CN106336024B - Four methylenephosphonic acid of isophorone diamine or its sodium salt and preparation method and application - Google Patents
Four methylenephosphonic acid of isophorone diamine or its sodium salt and preparation method and application Download PDFInfo
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- CN106336024B CN106336024B CN201610908960.7A CN201610908960A CN106336024B CN 106336024 B CN106336024 B CN 106336024B CN 201610908960 A CN201610908960 A CN 201610908960A CN 106336024 B CN106336024 B CN 106336024B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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Abstract
The invention belongs to water treatment field more particularly to four methylenephosphonic acid of isophorone diamine or its sodium salt and their preparation method and the applications in oil-field flooding or boiler feed water.Four methylenephosphonic acid of isophorone diamine provided by the present invention or its sodium salt, chemical stability is very superior, can adapt in long-term high rigidity, high alkalinity, high temperature, high H2S, the environment of high-sulfate bacterium, high iron bacteria and strong oxidizing property, it is wide to the adaptation range of water quality；Preparation method provided by the invention is simple to operation, and four methylenephosphonic acid of isophorone diamine and its sodium salt of preparation apply scale inhibitor excellent effect in oil-field flooding or boiler feed water, and scale inhibition performance reaches 85% or more.
Description
Technical field
The invention belongs to water treatment field more particularly to four methylenephosphonic acid of isophorone diamine or its sodium salt and preparation methods
And application.
Background technique
Organic phospho acid (salt) antisludging agent is a kind of phosphorus system water treatment agent for starting application the 1960s, solely due to it
Special scale-inhibiting properties make the development of water treatment agent make a breakthrough.It experienced the development of decades, organic phosphine is as scale inhibition
Inhibition still occupies leading position in water treatment field.Organic phosphine anti-incrustation corrosion inhibitor mainly has methylenephosphonic acid class and carboxyl phosphonic acid
(acyl) two major classes, the former has a very strong scale prevention ability to calcium carbonate, calcium sulfate and calcium silicates, and can stable iron, zinc, manganese well
Oxide, dispersibility is strong, especially suitable for high concentration multiple run, synthesis primary raw material be fat polyamine and phosphorous
Sour (phosphorus trichloride), and the latter has good calcium carbonate and calcium phosphate scale prevention ability, and having had in cooling water system
Grain dispersibility and certain corrosion inhibition, almost do not work with chlorine, are a kind of multi-functional medicaments, molecular weight 2000 with
On, the primary raw material of synthesis is the polymer containing carboxyl, therefore thinks that it is the combination of organic phospho acid and polymer, it is clear that preceding
The synthesis material of the latter two is sufficiently expensive, and synthesis technology is complicated.
Application No. is 97108420.3 Chinese invention patents to disclose the system of a kind of four methylenephosphonic acid of urea groups and its sodium salt
Preparation Method and purposes, this method be using urea, phosphorous acid (phosphorus trichloride), formaldehyde as four methylenephosphonic acid of Material synthesis urea groups, by
Amine in urea is amide, rather than real amino, due to the sucting electronic effect of carbonyl, so that the electron cloud on amino is close
Degree reduces the nucleophilic displacement of fluorine for the carbonyl being unfavorable on amino and formaldehyde.Therefore the reaction is not easy to carry out.
Application No. is 201510255372.3 Chinese invention patents to disclose four methylenephosphonic acid of 1,3- hexamethylene dimethylamine
Synthesis technology, 1,3- hexamethylene dimethylamine, four methylenephosphonic acid have scale inhibition, inhibition and bactericidal property concurrently, are resistant to certain high temperature ring
Border, but be easy to lose effect by these bacterial decompositions in the environment with sulfate bacterium, high iron bacteria, additionally, due to
Hexamethylene dimethylamine has 3 kinds of isomers, and also difference is larger for the methylenephosphonic acid anti-incrustation corrosion inhibitor effect of 3 kinds of structures synthesis, influences
Its overall effect.
Although existing organic phospho acid and phosphonic acid polymers have excellent scale inhibitor and dispersion performance, can adapt in
Certain hardness and hot environment, but be applied to oils recovery, boiler etc. it is acid it is higher, rich in oxidisability bacterium, anaerobic bacteria, persistently
When the harsh conditions such as high temperature, it is easily decomposed to the low molecular weights inorganic matter such as positive phosphorus, to lose the water treatmenting performances such as scale inhibitor.
Therefore it is superior to develop a kind of chemical stability, high rigidity, high alkalinity, hot environment can be adapted to for a long time, and high
H2S, the environment of high-sulfate bacterium, high iron bacteria and strong oxidizing property, and organic phospho acid (salt) the antisludging agent tool that scale inhibition performance is high
There is significant realistic meaning.
Summary of the invention
It is the present invention provides a kind of new fatty Cycloamine derivative, i.e., different to overcome above-mentioned disadvantage of the existing technology
Four methylenephosphonic acid of isophoronediamine or its sodium salt, the compound chemical stability is very superior, and scale inhibition effect is excellent, to water quality
Adaptation range is wide.
The present invention also provides the preparation method of above-mentioned four methylenephosphonic acid of isophorone diamine or its sodium salt, preparation method letters
It is single easy to operate；
The present invention also provides the applications of above-mentioned four methylenephosphonic acid of isophorone diamine or its sodium salt.
A kind of fat Cycloamine derivative, molecular structural formula are as follows:
When R is H in formula, referred to as four methylenephosphonic acid of isophorone diamine, molecular formula are as follows: C9H16N2(CH2PO3H2)4, molecular weight
Are as follows: 532, it is light yellow transparent solution；When R is Na in formula, referred to as four methene Alendronate salt of isophorone diamine, molecular formula are as follows:
C9H16N2(CH2PO3Na2)4, molecular weight 708 is light yellow transparent solution.
A kind of preparation method of four methylenephosphonic acid of above-mentioned isophorone diamine, with isophorone diamine, phosphorous acid and formaldehyde
For raw material, isophorone diamine and phosphorous acid are added in reaction kettle, adds salt acid for adjusting pH value to 2 ~ 5, is warming up to 80 ~ 100
DEG C formaldehyde is added dropwise, is added dropwise and improves temperature the reaction was continued to terminal, is concentrated by evaporation and removes HCl and formaldehyde and obtain isophorone
Four methylenephosphonic acid solution of diamines；
Preferably, the molar ratio of the isophorone diamine, phosphorous acid and formaldehyde is 1:4 ~ 5:5 ~ 8；The dropwise addition first
The time of aldehyde is 0.5 ~ 3 hour；The formaldehyde, which is added dropwise, improves temperature to 105 ~ 120 DEG C, and the reaction was continued 1 ~ 5 hour.
A kind of preferred preparation method of four methylenephosphonic acid of above-mentioned isophorone diamine is, with isophorone diamine, Asia
Phosphoric acid and formaldehyde are raw material, and the molar ratio of three kinds of raw materials is 1:4 ~ 5:5 ~ 6, and isophorone diamine and phosphorous acid are added to reaction
In kettle, salt acid for adjusting pH value is added to 3 ~ 4, is warming up to 90 ~ 95 DEG C of dropwise addition formaldehyde, time for adding is 1 ~ 2h, is added dropwise, and is heated up
To 110 ~ 115 DEG C, the reaction was continued 2 ~ 3 hours, and vacuum distillation removes HCl and formaldehyde, and to obtain four methylenephosphonic acid of isophorone diamine molten
Liquid.
A kind of preparation method of four methene Alendronate salt of above-mentioned isophorone diamine, with four methylenephosphonic acid of isophorone diamine
Solution and sodium hydroxide are raw material, and sodium hydroxide is added in four methylenephosphonic acid solution of isophorone diamine, adjust solution ph
To 6.0-8.0, filtering, collecting precipitating is four methene Alendronate salt of isophorone diamine.
A kind of application of four methylenephosphonic acid of above-mentioned isophorone diamine or its sodium salt in oil-field flooding or boiler feed water；Its
Described in four methylenephosphonic acid of isophorone diamine or its sodium salt can be used alone or compounded with other water treatment agents and make
With amount ranges 5-80ppm.
Beneficial effect
Four methylenephosphonic acid of isophorone diamine provided by the present invention or its sodium salt, chemical stability is very superior, can
It is adapted to long-term high rigidity, high alkalinity, high temperature, high H2S, the environment of high-sulfate bacterium, high iron bacteria and strong oxidizing property, it is right
The adaptation range of water quality is wide；Preparation method provided by the invention is simple to operation, four methylenephosphonic acid of isophorone diamine of preparation
And its sodium salt applies scale inhibitor excellent effect in oil-field flooding or boiler feed water, scale inhibition performance reaches 85% or more.
Specific embodiment
The present invention is further illustrated in conjunction with the embodiments, it should which explanation, following the description is merely to explain this
Invention, is not defined its content.
Embodiment 1
Using isophorone diamine, phosphorous acid and formaldehyde as raw material, according to the ratio that molar ratio is 1:4:5 by isophorone two
Amine and phosphorous acid are added in reaction kettle；It heats and is stirred continuously, control temperature≤50 DEG C, with hydrochloric acid regulating system pH value to 3,
95 DEG C are warming up to, formaldehyde is added dropwise, is added dropwise within 1 hour；Temperature is improved to 110 DEG C, the reaction was continued 3 hours；Vacuum distillation removes
HCl and formaldehyde obtain four methylenephosphonic acid pale yellow transparent aqueous solution of isophorone diamine.
Four methylenephosphonic acid of isophorone diamine and sodium hydroxide in the above way prepared is raw material, is adjusted with sodium hydroxide
Four methylenephosphonic acid pH value of isophorone diamine to 7.0, collect precipitating, obtain four methene Alendronate salt of isophorone diamine by filtering.
Embodiment 2
Using isophorone diamine, phosphorous acid and formaldehyde as raw material, according to the ratio that molar ratio is 1:5:8 by isophorone two
Amine and phosphorous acid are added in reaction kettle；It heats and is stirred continuously, temperature≤50 DEG C are controlled, with hydrochloric acid regulating system pH value to 5；
100 DEG C are warming up to, formaldehyde is added dropwise, is added dropwise within 3 hours；Temperature is improved to 105 DEG C, the reaction was continued 5 hours；Vacuum distillation removes
HCl and formaldehyde obtain four methylenephosphonic acid pale yellow transparent aqueous solution of isophorone diamine.
Four methylenephosphonic acid of isophorone diamine and sodium hydroxide in the above way prepared is raw material, is adjusted with sodium hydroxide
For four methylenephosphonic acid pH value of isophorone diamine to 8.0, filtering obtains four methene Alendronate salt of isophorone diamine.
Embodiment 3
Using isophorone diamine, phosphorous acid and formaldehyde as raw material, according to the ratio that molar ratio is 1:4:7 by isophorone two
Amine and phosphorous acid are added in reaction kettle；It heats and is stirred continuously, temperature≤50 DEG C are controlled, with hydrochloric acid regulating system pH value to 2；
80 DEG C are warming up to, formaldehyde is added dropwise, is added dropwise within 0.5 hour；Temperature is improved to 115 DEG C, the reaction was continued 5 hours；Vacuum distillation removes
HCl and formaldehyde are removed, four methylenephosphonic acid pale yellow transparent aqueous solution of isophorone diamine is obtained.
Four methylenephosphonic acid of isophorone diamine and sodium hydroxide in the above way prepared is raw material, is adjusted with sodium hydroxide
Four methylenephosphonic acid pH value of isophorone diamine is filtered to 6.0 to get four methene Alendronate salt of isophorone diamine.
Embodiment 4
Using isophorone diamine, phosphorous acid and formaldehyde as raw material, according to the ratio that molar ratio is 1:4.5:8 by isophorone
Diamines and phosphorous acid are added in reaction kettle；It heats and is stirred continuously, control temperature≤50 DEG C, extremely with hydrochloric acid regulating system pH value
2.0；80 DEG C are warming up to, formaldehyde is added dropwise, is added dropwise within 3 hours；Temperature is improved to 120 DEG C, the reaction was continued 1 hour；Vacuum distillation
HCl and formaldehyde are removed, four methylenephosphonic acid pale yellow transparent aqueous solution of isophorone diamine is obtained.
Four methylenephosphonic acid of isophorone diamine and sodium hydroxide in the above way prepared is raw material, is adjusted with sodium hydroxide
Four methylenephosphonic acid pH value of isophorone diamine is filtered to 7.0 to get four methene Alendronate salt of isophorone diamine.
Applicating example
Four methylenephosphonic acid of isophorone diamine prepared by above-described embodiment is taken to be added in boiler water-filling, dosage is
30ppm tests scale inhibition performance (%) by GB/T 16632-2008 (the measurement tosca methods of water treatment agent scale-inhibiting properties),
As a result see such as the following table 1:
Table 1
Four methylenephosphonic acid of isophorone diamine prepared by above-described embodiment is taken to be added in simulation oil field water filling, additional amount is
50ppm, wherein each component in the simulation oil field water filling are as follows: iron content 0.5mg/L, solid suspension (suspended particle
Diameter is 3 μm) concentration is 5mg/L, oil content 10mg/L, total salinity 5000mg/L, dissolved oxygen concentration 0.5mg, two
Sulfur oxide content is 10mg/L, saprophytic bacteria 104A/L, sulfate reducing bacteria 102A/L, by GB/T 16632-2008 (at water
Manage the measurement tosca method of agent scale-inhibiting properties) test scale inhibition performance (%), the result is shown in such as the following table 2:
Table 2
Claims (5)
1. a kind of fat Cycloamine derivative, which is characterized in that molecular structural formula are as follows:
When R is H in formula, referred to as four methylenephosphonic acid of isophorone diamine, molecular formula C9H16N2(CH2PO3H2)4, molecular weight are as follows:
532, it is light yellow transparent solution；When R is Na in formula, referred to as four methene Alendronate salt of isophorone diamine, molecular formula are as follows:
C9H16N2(CH2PO3Na2)4, molecular weight 708 is light yellow transparent solution.
2. fat Cycloamine derivative according to claim 1, it is characterised in that, four methylenephosphonic acid of isophorone diamine
The preparation method comprises the following steps: using isophorone diamine, phosphorous acid and formaldehyde as raw material, the molar ratio of three kinds of raw materials is 1:4 ~ 5:5 ~ 6, will
Isophorone diamine and phosphorous acid are added in reaction kettle, and salt acid for adjusting pH value is added to 3 ~ 4, is warming up to 90 ~ 95 DEG C of dropwise addition first
Aldehyde, time for adding are 1 ~ 2h, are added dropwise, and being warming up to 110 ~ 115 DEG C, the reaction was continued 2 ~ 3 hours, and vacuum distillation removes HCl and first
Aldehyde obtains four methylenephosphonic acid solution of isophorone diamine.
3. fat Cycloamine derivative according to claim 2, which is characterized in that molten with four methylenephosphonic acid of isophorone diamine
Liquid and sodium hydroxide are raw material, and sodium hydroxide is added in four methylenephosphonic acid solution of isophorone diamine, adjust solution ph to
6.0-8.0, filtering, collection are precipitated as four methene Alendronate salt of isophorone diamine.
4. a kind of four methylenephosphonic acid of isophorone diamine of any of claims 1-3 or four methene of isophorone diamine
Application of the phosphonic acids sodium salt in oil-field flooding or boiler feed water.
5. application according to claim 4, which is characterized in that four methylenephosphonic acid of isophorone diamine or its sodium salt
It can be used alone or be used in compounding with other water treatment agents, amount ranges 5-80ppm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834010A (en) * | 2014-03-21 | 2014-06-04 | 山东省泰和水处理有限公司 | Rosin-based grafted polyaspartic acid and preparation method thereof |
| CN104891685A (en) * | 2015-05-19 | 2015-09-09 | 山东省泰和水处理有限公司 | A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834010A (en) * | 2014-03-21 | 2014-06-04 | 山东省泰和水处理有限公司 | Rosin-based grafted polyaspartic acid and preparation method thereof |
| CN104891685A (en) * | 2015-05-19 | 2015-09-09 | 山东省泰和水处理有限公司 | A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) |
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