve, scale tank jar, whizzer is clean.
(2) crystal phosphorous acid is dissolved in recrystallization in the high purity water, and it is standby to get high-purity phosphorous acid;
(3) with in 1～50 part in high-purity phosphorous acid (mass fraction, down with), 1～60 part of input reactor of 30% hydrochloric acid, open stirring slowly, stir speed (S.S.) 30～80rpm begins to drip 2～16 parts of hexanediamines under-5～60 ℃, and the dropping time is 1～24hr;
(4) temperature that dropwises intensification is 50～120 ℃, and the amount of the formaldehyde of dropping is 1～60 part, and the dropping time is 1～12hr, and soaking time is 1～10hr;
(5) treat that temperature reduces to 50～100 ℃, add 0.001～0.5 part of crystal nucleating agent, until there being crystal to separate out; The crystal nucleating agent that adds is one or more in sodium sulfate, SODIUMNITRATE, sodium-chlor, sodium acetate, Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, sodium acetate+hydroxy ethylene diphosphonic acid (mass ratio is 1:3), hydroxy ethylene diphosphonic acid four sodium, ethylenediamine tetramethylene phosphonic acid (sodium), the hexamethylenediaminetetramethylene tetramethylene phosphonic acid;
(6) the intensification back continues to drip 2～40 parts in formaldehyde, and the dropping time is 0.1～10 hour, dropwises insulation 0～24 hour;
(7), cool to-10～50 ℃ by the rate of temperature fall that per hour falls 1～40 ℃;
(8) in the whizzer centrifuge dehydration, centrifugation rate is 500～5000r/min,, sieves packing with resulting solid phase prod drying.
More than 95%, the 70mg/L of the content of arsenic from liquid product before dropped to below the 0.5mg/L in the solid phase prod solid HDTMPA of above-mentioned explained hereafter in the active quantities of HDTMPA.
Indication production technique embodiment of the present invention is as follows:
Embodiment 1:
With high purity water once with each relevant device flushing such as reactor, condenser, pipeline, valve, whizzer.With high-purity phosphorous acid 2000kg, 30% hydrochloric acid 2000kg drops in the reactor, opens stirring slowly, stir speed (S.S.) 60rpm, and 50 ℃ drip hexanediamine 500kg, 4 hours dropping time down; Be warming up to 60 ℃ after dripping off, drip formaldehyde 1800kg, 2 hours dropping time, drip complete formaldehyde 75 ℃ of insulations 1 hour; After treating that temperature is reduced to 65 ℃, add crystal nucleating agent hexanediamine tetramethylene phosphonic acid solid 1200g, have crystal to separate out this moment; After being warming up to 85 ℃, drip formaldehyde 1100kg, the dropping time is 1 hour, dropwises, and is incubated 2 hours; Gradient cooling to 15 ℃, the gradient cooling rate-controlling is per hour being fallen 25 ℃, and have a large amount of crystal to separate out this moment.Centrifugal with whizzer, centrifugation rate is 5000r/min, and washs with high purity water, and drying is sieved, and packing obtains crystal 1600kg.After testing, product is 95% in the active quantities of HDTMPA, and the content of arsenic is 0.4mg/L.
Embodiment 2:
With high purity water once with each relevant device flushing such as reactor, condenser, pipeline, valve, whizzer.With high-purity phosphorous acid 1200kg, 30% hydrochloric acid 800kg drops in the reactor, opens stirring slowly, stir speed (S.S.) 60rpm, and 50 ℃ drip hexanediamine 320kg, 2 hours dropping time down; Be warming up to 60 ℃ after dripping off, drip formaldehyde 800kg, 2 hours dropping time, drip complete formaldehyde 75 ℃ of insulations 1 hour; After treating that temperature is reduced to 65 ℃, add crystal nucleating agent hexamethylenediaminetetramethylene tetramethylene phosphonic acid solid 800g, have crystal to separate out this moment; After being warming up to 85 ℃, drip formaldehyde 800kg, the dropping time is 1 hour, dropwises, and is incubated 2 hours; Gradient cooling to 35 ℃, the gradient cooling rate-controlling is per hour being fallen 15 ℃, and have a large amount of crystal to separate out this moment.Centrifugal with whizzer, centrifugation rate is 4000r/min, and washs with high purity water, and drying is sieved, and packing obtains crystal 1100kg.After testing, product is 97.5% in the active quantities of HDTMPA, and the content of arsenic is 0.2mg/L.
Embodiment 3:
Press the schedule of operation of embodiment 1, add crystal nucleating agent hydroxy ethylidene-diphosphate 1000g, other is with embodiment 1.After testing, product is 98% in the active quantities of HDTMPA, and the content of arsenic is 0.3mg/L.
Embodiment 4:
Press the schedule of operation of embodiment 1, adding crystal nucleating agent Amino Trimethylene Phosphonic Acid 1000g has crystal to separate out at this moment; After being warming up to 85 ℃, drip formaldehyde 1100kg, the dropping time is 1 hour, dropwises, and is incubated 2 hours; Gradient cooling to 25 ℃, the gradient cooling rate-controlling is per hour being fallen 5 ℃, and have a large amount of crystal to separate out this moment.Centrifugal with whizzer, centrifugation rate is 3000r/min, and washs with high purity water, and drying is sieved, and packing obtains crystal 1400kg.After testing, product is 98% in the active quantities of HDTMPA, and the content of arsenic is 0.2mg/L.
Claims (9)
1. preparation technology who is applicable to electronic grade solid hexanediamine tetramethylene phosphonic acid, it is characterized in that: preparation technology may further comprise the steps:
(1) early-stage preparations clean up reactor, condenser, pipeline, valve, scale tank jar, whizzer;
(2) crystal phosphorous acid is dissolved in recrystallization in the high purity water, and it is standby to get high-purity phosphorous acid;
(3) high-purity phosphorous acid 1～50 mass parts, 30% hydrochloric acid, 1～60 mass parts are dropped in the reactor, open stirring slowly, be warmed up to-5～60 ℃ and begin to drip hexanediamine 2～16 mass parts, the dropping time is 1～24hr;
(4) be warming up to 50～120 ℃ after dropwising, drip formaldehyde 1～60 mass parts, the dropping time is 1～12hr, dropwises insulation; Soaking time is 1～10hr;
(5) treat that temperature is fallen slightly after, add crystal nucleating agent, until there being crystal to separate out; The crystal nucleating agent that adds is that sodium sulfate, SODIUMNITRATE, sodium-chlor, sodium acetate, Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, mass ratio are one or more in 1: 3 the sodium acetate+hydroxy ethylene diphosphonic acid, hydroxy ethylene diphosphonic acid four sodium, ethylenediamine tetramethylene phosphonic acid, sodium ethylenediamine tetramethylenephosphonate, hexanediamine tetramethylene phosphonic acid;
(6) the intensification back continues to drip formaldehyde 2～40 mass parts, and the dropping time is 0.1～10 hour, dropwises, and is incubated 0～24 hour;
(7), cool to-10～50 ℃ by the rate of temperature fall that per hour falls 1～40 ℃;
(8) centrifuge washing, centrifugation rate are 500～5000r/min, and drying is sieved, packing.
2. preparation technology as claimed in claim 1, it is characterized in that: in step (1) early-stage preparations, washing is with high purity water reactor, condenser, pipeline, valve, scale tank jar, whizzer to be washed repeatedly, and washing repeatedly is that washing time is more than or equal to 2 times.
3. preparation technology as claimed in claim 1 is characterized in that: the high purity water that uses in the step (2) is meant that resistivity is 15～18M Ω/cm in the quality index.
4. preparation technology as claimed in claim 1, it is characterized in that: the add-on of high-purity phosphorous acid is 10～50 mass parts in the step (3), and the add-on of 30% hydrochloric acid is 10～50 mass parts, is warmed up to-5～60 ℃, the amount that drips hexanediamine is 2～14 mass parts, and the dropping time is 2～24hr.
5. preparation technology as claimed in claim 4 is characterized in that: in the step (4), the temperature that dropwises intensification is 60～120 ℃, and the amount of the formaldehyde of dropping is 5～50 mass parts.
6. preparation technology as claimed in claim 1 is characterized in that: temperature is fallen slightly and is meant that step (4) soaking time after 1～10 hour, is cooled to 50～100 ℃ naturally in the step (5); Add crystal nucleating agent amount be 0.001～0.5 mass parts, until there being crystal to separate out.
7. preparation technology as claimed in claim 5 is characterized in that: continue to drip formaldehyde 2～20 mass parts after step (6) heats up.
8. preparation technology as claimed in claim 1 is characterized in that: press per hour 1～20 ℃ rate of temperature fall in the step (7), cool to 0～50 ℃.
9. preparation technology as claimed in claim 1 is characterized in that: the whizzer centrifugation rate is 1000～5000r/min in the step (8).
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| CN102229619A (en) * | 2011-04-26 | 2011-11-02 | 河南清水源科技股份有限公司 | Tetraethylenepentamine heptamethylene phosphonic acid and preparation technology thereof |
| CN102229618A (en) * | 2011-04-26 | 2011-11-02 | 河南清水源科技股份有限公司 | Hexamethylenediamine tetramethylene phosphonic acid disodium salt and its production process |
| CN103483380B (en) * | 2013-09-09 | 2016-04-20 | 山东泰和水处理科技股份有限公司 | A kind of ethylenediamine tetramethylene phosphonic acid continuous production method |
| CN110804071B (en) * | 2019-11-08 | 2021-09-17 | 山东泰和水处理科技股份有限公司 | Production method of diethylenetriamine pentamethylene phosphonic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2599807A (en) * | 1950-06-01 | 1952-06-10 | Frederick C Bersworth | Alkylene polyamine methylene phosphonic acids |
| CN1049351A (en) * | 1989-08-04 | 1991-02-20 | 陶氏化学公司 | The purification process of aminomethy-lenephosphonic acids |
| CN1699381A (en) * | 2005-05-11 | 2005-11-23 | 江苏江海化工有限公司 | Hydroxy ethylidene diphosphonic acid with content of greater than or equal to 90 percent and process for making same |
| CN101016314A (en) * | 2007-02-13 | 2007-08-15 | 山东省泰和水处理有限公司 | Preparing process adapted for electronic grade solid aminotrimethylene phosphonic acid |
-
2008
- 2008-10-23 CN CN2008101581656A patent/CN101381377B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2599807A (en) * | 1950-06-01 | 1952-06-10 | Frederick C Bersworth | Alkylene polyamine methylene phosphonic acids |
| CN1049351A (en) * | 1989-08-04 | 1991-02-20 | 陶氏化学公司 | The purification process of aminomethy-lenephosphonic acids |
| CN1699381A (en) * | 2005-05-11 | 2005-11-23 | 江苏江海化工有限公司 | Hydroxy ethylidene diphosphonic acid with content of greater than or equal to 90 percent and process for making same |
| CN101016314A (en) * | 2007-02-13 | 2007-08-15 | 山东省泰和水处理有限公司 | Preparing process adapted for electronic grade solid aminotrimethylene phosphonic acid |
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