CN103694274A - Preparation method of low-chloride low-ammonia amino trimethylene phosphonic acid - Google Patents
Preparation method of low-chloride low-ammonia amino trimethylene phosphonic acid Download PDFInfo
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- CN103694274A CN103694274A CN201410019687.3A CN201410019687A CN103694274A CN 103694274 A CN103694274 A CN 103694274A CN 201410019687 A CN201410019687 A CN 201410019687A CN 103694274 A CN103694274 A CN 103694274A
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- phosphonic acid
- trimethylene phosphonic
- amino trimethylene
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Abstract
The invention provides a preparation method of low-chloride low-ammonia amino trimethylene phosphonic acid. A synthesis method comprises the steps of adding phosphorous acid and ammonium chloride into a reaction kettle, increasing the temperature, dropwise adding formaldehyde and maintaining backflow; after dropwise adding, preserving heat in a backflow state; after the heat preservation, performing negative-pressure external steaming until the solid content is over 80%; adding reverse osmosis water, increasing the temperature and performing negative-pressure external steaming until the solid content is over 80%; repeating the steps; after the product is qualified by detection, adding water for dilution until the solid content meets the requirement. The amino trimethylene phosphonic acid prepared by the method provided by the invention has the characteristics of low chloride content and low ammonia content (the content of chlorides based on Cl<-1> is less than or equal to 0.5%, and the ammonia content is less than or equal to 100mg/L), and can be applied to a strong-base environment; with low chlorine ion content, the amino trimethylene phosphonic acid can meet some requirements for high-end water treatment application.
Description
Technical field
The invention belongs to the synthetic field of water treatment agent, the preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine is provided.
Background technology
Amino Trimethylene Phosphonic Acid (Amino Trimethylene Phosphonic Acid) is a kind of organic phosphine acids anti-incrustation corrosion inhibitor, can form stable complex compound with the many kinds of metal ions such as iron, copper, zinc, oxide compound that can dissolution of metals surface.Amino Trimethylene Phosphonic Acid is generally used as the scale inhibitor of recirculated cooling water, oil-field flooding and dyeing water, the inhibiter in feedwater equipment, Scale inhibitors.In addition, can be used in conjunction with numerous buffers, Scale inhibitors.There is synergy with polycarboxylate etc., can increase anticorrosion-antiscaling effect, also can be used as clean-out system, remove metallic surface grease.Also can be used as the additive of washing composition, the sequestering agent of metal ion, cyanideless electro-plating additive and rare metal extraction agent etc.
Its resistance to acids and bases, resistance to oxychlorination performance are good compared with other organic phospho acid (salt).Can belong to ion with underwater gold, especially calcium ion forms six annulus inner complexs, thereby the good scale inhibition effect of tool the obvious threshold effect of tool.In light and textile industries, can make metal and nonmetallic clean-out system, bleaching and dyeing industrial peroxide stabiliser and laking agent, the complexing agent of cyanideless electro-plating industry.In addition,, due to the good scale effect of Amino Trimethylene Phosphonic Acid, at domestic detergent and cosmetic industry, also there is certain application.In electron trade, Amino Trimethylene Phosphonic Acid is owing to having good corrosion mitigating effect, antiscaling effect and the passivation effect to metallic surface, can be used for the cleaning of circuit version and metal finishing etc.
Patent publication No. CN102766158A discloses a kind of production technique of Amino Trimethylene Phosphonic Acid: (1) adds ammonium chloride, phosphorous acid aqueous solution and water in reactor, is heated to 60 ℃～70 ℃ and also fully stirs material is dissolved completely; Then drip formaldehyde solution, and temperature is controlled to 90 ℃～105 ℃, formaldehyde drips and finishes rear insulation 1.5～3 hours, and the HCl producing reclaims by HCl recovery device; (2) insulation turns and expects to still kettle after finishing, and is slowly warmed up to 110～120 ℃, removes unreacted ammonium chloride, formaldehyde, when steaming without material, and logical cooling water temperature, blowing obtains finished product.
Amino Trimethylene Phosphonic Acid and the reparation technology thereof of open content >=90% of patent publication No. CN1699380A: its reparation technology is that to take the Amino Trimethylene Phosphonic Acid that liquid weight percentage is 50% ~ 60% be raw material, carries out successively: get the raw materials ready according to following steps; Add nucleus sodium acetate; Stir; Add crystallization in motion agent dehydrated alcohol; Dehydration; Dry.
The Amino Trimethylene Phosphonic Acid liquid product that provided in the market, its chloride ion content is higher, and while adjusting alkali, ammonia taste is very large, and this processes and environment protection etc. has all brought very large pair impact as sea water desaltination, film high-end water treatment.
Therefore, study a kind of low chlorine, low ammonia Amino Trimethylene Phosphonic Acid product, can satisfy social needs greatly.Amino Trimethylene Phosphonic Acid water conditioner is on existing market, to account for 12% of water conditioner, consumption is very large, the market that existing whole world water conditioner is approximately 6,000,000,000 dollars, Amino Trimethylene Phosphonic Acid accounts for 7.2 hundred million dollars, having purposes widely aspect oil, papermaking, printing and dyeing, medicine, electronics cleaning, civilian washing, agricultural etc., there is good economic and social benefit.
Summary of the invention
In order to solve current Amino Trimethylene Phosphonic Acid liquid product chlorine, problem that ammonia content is high, to adapt to the application in high-end water treatment field.The invention provides the preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine.Phosphorous acid has following reaction principle with reacting of ammonium chloride, formaldehyde:
3H
3PO
3+3HCHO+NH
4Cl?=?N[CH
2PO
3H
2]
3+HCl+3H
2O
For realizing the concrete technology scheme that this goal of the invention takes, be:
(1) phosphorous acid and ammonium chloride are added to reactor, improve temperature to 70 ± 5 ℃, drip 40 ~ 60% formalin, keep refluxing;
(2) dropwise 90 ~ 115 ℃ of insulation reaction 1.5 ~ 3 hours;
(3) insulation finishes, and negative pressure is steamed outward;
(4) add reverse osmosis water, negative pressure is steamed outward;
(5) repeating step (4), detects and adds reverse osmosis water dilution after qualified.
The described outer temperature of steaming of negative pressure in above-mentioned (3) and (4) is 80 ~ 110 ℃.
The described outer pressure steaming of negative pressure in above-mentioned (3) and (4) is-0.07 ~-0.098MPa.
Above-mentioned (3) described negative pressure is steamed to solid content >=80% outward.
Above-mentioned (4) described reverse osmosis water that adds is adjusted to 30 ~ 60% solid contents.
Above-mentioned (5) described step (4) multiplicity is 1 ~ 5 time.
The beneficial features that the present invention has is: by phosphorous acid, ammonium chloride and formaldehyde, generate liquid Amino Trimethylene Phosphonic Acid, through negative pressure repeatedly, steam outward, effectively reduce the content of chlorine and ammonia, muriate is with Cl
-1meter≤0.5%, ammonia content≤100mg/L, makes it at alkaline condition, use and can not produce strong ammonia taste, has met the requirement to industries such as the harsher film processing of chlorion requirement, sea water desaltinations simultaneously, has expanded the Application Areas of Amino Trimethylene Phosphonic Acid.
Embodiment
Embodiment 1
The preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine specifically realizes by following steps:
(1) phosphorous acid and ammonium chloride are added to reactor, be heated to 70 ± 5 ℃, drip 45% formalin, keep refluxing;
(2) dropwise 105 ± 5 ℃ of insulation reaction 2h;
(3), in 100 ℃, negative pressure-0.075MPa steams outward to solid content 80%;
(4) add reverse osmosis water to solid content 40%, improve temperature to 100 ℃, negative pressure-0.075MPa, outer steaming to solid content 80%;
(5) repeating step is (4) 3 times, and it is qualified to detect, and adds reverse osmosis water dilution.
Embodiment 2
The preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine specifically realizes by following steps:
(1) phosphorous acid and ammonium chloride are added to reactor, be heated to 70 ± 5 ℃, drip 40% formalin, keep refluxing;
(2) dropwise 100 ± 5 ℃ of insulation reaction 3h;
(3), in 80 ℃, negative pressure-0.08MPa steams outward to solid content 80%;
(4) add reverse osmosis water to solid content 40%, improve temperature to 80 ℃, negative pressure-0.08MPa, outer steaming to solid content 80%;
(5) repeating step is (4) 4 times, and it is qualified to detect, and adds reverse osmosis water dilution.
Embodiment 3
The preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine specifically realizes by following steps:
(1) phosphorous acid and ammonium chloride are added to reactor, be heated to 70 ± 5 ℃, drip 55% formalin, keep refluxing;
(2) dropwise 95 ± 5 ℃ of insulation reaction 3h;
(3), in 80 ℃, negative pressure-0.075MPa steams outward to solid content 80%;
(4) add reverse osmosis water to solid content 40%, improve temperature to 80 ℃, negative pressure-0.075MPa, outer steaming to solid content 80%;
(5) repeating step is (4) 3 times, and it is qualified to detect, and adds reverse osmosis water dilution.
Claims (6)
1. a preparation method for the low ammonia Amino Trimethylene Phosphonic Acid of low chlorine, concrete technology step is as follows:
(1) phosphorous acid and ammonium chloride are added to reactor, improve temperature to 70 ± 5 ℃, drip 40 ~ 60% formalin, keep refluxing;
(2) dropwise 90 ~ 115 ℃ of insulation reaction 1.5 ~ 3 hours;
(3) insulation finishes, and negative pressure is steamed outward;
(4) add reverse osmosis water, negative pressure is steamed outward;
(5) repeating step (4), detects and adds reverse osmosis water dilution after qualified.
2. the preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine according to claim 1, is characterized in that: the described outer temperature of steaming of negative pressure in above-mentioned steps (3) and (4) is 80 ~ 110 ℃.
3. the preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine according to claim 2, is characterized in that: the described outer pressure steaming of negative pressure in above-mentioned steps (3) and (4) is-0.07 ~-0.098MPa.
4. the preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine according to claim 1, is characterized in that: the described negative pressure of above-mentioned steps (3) is steamed to solid content >=80% outward.
5. the preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine according to claim 1, is characterized in that: the described reverse osmosis water that adds of above-mentioned steps (4) is adjusted to 30 ~ 60% solid contents.
6. the preparation method of the low ammonia Amino Trimethylene Phosphonic Acid of a kind of low chlorine according to claim 1, is characterized in that: described step (4) multiplicity of above-mentioned steps (5) is 1 ~ 5 time.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410019687.3A CN103694274A (en) | 2014-01-16 | 2014-01-16 | Preparation method of low-chloride low-ammonia amino trimethylene phosphonic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397478A (en) * | 2016-08-31 | 2017-02-15 | 南通联膦化工有限公司 | Production process of low-chloride amido-trimethylene phosphonic acid (ATMP) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3288846A (en) * | 1961-11-13 | 1966-11-29 | Monsanto Co | Processes for preparing organophosphonic acids |
| CN102070665A (en) * | 2011-01-04 | 2011-05-25 | 山东省泰和水处理有限公司 | Process for arsenic removal of 1-hydroxy ethylidene-1,1-diphosphonic acid |
| CN102766158A (en) * | 2011-05-06 | 2012-11-07 | 江苏大明科技有限公司 | Production technology of amino trimethylene phosphonic acid (ATMP) |
| CN103275121A (en) * | 2013-06-06 | 2013-09-04 | 山东省泰和水处理有限公司 | Continuous production process for amino trimethylene phosphonic acid |
| CN103275120A (en) * | 2013-06-05 | 2013-09-04 | 山东省泰和水处理有限公司 | Low-trimethylene-content amino trimethylene phosphonic acid and preparation method thereof |
| 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) |
| CN103509052A (en) * | 2012-06-21 | 2014-01-15 | 河南清水源科技股份有限公司 | Preparation method for high-purity amino trimethylene phosphonic acid |
-
2014
- 2014-01-16 CN CN201410019687.3A patent/CN103694274A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3288846A (en) * | 1961-11-13 | 1966-11-29 | Monsanto Co | Processes for preparing organophosphonic acids |
| CN102070665A (en) * | 2011-01-04 | 2011-05-25 | 山东省泰和水处理有限公司 | Process for arsenic removal of 1-hydroxy ethylidene-1,1-diphosphonic acid |
| CN102766158A (en) * | 2011-05-06 | 2012-11-07 | 江苏大明科技有限公司 | Production technology of amino trimethylene phosphonic acid (ATMP) |
| CN103509052A (en) * | 2012-06-21 | 2014-01-15 | 河南清水源科技股份有限公司 | Preparation method for high-purity amino trimethylene phosphonic acid |
| CN103275120A (en) * | 2013-06-05 | 2013-09-04 | 山东省泰和水处理有限公司 | Low-trimethylene-content amino trimethylene phosphonic acid and preparation method thereof |
| CN103275121A (en) * | 2013-06-06 | 2013-09-04 | 山东省泰和水处理有限公司 | Continuous production process for amino trimethylene phosphonic 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397478A (en) * | 2016-08-31 | 2017-02-15 | 南通联膦化工有限公司 | Production process of low-chloride amido-trimethylene phosphonic acid (ATMP) |
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Application publication date: 20140402 |