CN104891685A - A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) - Google Patents
A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) Download PDFInfo
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- CN104891685A CN104891685A CN201510255372.3A CN201510255372A CN104891685A CN 104891685 A CN104891685 A CN 104891685A CN 201510255372 A CN201510255372 A CN 201510255372A CN 104891685 A CN104891685 A CN 104891685A
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- formaldehyde
- methylenephosphonic acid
- hexamethylene dimethylamine
- cyclohexanebis
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Abstract
A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) is provided. The 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) is synthesized by adopting 1,3-cyclohexanebis(methylamine), phosphorous acid and formaldehyde in a mole ratio of 1:4-4.5:4-8 as raw materials and by heating and reacting in a water system under acid conditions of hydrochloric acid. The target product that is the 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) is used as a scale and corrosion inhibitor for industrial and living water treatment.
Description
Technical field
The invention belongs to field of fine chemical, specifically a kind of synthesis technique of 1,3-hexamethylene dimethylamine four methylenephosphonic acid.
Background technology
Process water also exists the harm such as serious fouling, corrosion and bacterium algae grow as recirculated cooling water, oil field water, feedwater etc., becomes the principal element of restriction production development.Utilize the method adding chemical agent prevent or solve fouling, corrosion etc. come stabilizing water quality be in process water the most directly and effective means, fouling and corrosion that as added in recirculated cooling water, the anti-incrustation corrosion inhibitor having scale effect and corrosion inhibition concurrently can control metal heat-exchange equipment simultaneously, especially underdeposit corrosion.The domestic formula being usually used in Treatment of Industrial Water mostly is organic phosphine class formula at present; it mainly becomes as the amino methane phosphonic acid based containing phosphonate group; conventional organic phospho acid comprises: Amino Trimethylene Phosphonic Acid, ethylene diamine tetra methylene phosphonic acid hydroxy ethylene diphosphonic acid, phosphinylidyne butane 1; 2,4-tricarboxylic acid etc.
Hexanaphthene be its bond angle of six-ring close to 109 ° 28 ', the deflection angle of key is little, and tension force is little, and it is also the best naphthenic hydrocarbon of stability that its chemical stability is better than hexane.1,3-hexamethylene dimethylamine four methylenephosphonic acid straight-chain paraffin amine methylenephosphonic acid that is heat-resisting and the more equal carbon number of stability that is acid and alkali-resistance is better after deliberation, and scale inhibition effect is excellent.The harsh operating environment that oil field reinjection water, boiler feed water etc. are in high temperature for a long time can be adapted to.
1,3-hexamethylene dimethylamine four methylenephosphonic acid is with 1,3-hexamethylene dimethylamine, formaldehyde and phosphorous acid are synthesized by Mannich reaction, also can by phosphorus trichloride hydrolysis method namely according to 1, the route synthesis of 3-hexamethylene dimethylamine, formaldehyde and phosphorus trichloride, this process due to phosphorus trichloride hydrolysis heat release violent and produce the hydrogenchloride of macro-corrosion, therefore industrializing implementation does not generally take this technique.
Summary of the invention
The present invention 1,3-hexamethylene dimethylamine four methylenephosphonic acid straight-chain paraffin amine methylenephosphonic acid that is heat-resisting and the more equal carbon number of stability that is acid and alkali-resistance is better, and scale inhibition efficiency is higher.The Treatment of Industrial Water such as recirculated cooling water, oil-field flooding, feedwater can be widely used in through applied research.Its addition is few; be used alone 5ppm concentration can reach and conventional organic phosphine anti-incrustation corrosion inhibitor hydroxy ethylene diphosphonic acid, Amino Trimethylene Phosphonic Acid, phosphinylidyne butane 1; 2; the effect that 4-tricarboxylic acid is equal; addition according to different hardness 1,3-hexamethylene dimethylamine four methylenephosphonic acid of water quality is generally 3 ~ 10ppm.
1,3-hexamethylene dimethylamine four methylenephosphonic acid synthesizes especially by following technique:
1,3-hexamethylene dimethylamine, phosphorous acid, concentrated hydrochloric acid and reverse osmosis water are added reactor; Control temperature < 100 DEG C drips formaldehyde; Dropwise, control temperature 80 ~ 150 DEG C reaction 1 ~ 8 hour; Underpressure distillation is except de-chlorine hydride and formaldehyde.
Above-mentioned concentrated hydrochloric acid add-on makes system pH value≤1.5.
Above-mentioned formaldehyde dropping temperature preferably 50 ~ 80 DEG C, time for adding is 1 ~ 4 hour.
Above-mentioned temperature of reaction is 95 ~ 115 DEG C, and the reaction times is 2 ~ 5 hours.
Above-mentioned technique 1,3-hexamethylene dimethylamine, phosphorous acid and formaldehyde mol ratio be 1:4 ~ 4.5:4 ~ 8.
Excellent innovative point of the present invention: the present invention proposes a kind of methylenephosphonic acid anti-incrustation corrosion inhibitor containing cycloalkyl, this medicament has scale inhibition, inhibition and bactericidal property concurrently; This pharmacy security, nontoxic; This pharmaceutical preparations can be widely used in the water treatment system such as recirculated cooling water, feedwater; It is more superior that this pharmaceutical preparations compares the conventional medicament pyrohydrolysis stability such as Amino Trimethylene Phosphonic Acid, ethylene diamine tetra methylene phosphonic acid hydroxy ethylene diphosphonic acid, phosphinylidyne butane 1,2,4-tricarboxylic acid, can resistance to 280 DEG C of high temperature 48 hours continuously, percent hydrolysis≤5%.
Embodiment
Embodiment 1(most preferred embodiment)
142kg1,3-hexamethylene dimethylamine, 328kg phosphorous acid and reverse osmosis water are added reactor; With concentrated hydrochloric acid regulation system pH value≤1.5; Control temperature 85 ± 2 DEG C drips 144kg formaldehyde; Within 1.5 hours, dropwise, control temperature 105 DEG C, react 3 hours; Underpressure distillation is except de-chlorine hydride and formaldehyde.
Embodiment 2
142kg1,3-hexamethylene dimethylamine, 344kg phosphorous acid and reverse osmosis water are added reactor; With concentrated hydrochloric acid regulation system pH value≤1.5; Control temperature 80 ± 2 DEG C drips 132kg formaldehyde; Within 1.0 hours, dropwise, control temperature 105 DEG C, react 4 hours; Underpressure distillation is except de-chlorine hydride and formaldehyde.
Embodiment 3
142kg1,3-hexamethylene dimethylamine, 352kg phosphorous acid and reverse osmosis water are added reactor; With concentrated hydrochloric acid regulation system pH value≤1.5; Control temperature 85 ± 2 DEG C drips 150kg formaldehyde; Within 2.5 hours, dropwise, control temperature 115 DEG C, react 5 hours; Underpressure distillation is except de-chlorine hydride and formaldehyde.
Embodiment 4
142kg1,3-hexamethylene dimethylamine, 328kg phosphorous acid and reverse osmosis water are added reactor; With concentrated hydrochloric acid regulation system pH value≤1.5; Control temperature 60 ± 2 DEG C drips 180kg formaldehyde; Within 3 hours, dropwise, control temperature 100 DEG C, react 2 hours; Underpressure distillation is except de-chlorine hydride and formaldehyde.
Embodiment 5
142kg1,3-hexamethylene dimethylamine, 336kg phosphorous acid and reverse osmosis water are added reactor; With concentrated hydrochloric acid regulation system pH value≤1.5; Control temperature 90 ± 2 DEG C drips 144kg formaldehyde; Within 1.0 hours, dropwise, control temperature 115 DEG C, react 5 hours; Underpressure distillation is except de-chlorine hydride and formaldehyde.
Embodiment 6
142kg1,3-hexamethylene dimethylamine, 328kg phosphorous acid and reverse osmosis water are added reactor; With concentrated hydrochloric acid regulation system pH value≤1.5; Control temperature 95 ± 2 DEG C drips 144kg formaldehyde; Within 3 hours, dropwise, control temperature 105 DEG C, react 5 hours; Underpressure distillation is except de-chlorine hydride and formaldehyde.
Following table records the embodiment of the present application 1 ~ 6 product scale inhibition performance by static-state scale inhibition method
| Addition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| 3ppm | 83.99% | 80.13% | 81.91% | 84.11% | 73.55% | 68.82% |
| 5ppm | 86.14% | 82.34% | 82.35% | 85.65% | 79.35% | 77.67% |
| 10ppm | 94.04% | 90.03% | 88.14% | 91.31% | 85.25% | 81.88% |
Claims (5)
1. the synthesis technique of hexamethylene dimethylamine four methylenephosphonic acid, is characterized in that, synthesis technique comprises and 1,3-hexamethylene dimethylamine, phosphorous acid, concentrated hydrochloric acid and reverse osmosis water are added reactor; Control temperature < 100 DEG C drips formaldehyde; Dropwise, control temperature 80 ~ 150 DEG C reaction 1 ~ 8 hour; Underpressure distillation is except de-chlorine hydride and formaldehyde.
2. the synthesis technique of 1,3-hexamethylene dimethylamine four methylenephosphonic acid according to claim 1, it is characterized in that, formaldehyde dropping temperature is preferably 50 ~ 80 DEG C, and time for adding is 1 ~ 4 hour.
3. the synthesis technique of 1,3-hexamethylene dimethylamine four methylenephosphonic acid according to claim 1, it is characterized in that, concentrated hydrochloric acid add-on makes system pH value≤1.5.
4. the synthesis technique of 1,3-hexamethylene dimethylamine four methylenephosphonic acid according to claim 1, it is characterized in that, temperature of reaction is 95 ~ 115 DEG C, and the reaction times is 2 ~ 5 hours.
5. the synthesis technique of 1,3-hexamethylene dimethylamine four methylenephosphonic acid according to claim 1, is characterized in that, the mol ratio of 1,3-hexamethylene dimethylamine, phosphorous acid and formaldehyde is 1:4 ~ 4.5:4 ~ 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336024A (en) * | 2016-10-17 | 2017-01-18 | 山东泰和水处理科技股份有限公司 | Isophorone diamine tetramethylene phosphonic acid or sodium salt thereof, preparation method and application |
| CN107903286A (en) * | 2017-10-17 | 2018-04-13 | 山东泰和水处理科技股份有限公司 | A kind of two methylenephosphonic acid of fire retardant cyclohexylamine and preparation method thereof |
| CN114752065A (en) * | 2022-04-20 | 2022-07-15 | 南阳柯丽尔科技有限公司 | Iron-loaded tertiary amino monophosphonic acid resin for rare earth enrichment and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420510A (en) * | 2012-05-25 | 2013-12-04 | 鲍宜仿 | Preparation method of tetra sodium salt of amino trimethylene phosphonic acid compound scale inhibitor |
| CN104086590A (en) * | 2014-07-14 | 2014-10-08 | 山东省泰和水处理有限公司 | Preparation method of abietylamino methylene phosphonic acid |
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2015
- 2015-05-19 CN CN201510255372.3A patent/CN104891685A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420510A (en) * | 2012-05-25 | 2013-12-04 | 鲍宜仿 | Preparation method of tetra sodium salt of amino trimethylene phosphonic acid compound scale inhibitor |
| CN104086590A (en) * | 2014-07-14 | 2014-10-08 | 山东省泰和水处理有限公司 | Preparation method of abietylamino methylene phosphonic acid |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336024A (en) * | 2016-10-17 | 2017-01-18 | 山东泰和水处理科技股份有限公司 | Isophorone diamine tetramethylene phosphonic acid or sodium salt thereof, preparation method and application |
| CN106336024B (en) * | 2016-10-17 | 2019-10-25 | 山东泰和水处理科技股份有限公司 | Four methylenephosphonic acid of isophorone diamine or its sodium salt and preparation method and application |
| CN107903286A (en) * | 2017-10-17 | 2018-04-13 | 山东泰和水处理科技股份有限公司 | A kind of two methylenephosphonic acid of fire retardant cyclohexylamine and preparation method thereof |
| CN107903286B (en) * | 2017-10-17 | 2020-08-04 | 山东泰和水处理科技股份有限公司 | Fire retardant cyclohexylamine dimethylidene phosphonic acid and preparation method thereof |
| CN114752065A (en) * | 2022-04-20 | 2022-07-15 | 南阳柯丽尔科技有限公司 | Iron-loaded tertiary amino monophosphonic acid resin for rare earth enrichment and preparation method thereof |
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Application publication date: 20150909 |