CN102146149A - Novel scale inhibition and dispersion agent - Google Patents
Novel scale inhibition and dispersion agent Download PDFInfo
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- CN102146149A CN102146149A CN2010191020444A CN201019102044A CN102146149A CN 102146149 A CN102146149 A CN 102146149A CN 2010191020444 A CN2010191020444 A CN 2010191020444A CN 201019102044 A CN201019102044 A CN 201019102044A CN 102146149 A CN102146149 A CN 102146149A
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- maleic anhydride
- monomer
- thionamic acid
- dispersion agent
- radical
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Abstract
The invention discloses a novel scale inhibition and dispersion agent. The novel scale inhibition and dispersion agent with excellent calcium carbonate scale inhibition performance and a certain calcium phosphate scale dispersion performance is prepared from maleic anhydride monomers and sulfamic acid monomers under the action of a catalyst in a peroxide and sodium hypophosphite initiation system. The scale inhibition and dispersion agent product has simple reaction process and stable and reliable technique. No three wastes are discharged, and environment pollution is not caused.
Description
Affiliated technical field
The present invention relates to the Scale inhibitors in a kind of Treatment of Industrial Water field, particularly a kind of novel dirt dispersion agent, the scale inhibition that is applied to industrial circulating cooling water disperses.
Background technology
At present, process water quantity is very huge, and the overwhelming majority must recycle, and especially keeps the cooling water of production.The Treatment of Industrial Water medicament especially exploitation of dirt dispersion agent uses just for satisfying this needs.
The kind of dirt dispersion agent is a lot of both at home and abroad, and the deposition of lime carbonate mainly adopts inorganic phosphorus such as tertiary sodium phosphate based on the phosphorus line formulation product in the Control Circulation water coolant, poly-phosphorus such as tripoly phosphate sodium STPP, Sodium hexametaphosphate 99 sodium, or organic phosphine is product such as HEDP, ATMP.The use of phosphorus line formulation can bring certain problem.At first, can't avoid that phosphorus is the enrichment of material in the water body, cause microorganism in the water body grow in addition out of hand, consume the dissolved oxygen in the water body, hydrobiological existence and growth are constituted a threat to, water bodys such as river, river, lake, sea are polluted, often need be used a large amount of biocides with the microorganism in the control water.Secondly, the positive phosphorus concentration that decomposes in circulation cooling water is increased to a certain amount of, can bring the deposition problems of calcium phosphate, therefore needs composite AMPS multipolymer to disperse calcium phosphate scale.Also have multi-functional poly carboxylic acid (salt), various series copolymer in addition, stop carbonate sedimentary effect in water still undesirable but compare with organic phosphine, also must be aided with organic phosphine is that product reaches the purpose that stops carbonate deposition.Simultaneously, poly carboxylic acid (salt) reaches all high problems of ubiquity cost of the present various AMPS multipolymers that use.Research and development to scale inhibition, dispersion agent at present mainly concentrate on synthesizing various multipolymers.Just develop towards following several directions.1. potion multipotency.2. reduce cost.3. environmentally friendly machine.The exploitation of the low-cost low-phosphorous or without phosphorus dirt dispersion agent with ideal resistance calcium carbonate scale effect has become the urgent task of industrial circulating cooling water process field.
Summary of the invention
Problem to be solved by this invention is, overcomes the deficiencies in the prior art, and to reduce the water treatment agent cost, reduce or avoid phosphorus be material to water pollution, the scale inhibition and dispersion performance that improves water treatment agent is purpose, and a kind of novel dirt dispersion agent is provided.This dirt dispersion agent not only Recipe is reasonable, makes simply, and also the potion multipotency, reduced cost, reduced environmental pollution.
The technical solution used in the present invention is: concrete synthesis technique is as follows:
A, utilization self-control effective catalyst decompose generation OH radical;
B, produce maleic anhydride-thionamic acid monomer;
C, OH radical excite maleic anhydride monomer to form the maleic anhydride monomer radical;
D, OH radical excite maleic anhydride-thionamic acid monomer to form maleic anhydride-thionamic acid monomer free base;
E. the maleic anhydride monomer radical excites the maleic anhydride monomer polymerization;
F, maleic anhydride-thionamic acid monomer free base excite maleic anhydride-thionamic acid monomer polymerization;
G, maleic anhydride and maleic anhydride-thionamic acid copolymerization generates novel dirt dispersion agent, represents the maleic anhydride polymkeric substance with A, and B represents maleic anhydride-thionamic acid polymkeric substance, and then copolyreaction formula is:
(n+1)A+(n+1)B→A
n+1B
m+1。
Make the equipment technical process, with maleic anhydride monomer and thionamic acid monomer, catalyzer, superoxide, inferior sodium phosphate is sequentially added into by surge tank, vacuum pump, vacuum tank, reactor, mechanical stirrer, receiving tank, the catalyzer scale tank, the monomer scale tank, condenser, during the making that snubber is formed by pipe connecting is equipped, by operation, under catalyst action and superoxide and inferior sodium phosphate initiator system, synthesize novel dirt dispersion agent with maleic anhydride monomer and homemade cheap thionamic acid monomer with good resistance calcium carbonate scale performance and certain dispersion calcium phosphate scale performance.Dirt dispersion agent product reaction process of the present invention is simple, and process stabilizing is reliable, does not have " three wastes " discharging, does not cause environmental pollution.Sufficient raw.This product has been owing to adopted cheap thionamic acid monomer, thereby reduced the cost of water treatment agent widely, economize on resources, and under the same conditions, scale inhibition and dispersion performance is better than traditional water treatment agent monomer.For example, in the scope of pH value 7-9, resistance calcium carbonate scale and calcium phosphate scale performance obviously are better than polymaleic anhydride and other dispersion agents.Simultaneously, this product belongs to low-phosphorous no phosphorus product, and having avoided phosphorus is the water pollution of material to rivers,lakes and seas.
The invention has the beneficial effects as follows that reaction process is simple, process stabilizing is reliable, does not have " three wastes " discharging, does not cause environmental pollution.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is a making equipment configuration synoptic diagram of the present invention.
Accompanying drawing number is: 1, surge tank, 2, vacuum pump, 3, vacuum tank, 4, reactor, 5, mechanical stirrer, 6, receiving tank, 7, the catalyzer scale tank, 8, the monomer scale tank, 9, condenser, 10, snubber, 11, pipe connecting.
Embodiment
Concrete synthesis technique is as follows:
A, utilization self-control effective catalyst decompose generation OH radical;
B, produce maleic anhydride-thionamic acid monomer;
C, OH radical excite maleic anhydride monomer to form the maleic anhydride monomer radical;
D, OH radical excite maleic anhydride-thionamic acid monomer to form maleic anhydride-thionamic acid monomer free base;
E, maleic anhydride monomer radical excite the maleic anhydride monomer polymerization;
F, maleic anhydride-thionamic acid monomer free base excite maleic anhydride-thionamic acid monomer polymerization;
G, maleic anhydride and maleic anhydride-thionamic acid copolymerization generates novel dirt dispersion agent, represents the maleic anhydride polymkeric substance with A, and B represents maleic anhydride-thionamic acid polymkeric substance, and then copolyreaction formula is:
(n+1)A+(n+1)B→A
n+1B
m+1
With reference to Fig. 1, make the equipment technical process, with maleic anhydride monomer and thionamic acid monomer, catalyzer, superoxide, inferior sodium phosphate is sequentially added into by surge tank (1), vacuum pump (2), vacuum tank (3), reactor (4), mechanical stirrer (5), receiving tank (6), catalyzer scale tank (7), (8) 2 of monomer scale tanks, condenser (9), snubber (10) is assembled into one by pipe connecting (11) in the making equipment of forming, by operation, under catalyst action and superoxide and inferior sodium phosphate initiator system, synthesize novel dirt dispersion agent with maleic anhydride monomer and homemade cheap thionamic acid monomer with good resistance calcium carbonate scale performance and certain dispersion calcium phosphate scale performance.Dirt dispersion agent product reaction process of the present invention is simple, and process stabilizing is reliable, does not have " three wastes " discharging, does not cause environmental pollution.Sufficient raw.This product has been owing to adopted cheap thionamic acid monomer, thereby reduced the cost of water treatment agent widely, economize on resources, and under the same conditions, scale inhibition and dispersion performance is better than traditional water treatment agent monomer.For example, in the scope of pH value 7-9, resistance calcium carbonate scale and calcium phosphate scale performance obviously are better than polymaleic anhydride and other dispersion agents.Simultaneously, this product belongs to low-phosphorous no phosphorus product, and having avoided phosphorus is the water pollution of material to rivers,lakes and seas.
Embodiment 1:
Earlier maleic anhydride (purity 99.5%) 65 grams and thionamic acid (purity 99%) 32.5 grams are added under whipped state in 500 milliliters of four-hole glass reactions making equipments; under the CO2 gas shield; beginning is heating slowly, is heated to 60-80 ℃ with 30 fens clock times, keeps 1 hour.Be warmed up to 100-110 ℃ with 1 hour again, carried out ammonolysis reaction 1 hour.Cool to 60 ℃, add water 60 gram, and then add from each 5 milligrams of controlling catalyst TL-A and TL-B, add inferior sodium phosphate (purity 99%) 25 grams again, inferior sodium phosphate is divided under 60 ℃ of conditions and is added for three times, is warmed up to 90 ℃.Beginning at the uniform velocity drips peroxide initiator under 90 ℃ of conditions, and peroxide initiator 21 gram (30%) aqueous solution were added dropwise to complete with 3 hours, and temperature of reaction is controlled at 100-110 ℃, then 100-110 ℃ of insulation reaction 2 hours.Cool to 65 ℃, add water 219 grams and stir evenly discharging, make faint yellow aqueous products.
Embodiment 2:
Earlier maleic anhydride (purity 99.5%) 72.5 grams and thionamic acid (purity 99%) 25 grams are added under whipped state in 500 milliliters of four-hole glass reactions making equipments; under the CO2 gas shield; beginning is heating slowly, is heated to 60-80 ℃ with 30 fens clock times, keeps 1 hour.Be warmed up to 100-110 ℃ with 1 hour again, carried out ammonolysis reaction 1 hour.Cool to 60 ℃, add water 60 gram, and then add from each 5 milligrams of controlling catalyst TL-A and TL-B, add inferior sodium phosphate (purity 99%) 25 grams again, inferior sodium phosphate is divided under 60 ℃ of conditions and is added for three times, is warmed up to 90 ℃.Beginning at the uniform velocity drips peroxide initiator under 90 ℃ of conditions, and peroxide initiator 21 gram (30%) aqueous solution were added dropwise to complete with 3 hours, and temperature of reaction is controlled at 100-110 ℃, then 100-110 ℃ of insulation reaction 2 hours.Cool to 65 ℃, add water 219 grams and stir evenly discharging, make faint yellow aqueous products.
Embodiment 3:
Earlier maleic anhydride (purity 99.5%) 60 grams and thionamic acid (purity 99%) 20 grams are added under whipped state in the 500ml four-hole glass reaction making equipment; under the CO2 gas shield; beginning is heating slowly, is heated to 60-80 ℃ with 30 fens clock times, keeps 1 hour.Be warmed up to 100-110 ℃ with 1 hour again, carried out ammonolysis reaction 1 hour.Cool to 60 ℃, add water 60 gram, add sulfuric acid 17.5 grams, and then add from each 5 milligrams of controlling catalyst TL-A and TL-B, add inferior sodium phosphate (purity 99%) 25 grams again, inferior sodium phosphate is divided under 60 ℃ of conditions and is added for three times, is warmed up to 90 ℃.Beginning at the uniform velocity drips peroxide initiator under 90 ℃ of conditions, and peroxide initiator 21 gram (30%) aqueous solution were added dropwise to complete with 3 hours, and temperature of reaction is controlled at 100-110 ℃, then 100-110 ℃ of insulation reaction 2 hours.Cool to 65 ℃, add water 219 grams and stir evenly discharging, make faint yellow aqueous products.
This after testing novel dirt dispersion agent product performance such as following table:
| Lot number | Solid content (%) | Relative viscosity | 80 ℃ of resistance calcium carbonate scale 5ppm 10 hours | 80 ℃ of resistance calcium phosphate scale 10ppm 10 hours |
| 1 | 28.5 | 1.045 | 94 | 92 |
| 2 | 29.0 | 1.056 | 94 | 91 |
| 3 | 28.9 | 1.065 | 95 | 92 |
This project adopts cheap thionamic acid monomer and the novel dirt dispersion agent of maleic anhydride monomer synthetic to have following advantage compared with similar products:
| Project | AA/AMPS (domestic) | T225 (abroad) | HPMA (domestic) | This product |
| Performance | The resistance calcium carbonate scale is poor, and the resistance calcium phosphate scale is good | The resistance calcium carbonate scale is poor, and the resistance calcium phosphate scale is good | The resistance calcium carbonate scale is good, and the resistance calcium phosphate scale is poor | The resistance calcium carbonate scale is good, and the resistance calcium phosphate scale is good |
| Cost | High | High | Higher | Low |
| Price | High | High | Higher | Low |
Claims (2)
1. novel dirt dispersion agent is characterized in that: concrete synthesis technique is as follows:
A, utilization self-control effective catalyst decompose generation OH radical;
B, produce maleic anhydride-thionamic acid monomer;
C, OH radical excite maleic anhydride monomer to form the maleic anhydride monomer radical;
D, OH radical excite maleic anhydride-thionamic acid monomer to form maleic anhydride-thionamic acid monomer free base;
E. the maleic anhydride monomer radical excites the maleic anhydride monomer polymerization;
F, maleic anhydride-thionamic acid monomer free base excite maleic anhydride-thionamic acid monomer polymerization;
G, maleic anhydride and maleic anhydride-thionamic acid copolymerization generates novel dirt dispersion agent, represents the maleic anhydride polymkeric substance with A, and B represents maleic anhydride-thionamic acid polymkeric substance, and then copolyreaction formula is:
(n+1)A+(n+1)B→A
n+1B
m+1。
2. a kind of novel dirt dispersion agent according to claim 1 is characterized in that: the making equipment is assembled into one by pipe connecting by surge tank, vacuum pump, vacuum tank, reactor, mechanical stirrer, receiving tank, catalyzer scale tank, monomer scale tank, condenser, snubber and forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010191020444A CN102146149A (en) | 2010-02-09 | 2010-02-09 | Novel scale inhibition and dispersion agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010191020444A CN102146149A (en) | 2010-02-09 | 2010-02-09 | Novel scale inhibition and dispersion agent |
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| Publication Number | Publication Date |
|---|---|
| CN102146149A true CN102146149A (en) | 2011-08-10 |
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|---|---|---|---|
| CN2010191020444A Pending CN102146149A (en) | 2010-02-09 | 2010-02-09 | Novel scale inhibition and dispersion agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450860A (en) * | 2012-06-01 | 2013-12-18 | 天津中油渤星工程科技有限公司 | Dispersant for improving compatibility of cement mortar and drilling fluid |
| CN103525588A (en) * | 2013-09-25 | 2014-01-22 | 广东工业大学 | Biodegradable high molecular washing assistant as well as preparation method thereof |
| CN104445646A (en) * | 2014-11-25 | 2015-03-25 | 苏州佑君环境科技有限公司 | Scale removal and prevention agent for boiler and preparation method of scale removal and prevention agent |
| TWI699336B (en) * | 2019-12-06 | 2020-07-21 | 中國鋼鐵股份有限公司 | Scale inhibitor for coking wastewater and method for inhibiting scale in coking wastewater |
-
2010
- 2010-02-09 CN CN2010191020444A patent/CN102146149A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450860A (en) * | 2012-06-01 | 2013-12-18 | 天津中油渤星工程科技有限公司 | Dispersant for improving compatibility of cement mortar and drilling fluid |
| CN103525588A (en) * | 2013-09-25 | 2014-01-22 | 广东工业大学 | Biodegradable high molecular washing assistant as well as preparation method thereof |
| CN104445646A (en) * | 2014-11-25 | 2015-03-25 | 苏州佑君环境科技有限公司 | Scale removal and prevention agent for boiler and preparation method of scale removal and prevention agent |
| TWI699336B (en) * | 2019-12-06 | 2020-07-21 | 中國鋼鐵股份有限公司 | Scale inhibitor for coking wastewater and method for inhibiting scale in coking wastewater |
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Application publication date: 20110810 |