CN107720982A - A kind of without phosphorus water treatment agent and preparation method thereof - Google Patents
A kind of without phosphorus water treatment agent and preparation method thereof Download PDFInfo
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- CN107720982A CN107720982A CN201711085603.6A CN201711085603A CN107720982A CN 107720982 A CN107720982 A CN 107720982A CN 201711085603 A CN201711085603 A CN 201711085603A CN 107720982 A CN107720982 A CN 107720982A
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- treatment agent
- water treatment
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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
-
- 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
- C02F2103/023—Water in cooling circuits
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to a kind of without phosphorus water treatment agent and preparation method thereof.A kind of without phosphorus water treatment agent obtains afterwards so that the monomer progress of polyethylene glycol ester monomer, starch ester monomer and the unsaturated double-bond containing vinyl is free-radical polymerized, and its general structure is as follows：
Description
Technical field
The invention belongs to industrial recirculated cooling water technical field, and in particular to suitable for cold under high-temperature high-hardness water
But water treatment agent of water system and preparation method thereof.
Background technology
Water is the basis of human survival and development, with the development of industrial society, using freshwater resources containing in the earth
Amount is gradually decreased, and industrial water is gradually increasing in the consumption accounting of freshwater resources, and with the reduction of freshwater resources, people start
Pay attention to the repeat usage of freshwater resources.In industrial fresh water in use, cooling water accounts for more than 70%, and has what is be gradually increasing
Trend, in order to save the usage amount of industrial colling, currently used method is to allow cooling water circulation to utilize, and is returned using cooling water
Receive after the cooling water after heating is carried out recovery Temperature fall by tower and reuse.It is general to recycle cooling water 3-6 times, greatly
Reduce the usage amount of industrial water.
With the recycling of cooling water, inorganic ion（Such as calcium ion）Can produce at high temperature be difficult to remove it is inorganic
Salt calcium dirt, such as：Calcium carbonate, calcium sulfate etc., these inorganic salts calcium dirt will make cooling water once being formed at the inner surface of pipeline
Cooling efficiency be remarkably decreased, or even pipeline can be blocked, cause the failure of heat transmission equipment, make the temperature control of consersion unit, very
To cause stop production or explosion danger.In order to suppress the generation of these inorganic salts calcium dirt, appropriate water process can be often added in industry
Agent, such as conventional PBTC, HEDP of in the market etc., but these antisludging agents all contain environmentally harmful P elements, with country
Environmental protection policy it is increasingly strict, phosphorous water treatment agent will be phased out.Some scientific research institutions start to research and develop research of non-phosphorus scale inhibitor at present,
Such as conventional PAA, PESA etc., these antisludging agents are not phosphorous, environmentally friendly, but these antisludging agents are added to circulating water
Calcium gelatin phenomenon is easily produced in system, there is the defects of certain.
Conventional water treatment agent is typically phosphorous currently on the market, and environmental pollution is serious, and without phosphorus water treatment agent is difficult to should
In the case of high temperature and high rigidity.Therefore, it is to be applied without the serious P elements of environmental pollution, and can to develop a kind of
In high temperature high rigidity circulation, update and environmental protection for China's water treatment agent have great application value
And environment protection significance.
The content of the invention
It is an object of the invention to provide a kind of without phosphorus water treatment agent, the water treatment agent has excellent scale-inhibiting properties,
It is environmentally friendly and can be applicable to high temperature high alkalinity environment.
A kind of without phosphorus water treatment agent is with polyethylene glycol ester monomer, starch ester monomer and the list of the unsaturated double-bond containing vinyl
After body progress is free-radical polymerized, its general structure is as follows：
In above formula：A is soluble starch, and B is the constitutional repeating unit after the monomer copolymerization of the unsaturated double-bond containing vinyl, is polymerize
It is 1 ~ 5000 to spend x, y, and number of repeat unit m, n is 1 ~ 100.
The operating procedure for preparing the phosphate-free water treatment agent is as follows：
（1）In nitrogen（N2）Under atmosphere, on the basis of polyethylene glycol quality, by polyethylene glycol and 0.05~5 times of polyethylene glycol quality
Maleic anhydride add reactor in, at 30 ~ 120 DEG C react 1 ~ 10h, obtain macrogol ester reaction monomers；
（2）In nitrogen（N2）Under atmosphere, on the basis of soluble starch quality, by soluble starch and 0.05~5 times of soluble shallow lake
The maleic anhydride of silty amount is added in reactor, and 1 ~ 10h is reacted at 30 ~ 120 DEG C, obtains soluble starch ester reaction monomers；
（3）Macrogol ester and starch ester are mixed, reaction temperature is 50 ~ 95 DEG C, adds 0.2 ~ 5 times of macrogol ester reaction
The water of the monomer of the unsaturated double-bond containing vinyl of monomer mass, 0.1 ~ 5 times of macrogol ester reaction monomers quality, drips after mixing
Add the inorganic initiator aqueous solution that mass percentage concentration is 5%~50%, the addition of inorganic initiator is gathered for 0.01 ~ 0.5 times
Glycol ester reaction monomers quality, 1~5h are dripped off, and are continued to react 0.5~10h at 50 ~ 95 DEG C after dripping off, are cooled to room temperature, make
Obtain 5 ~ 70wt% of solid content without phosphorus water treatment agent.
The technical scheme further limited is as follows：
Step（3）Described in the monomer of unsaturated double-bond containing vinyl be acrylic acid, methacrylic acid, methyl acrylate, acrylic acid
One or more of ethyl ester, propyl acrylate, butyl acrylate, maleic anhydride, hydroxypropyl acrylate, maleic acid, itaconic acid.
Step（3）Described in inorganic initiator be sodium peroxydisulfate, potassium peroxydisulfate, lay particular stress on sulfinic acid sodium, lay particular stress on sulfinic acid potassium,
One or more of persulfonic acid sodium, persulfonic acid potassium, hydrogen peroxide.
The advantageous effects of the present invention embody in the following areas：
（1）The water treatment agent is not phosphorous, environment-friendly, is a kind of new Environment-friendlywater water treatment agent.Its preparation technology green ring
Border is friendly, and building-up process uses " treating different things alike " mode using environmentally friendly, inexpensive water as reaction dissolvent, course of reaction, without dividing
From simple to operate, production cost is relatively low.
（2）The water treatment agent contains the carboxylic acid ion that can be largely chelated with calcium ion, to industrial circulating cooling water system
In calcium phosphate, calcium carbonate and calcium sulfate scale have efficient inhibitory action.
（3）The compatibility of the water treatment agent is good, can with the water treatment agent compounding use such as organic phosphate, zinc salt corrosion inhibiter,
Also can be used alone.
（4）Contain substantial amounts of starch ester monomer in the water treatment agent, it is biodegradable, it is environment-friendly.
Embodiment
With reference to specific embodiment, the present invention is further described.
Embodiment 1：
（1）In nitrogen（N2）Add 80g polyethylene glycol and 100g maleic anhydrides in the reactor of atmosphere protection, it is anti-at 70 DEG C
2.5h is answered, obtains macrogol ester；
（2）In nitrogen（N2）Add 70g soluble starches and 80g maleic anhydrides in the reactor of atmosphere protection, it is anti-at 50 DEG C
2.5h is answered, obtains starch ester；
（3）By step（1）Obtained macrogol ester and step（2）Obtained starch ester mixes, and is warming up to 60 DEG C；Add
65g maleic anhydrides, 90g water, mix；Sodium peroxydisulfate solution is added dropwise, after being added dropwise, continues to react 2h at 80 DEG C, is down to room
Wen Hou, a kind of without phosphorus water treatment agent is made（1）.Sodium peroxydisulfate solution is dissolved in 40g water by 6g sodium peroxydisulfates to be made.
Without phosphorus water treatment agent（1）Structural formula be：
A structural formula is：
A is soluble starch, and degree of polymerization x is 1000, y 2500, and number of repeat unit m is 50, n 50.
Without phosphorus water treatment agent（1）Dosage when being 6mg/L, to CaCO3Scale inhibition performance is 92.5%, to CaSO4Scale inhibition performance
For 98.8%.
The present invention static-state scale inhibition performance test experiment in calcium carbonate, calcium sulfate scale inhibition performance calculating according to《Middle Chinese
People republic oil and gas industry standard-SY/T5673-1993》Carry out.
Embodiment 2：
（1）In nitrogen（N2）Add 90g polyethylene glycol and 110g maleic anhydrides in the reactor of atmosphere protection, it is anti-at 65 DEG C
2.0h is answered, obtains macrogol ester；
（2）In nitrogen（N2）Add 90g soluble starches and 75g maleic anhydrides in the reactor of atmosphere protection, it is anti-at 60 DEG C
2.5h is answered, obtains starch ester；
（3）By step（1）Obtained macrogol ester and step（2）Obtained starch ester mixes, and is warming up to 75 DEG C；Add
50g methacrylic acids, 80g water, mix；Persulfonic acid sodium solution is added dropwise, after being added dropwise, continues to react 1.5h at 80 DEG C, drops
To room temperature, a kind of without phosphorus water treatment agent is made（2）.Persulfonic acid sodium solution is dissolved in 40g water by 5g persulfonic acid sodium to be made.
Water treatment agent（2）Structural formula is with reference to embodiment 1, and degree of polymerization x is 700, y 260, and number of repeat unit m is 30, n is
25。
Without phosphorus water treatment agent（2）Dosage when being 6mg/L, to CaCO3Scale inhibition performance is 90.5%, to CaSO4Scale inhibition performance
For 97.5%.
Example example 3：
（1）In nitrogen（N2）Add 100g polyethylene glycol and 110g maleic anhydrides in the reactor of atmosphere protection, it is anti-at 50 DEG C
2.5h is answered, obtains macrogol ester；
（2）In nitrogen（N2）90g soluble starches and 110g maleic anhydrides are added in the reactor of atmosphere protection, at 45 DEG C
2.5h is reacted, obtains starch ester；
（3）By step（1）Obtained macrogol ester and step（2）Obtained starch ester mixes, and is warming up to 70 DEG C；Add
35g maleic anhydrides, 20g methyl acrylates, 80g water, mix；Sodium peroxydisulfate solution is added dropwise, after being added dropwise, continues at 80 DEG C
2.5h is reacted, after being down to room temperature, a kind of without phosphorus water treatment agent is made（3）.Sodium peroxydisulfate solution is dissolved in 50g by 8g sodium peroxydisulfates
It is made in water.
Water treatment agent（3）Structural formula is with reference to embodiment 1, and degree of polymerization x is 90, y 170, and number of repeat unit m is 60, n is
80。
Without phosphorus water treatment agent（3）Dosage when being 6mg/L, to CaCO3Scale inhibition performance is 94.5%, to CaSO4Scale inhibition performance
For 99.3%.
Example example 4：
（1）In nitrogen（N2）60g polyethylene glycol and 80g maleic anhydrides are added in the reactor of atmosphere protection, is reacted at 55 DEG C
2.0h, obtain macrogol ester；
（2）In nitrogen（N2）Add 50g soluble starches and 75g maleic anhydrides in the reactor of atmosphere protection, it is anti-at 60 DEG C
2.5h is answered, obtains starch ester；
（3）By step（1）Obtained macrogol ester and step（2）Obtained starch ester mixes, and is warming up to 70 DEG C；Add
45g itaconic acids, 70g water, mix；Persulfonic acid potassium solution is added dropwise, after being added dropwise, continues to react 2h at 70 DEG C, is down to room temperature
Afterwards, a kind of without phosphorus water treatment agent is made（4）.Persulfonic acid potassium solution is dissolved in 40g water by 5g persulfonic acid potassium to be made.
Water treatment agent（4）Structural formula is with reference to embodiment 1, and degree of polymerization x is 1200, y 2000, and number of repeat unit m is 60, n
For 70.
Without phosphorus water treatment agent（4）When dosage is 6mg/L, to CaCO3Scale inhibition performance is 89.5%, to CaSO4Scale inhibition performance
For 97.4%.
Example example 5：
（1）In nitrogen（N2）Add 90g polyethylene glycol and 120g maleic anhydrides in the reactor of atmosphere protection, it is anti-at 60 DEG C
1.5h is answered, obtains macrogol ester；
（2）In nitrogen（N2）Add 80g soluble starches and 90g maleic anhydrides in the reactor of atmosphere protection, it is anti-at 45 DEG C
2.0h is answered, obtains starch ester；
（3）By step（1）Obtained macrogol ester and step（2）Obtained starch ester mixes, and is warming up to 55 DEG C, adds
60g acrylic acid, 80g water, mix；Sodium peroxydisulfate and potassium peroxydisulfate mixed solution is added dropwise, after being added dropwise, continues anti-at 70 DEG C
1.5h is answered, after being down to room temperature, a kind of without phosphorus water treatment agent is made（5）.Sodium peroxydisulfate is with potassium peroxydisulfate mixed solution by 4g mistakes
Sodium sulphate is dissolved in 30g water with 2g potassium peroxydisulfates to be made.
Water treatment agent（5）Structural formula is with reference to embodiment 1, and degree of polymerization x is 800, y 2000, and number of repeat unit m is 40, n is
70。
Without phosphorus water treatment agent（5）When dosage is 6mg/L, to CaCO3Scale inhibition performance is 93.5%, to CaSO4Scale inhibition performance
For 99.1%.
In terms of the water treatment agent scale inhibition result of embodiment, water treatment agent scale inhibition effect of the invention is notable.
Claims (4)
- A kind of 1. without phosphorus water treatment agent, it is characterised in that：With polyethylene glycol ester monomer, starch ester monomer and insatiable hunger containing vinyl With the monomer of double bond carry out it is free-radical polymerized after, its general structure is as follows：In above formula：A is soluble starch, and B is the constitutional repeating unit after the monomer copolymerization of the unsaturated double-bond containing vinyl, is polymerize It is 1 ~ 5000 to spend x, y, and number of repeat unit m, n is 1 ~ 100.
- 2. prepare the method for water treatment agent without phosphorus described in claim 1, it is characterised in that operating procedure is as follows：（1）In nitrogen（N2）Under atmosphere, on the basis of polyethylene glycol quality, by polyethylene glycol and 0.05~5 times of polyethylene glycol quality Maleic anhydride is added in reactor, and 1 ~ 10h is reacted at 30 ~ 120 DEG C, obtains macrogol ester reaction monomers；（2）In nitrogen（N2）Under atmosphere, on the basis of soluble starch quality, by soluble starch and 0.05~5 times of soluble starch The maleic anhydride of quality is added in reactor, and 1 ~ 10h is reacted at 30 ~ 120 DEG C, obtains soluble starch ester reaction monomers；（3）Macrogol ester and starch ester are mixed, reaction temperature is 50 ~ 95 DEG C, adds 0.2 ~ 5 times of macrogol ester reaction The water of the monomer of the unsaturated double-bond containing vinyl of monomer mass, 0.1 ~ 5 times of macrogol ester reaction monomers quality, drips after mixing Add the inorganic initiator aqueous solution that mass percentage concentration is 5%~50%, the addition of inorganic initiator is gathered for 0.01 ~ 0.5 times Glycol ester reaction monomers quality, 1~5h are dripped off, and are continued to react 0.5~10h at 50 ~ 95 DEG C after dripping off, are cooled to room temperature, make Obtain 5 ~ 70wt% of solid content without phosphorus water treatment agent.
- 3. the preparation method of without phosphorus water treatment agent according to claim 2, it is characterised in that：Step（3）Described in contain second Alkenyl unsaturated double-bond monomer is acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid One or more of butyl ester, maleic anhydride, hydroxypropyl acrylate, maleic acid, itaconic acid.
- 4. the preparation method of without phosphorus water treatment agent according to claim 2, it is characterised in that：Step（3）Described in it is inorganic Initiator is sodium peroxydisulfate, potassium peroxydisulfate, lays particular stress on sulfinic acid sodium, lays particular stress on sulfinic acid potassium, persulfonic acid sodium, persulfonic acid potassium, peroxidating One or more of hydrogen.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022070020A1 (en) * | 2020-09-30 | 2022-04-07 | Sabic Global Technologies B.V. | Application of surfmers to mitigate fouling in olefins plants |
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2017
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