CN104291454A - Composite anti-sludging agent used for recirculated cooling seawater - Google Patents
Composite anti-sludging agent used for recirculated cooling seawater Download PDFInfo
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- CN104291454A CN104291454A CN201410432588.8A CN201410432588A CN104291454A CN 104291454 A CN104291454 A CN 104291454A CN 201410432588 A CN201410432588 A CN 201410432588A CN 104291454 A CN104291454 A CN 104291454A
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- seawater
- scale inhibitor
- poly
- scale
- succinic acid
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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
-
- 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
- C02F2103/08—Seawater, e.g. for desalination
-
- 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
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- Chemical & Material Sciences (AREA)
- 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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a composite anti-sludging agent used for recirculated cooling seawater, which is composed of a polyepoxysuccinic acid solution and a hydrolytic polymaleic anhydride solution, mass ratio of polyepoxysuccinic acid to hydrolytic polymaleic anhydride in the composite anti-sludging agent is 1: 0.8-1.2, compared with a single anti-sludging agent monomer, the anti-sludging effect of the composite anti-sludging agent has the advantages of good effect, easy degradation and low cost.
Description
Technical field
The invention belongs to seawater Scale inhibitors technical field, be specifically related to a kind of composite scale inhibitor for circulating cooling seawater.
Background technology
Marine circulating cooling system take seawater as heat-eliminating medium, and complete after once cooling through heat-exchange equipment, seawater cools and the process recycled through cooling tower.Since the seventies, people, while nuisanceless anticorrosion, the anti-halobios adhersion once-though cooling technology of exploration, use for reference the hydronic relevant technological of fresh water and technology, have carried out the research-and-development activity of marine circulating cooling system technology.Marine circulating cooling system technology is compared with once-though cooling technology, fresh water recirculation refrigerating technology, and water withdrawal is little, water price is low, has more advantage economically.Marine circulating cooling system technology decreases more than 95% than the blowdown flow rate of once-though cooling technology, is conducive to protection of the environment, preventing pollution, maintaining ecological balance.
The subject matter of application marine circulating cooling system technology is: the high and complicated component of seawater saltiness, high two orders of magnitude of the general fresh water of Conductivity Ratio, during corrosion, the resistive retardance of seawater is more much smaller than fresh water, and muriate ratio is very large in salinity contained by seawater, the chlorinity of seawater is up to 19 ‰, therefore most metals such as iron, steel, cast iron etc. can not set up passive state in the seawater, and seawater has stronger corrodibility compared with fresh water.Meanwhile, in seawater, the kind of microorganism and mcroorganism is many, content is high, easily produces biodeterioration, and then causes endangering larger microbiological corrosion or underdeposit corrosion.In addition, the incrustation ion in seawater is as Ca
2+, Mg
2+, HCO
3 -, SO
4 2-deng concentration far above fresh water, with cycles of concentration improve, fouling tendency strengthen, common dirt dispersion agent can not effectively control chemical dirt deposition.Therefore, seawater is adopted to there is the problem such as salt sedimentation, salt fog splashing of serious corrosion and scaling and fouling organism attachment issue and seawater cooling tower as recirculated cooling water.Circularly-cooling sea water process has larger difficulty than fresh water circulation.
At present, in recirculating cooling water system, add anti-incrustation corrosion inhibitor remain the common method controlling fouling and corrosion, seawater dirt dispersion agent technology is the gordian technique preventing marine circulating cooling system scaling.
The exploitation of Scale inhibitors and research experienced by the stages such as inorganic salt, polyelectrolyte, natural polymer, organic phosphoric acid, co-poly carboxylic acid.
Along with the increasingly serious of Global Environmental Problems and the increasing of environmental protection dynamics; along with the development of science and technology; protection of the environment, improvement sewage and water saving have meaning of equal importance; the research of Scale inhibitors deepens continuously and reaches its maturity; the research and development of Scale inhibitors develop into nontoxic, readily biodegradable type gradually from poisonous, difficult for biological degradation type; namely research and development is applicable to without phosphorus or low-phosphorous, the non-nitrogen of environment protection demand and biodegradable environmentally friendly Scale inhibitors, namely, novel green Scale inhibitors to human body safety more friendly to environment.Green scale inhibitor is while scale inhibition; not only can economize on water and improve the effective rate of utilization of water; avoid and reduce the pollution of discharge of poisonous waste to water body; the red tide public hazards that water body causes because of eutrophication can also be alleviated; the chance of rehabilitation is brought to the ecotope wrecking and can't bear the heavy load; be conducive to protection of the environment; alleviate increasingly serious environmental problem; create more economic benefit and social benefit; for recycling economy and Sustainable development extremely important, will the research direction of most main flow in Treatment of Industrial Water field be become.
Green scale inhibitor is the Novel scale inhibitor developed along with the rise of Green Chemistry, and it is the high molecular weight water soluble polymer that a class has good scale inhibition effect contaminate environment hardly again.That researchs and develops both at home and abroad at present mainly contains poly aspartic acid and poly-epoxy succinic acid, also has investigation and application to polyacrylic acid and hydrolytic polymaleic anhydride.
Poly aspartic acid and poly-epoxy succinic acid, not only there is scale inhibition and dispersion, and there is biodegradable, become two kinds of generally acknowledged green scale inhibitors, poly aspartic acid also because of structure and natural amino acids seemingly, oil-field water process at sea and agriculture production obtain application.
Poly-epoxy succinic acid take maleic anhydride as raw material, polymerization under catalyst action and obtained; First developed by U.S. Betz laboratory and Betzdearbon company for the 20 poly-beginning of the nineties in century; Its compound formula is
n is generally about 2 ~ 50, is preferably H at about 25, Me
+or water-soluble cationic, as Na
+, NH
4 +or K
+; Because it inserts Sauerstoffatom in polycarboxylic acid Scale inhibitors molecule, make it to be provided with biodegradable, be thus acknowledged as the green chemical of one " environmental friendliness ", the domestic existing report about poly-epoxy succinic acid scale inhibition active testing result.Poly-epoxy succinic acid type water conditioner has good biodegradability, and be applicable to high-alkali high solid water system etc., its scale inhibition activity is higher, and minimum dosage (3mg/L) can reach good scale inhibition effect.The research of recent year poly-epoxy succinic acid is awfully hot, has a lot of relevant research report and patent to come out, also have some poly-epoxy succinic acid commodity to put on market, but the degree of recognition of practical application is not high.
Poly aspartic acid inspires a kind of green scale inhibitor in recent years succeeding in developing by animal metabolism process, A P Wheele and C S Siked finds in the organic research of calcium carbonate, the glycoprotein obtained from the albumen parent infiltrating oyster shells has the effect stoping tosca, is a kind of potential Scale inhibitors.Because one of raw material preparing poly aspartic acid L-Aspartic acid can extract from nature, poly aspartic acid has good biodegradable and excellent scale inhibition and dispersion performance, and thus poly aspartic acid is generally acknowledged Green Water Treatment Reagents.
To poly aspartic acid most study is the U.S., Germany and Japanese, and particularly the Doular company of the U.S. obtains multinomial patent at this point.More external water treatment companies, to polymkeric substance in addition modification, introduce the groups such as hydroxyl, ether, hydroxyalkyl amine, hydroxy alkoxy base hydrocarbon, carboxyl, sulfoalkyl, phosphoric acid and improve their rejection ability to various insoluble dirt.Start suitability for industrialized production poly aspartic acid abroad, and domesticly to have started late, just have relevant report in recent years.Zhou Xiaowei, Zhou Baiqing find after deliberation, and adopting in the poly aspartic acid of different methods synthesis, take maleic anhydride as the poly aspartic acid of Material synthesis, to the scale inhibition performance of calcium sulfate, barium sulfate, Strontium Sulphate close to 100%, also have higher scale inhibition performance to Calcium Fluoride (Fluorspan).The work of the people such as Xiong Rongchun gives the structural characterization of poly aspartic acid, have studied the impact of the factors such as relative molecular weight, pH value, basicity on resistance calcium carbonate effect, show that poly aspartic acid still has good scale inhibition effect to calcium carbonate under high calcium, high-alkali, high ph-values condition.
Polyacrylic acid is a kind of dirt dispersion agent of excellent property, is widely used in recirculated cooling water, oil-field flooding and boiler water processing, has the effect that good suppression incrustation scale generated and peeled off old dirt.Polyacrylic acid is nontoxic, soluble in water, can run and non-scaling under alkalescence and medium cycles of concentration condition.
Hydrolytic polymaleic anhydride is a kind of transparent liquid of brown color, with hydroxyl or sulfonic polymkeric substance the same, the chain ion with a large amount of electric charge such as hydrogen ion and acid radical anion can be dissociated into after water-soluble.Hydrolytic polymaleic anhydride, as a kind of polyelectrolyte of low relative molecular mass, owing to having higher chemical stability and thermostability, and still can keep good scale inhibition effect at relatively high temperatures, receive much attention in recent years in Treatment of Industrial Water research.Carboxyl functional group in this type of Scale inhibitors is to Ca
2+, Mg
2+, Fe
2+, Ba
2+plasma has stronger sequestering power, compared with polyacrylic acid, not only has good dispersion, cohesion, can also in inorganic scale crystallisation process, disturb the normal alignment of lattice better and play scale effect.But there is the shortcomings such as the large and part difficult degradation of consumption in single Scale inhibitors.
Therefore, be badly in need of at present researching and developing out for harshness circulation concentrated seawater, more efficiently green scale inhibitor, significant to marine circulating cooling system safety, economical operation.
Summary of the invention
The object of the present invention is to provide a kind of composite scale inhibitor for circulating cooling seawater, this composite scale inhibitor scale inhibition effect is more effective than the Scale inhibitors of Scale inhibitors monomer, and degraded easily, and cost is low.
Above-mentioned purpose of the present invention is achieved through the following technical solutions: a kind of composite scale inhibitor for circulating cooling seawater, by poly-epoxy succinic acid (english abbreviation is PESA) solution and hydrolytic polymaleic anhydride (english abbreviation is HPMA) solution composition, in described composite scale inhibitor, the mass ratio of poly-epoxy succinic acid and hydrolytic polymaleic anhydride is 1:0.8 ~ 1.2.
As one of the present invention preferably embodiment, in composite scale inhibitor of the present invention, the mass ratio of poly-epoxy succinic acid and hydrolytic polymaleic anhydride is 1:1.
When composite scale inhibitor of the present invention is used for circulating cooling seawater scale inhibition, the consumption of described poly-epoxy succinic acid solution is that in the original seawater of every 1L, 0.25 ~ 1mg, circulation time are concentrated 1 ~ 3.5 times again, and the consumption of described hydrolytic polymaleic anhydride solution is that in the original seawater of every 1L, 0.25 ~ 1mg, circulation time are concentrated 1 ~ 3.5 times again.
As one of the present invention preferably embodiment, when composite scale inhibitor of the present invention is used for circulating cooling seawater scale inhibition, the consumption of described poly-epoxy succinic acid solution is 0.5mg in the original seawater of every 1L, circulation time is concentrated 1 ~ 2.5 times again, the consumption of described hydrolytic polymaleic anhydride solution is 0.5mg in the original seawater of every 1L, and circulation time is concentrated 1 ~ 2.5 times again.
The initial mass percentage composition of poly-epoxy succinic acid solution of the present invention is preferably 30 ~ 50%.
The initial mass percentage composition of poly-epoxy succinic acid solution of the present invention is preferably 40%.
The initial mass percentage composition of hydrolytic polymaleic anhydride solution of the present invention is preferably 30 ~ 50%.
The initial mass percentage composition of hydrolytic polymaleic anhydride solution of the present invention is preferably 40%.
Compared with prior art, tool of the present invention has the following advantages:
(1) when the dosage of Scale inhibitors monomer is identical, good more independent than monomer of the scale inhibition effect of composite scale inhibitor, namely the scale inhibition effect of composite scale inhibitor is good;
(2) scale inhibition effect in order to play, the dosage that specify that the proportioning of Scale inhibitors monomer in composite scale inhibitor He should add, namely composite scale inhibitor is practical;
(3) scale inhibition effect due to poly-epoxy succinic acid is better than hydrolytic polymaleic anhydride, but the height of cost ratio hydrolytic polymaleic anhydride, therefore, when Scale inhibitors dosage is identical, composite scale inhibitor price is starkly lower than poly-epoxy succinic acid monomer, and namely the cost of composite scale inhibitor is low.
Embodiment
The present invention will be described to enumerate a part of specific embodiment below, be necessary to herein means out be following specific embodiment only for the invention will be further described, do not represent limiting the scope of the invention.Some nonessential amendments that other people make according to the present invention and adjustment still belong to protection scope of the present invention.
Embodiment 1
The present embodiment is used for the composite scale inhibitor of circulating cooling seawater, by poly-epoxy succinic acid solution and hydrolytic polymaleic anhydride solution composition, the mass ratio of the two is 1:1, wherein the initial mass percentage composition of poly-epoxy succinic acid solution is 40%, the initial mass percentage composition of hydrolytic polymaleic anhydride solution is 40%, when composite scale inhibitor is used for circulating cooling seawater scale inhibition, the consumption of poly-epoxy succinic acid solution is 0.5mg in the original seawater of the every 1L initial concentration of poly-epoxy succinic acid solution (namely in original seawater), circulation time is concentrated 2.5 times again, the consumption of hydrolytic polymaleic anhydride solution is 0.5mg in the original seawater of every 1L, circulation time is concentrated 2.5 times again.
Embodiment 2
The present embodiment is used for the composite scale inhibitor of circulating cooling seawater, by poly-epoxy succinic acid solution and hydrolytic polymaleic anhydride solution composition, the mass ratio of the two is 1:0.8, wherein the initial mass percentage composition of poly-epoxy succinic acid solution is 30%, the initial mass percentage composition of hydrolytic polymaleic anhydride solution is 30%, when composite scale inhibitor is used for circulating cooling seawater scale inhibition, the consumption of poly-epoxy succinic acid solution is 0.35mg in the original seawater of every 1L, circulation time is concentrated 2 times again, the consumption of hydrolytic polymaleic anhydride solution is 0.28mg in the original seawater of every 1L, circulation time is concentrated 2 times again.
Embodiment 3
The present embodiment is used for the composite scale inhibitor of circulating cooling seawater, by poly-epoxy succinic acid solution and hydrolytic polymaleic anhydride solution composition, the mass ratio of the two is 1:1.2, wherein the initial mass percentage composition of poly-epoxy succinic acid solution is 50%, the initial mass percentage composition of hydrolytic polymaleic anhydride solution is 50%, when composite scale inhibitor is used for circulating cooling seawater scale inhibition, the consumption of poly-epoxy succinic acid solution is 0.8mg in the original seawater of every 1L, be concentrated 3 times again, the consumption of hydrolytic polymaleic anhydride solution is 0.96mg in the original seawater of every 1L, then is concentrated 3 times.
Embodiment 4
The different concns composite scale inhibitor recorded by tosca method (National Standard of the People's Republic of China " mensuration-tosca method of water conditioner scale-inhibiting properties " (GB/T 16632-1996)) and the scale-inhibiting properties of compositing monomer thereof, as shown in table 1.Wherein the initial mass percentage composition of poly-epoxy succinic acid solution is 40%, and the initial mass percentage composition of hydrolytic polymaleic anhydride solution is 40%, and the mass ratio of the two is 1:1.
The scale inhibition effect of table 1 different concns composite scale inhibitor and compositing monomer thereof
As shown in Table 1, the scale-inhibiting properties of the composite scale inhibitor recorded by tosca method, strengthen with the increase of composite scale agent concentration, when particularly composite scale agent concentration is increased to 12.5mg/L (wherein (PESA+HPMA) concentration is 5.0mg/L), scale-inhibiting properties increases obviously, but when composite scale agent concentration is increased to 25mg/L (wherein (PESA+HPMA) concentration is 10.0mg/L), increase the concentration of composite scale inhibitor again, the increase of its scale-inhibiting properties is not obvious; When in composite scale inhibitor, the concentration of PESA is identical with the PESA concentration of PESA monomer Scale inhibitors, the scale-inhibiting properties of composite scale inhibitor is obviously better than the scale-inhibiting properties of PESA monomer.When in composite scale inhibitor, the concentration of HPMA is identical with the HPMA concentration of HPMA monomer Scale inhibitors, the scale-inhibiting properties of composite scale inhibitor is also obviously better than the scale-inhibiting properties of HPMA monomer, illustrates to there is collaborative scale effect between PESA and the HPMA that 1:1 is composite; By composite for Scale inhibitors monomer PESA and HPMA, not only increase scale inhibition effect, also can reduce costs, because HPMA is more cheap than PESA.
Embodiment 5 is for the application of the composite scale inhibitor of circulating cooling seawater
(1) poly-epoxy succinic acid solution and the scale inhibition effect of hydrolytic polymaleic anhydride solution in concentrated seawater of concentration to be 1mg/L composite scale inhibitor (wherein the concentration of poly-epoxy succinic acid solution and hydrolytic polymaleic anhydride solution is respectively 0.5mg/L) and concentration be 1mg/L.
1mg/L composite scale inhibitor and compositing monomer thereof the scale inhibition result in concentrated seawater is as table 2.
Table 2 1mg/L composite scale inhibitor and compositing monomer thereof the scale inhibition effect in concentrated seawater
As shown in Table 2, do not add the concentrated 1.7 times of just obvious foulings of the seawater of Scale inhibitors, when the concentration of composite scale inhibitor and compositing monomer PESA, HPMA is 1mg/L, seawater concentrates 2.7,2.0,2.3 times respectively and starts fouling, illustrates that composite scale inhibitor has scale inhibition effect in concentrated seawater.
(2) poly-epoxy succinic acid solution and the scale inhibition effect of hydrolytic polymaleic anhydride solution in concentrated seawater of concentration to be 2mg/L composite scale inhibitor (wherein poly-epoxy succinic acid solution and hydrolytic polymaleic anhydride strength of solution are respectively 1mg/L) and concentration be 2mg/L.
2mg/L composite scale inhibitor and compositing monomer thereof the scale inhibition result in concentrated seawater is as table 3.
Table 3 2mg/L composite scale inhibitor and compositing monomer thereof the scale inhibition effect in concentrated seawater
As shown in Table 3, do not add the concentrated 1.7 times of just obvious foulings of the seawater of Scale inhibitors, when the concentration of composite scale inhibitor and compositing monomer PESA, HPMA is 2mg/L, seawater concentrates 3.7,2.9,3.0 times respectively and starts fouling, illustrate that 2mg/L composite scale inhibitor not only has scale inhibition effect in concentrated seawater, and scale inhibition effect is better.
The above embodiment of the present invention is not limiting the scope of the present invention; embodiments of the present invention are not limited thereto; all this kind is according to foregoing of the present invention; according to ordinary technical knowledge and the customary means of this area; do not departing under the present invention's above-mentioned basic fundamental thought prerequisite; to hindering the amendment of other various ways of making of said structure, replacement or change, all should drop within protection scope of the present invention.
Claims (8)
1. for a composite scale inhibitor for circulating cooling seawater, it is characterized in that: by poly-epoxy succinic acid solution and hydrolytic polymaleic anhydride solution composition, in described composite scale inhibitor, the mass ratio of poly-epoxy succinic acid and hydrolytic polymaleic anhydride is 1:0.8 ~ 1.2.
2. the composite scale inhibitor for circulating cooling seawater according to claim 1, is characterized in that: in described composite scale inhibitor, the mass ratio of poly-epoxy succinic acid and hydrolytic polymaleic anhydride is 1:1.
3. the composite scale inhibitor for circulating cooling seawater according to claim 1 and 2, it is characterized in that: when described composite scale inhibitor is used for circulating cooling seawater scale inhibition, the consumption of described poly-epoxy succinic acid solution is 0.25 ~ 1mg in the original seawater of every 1L, circulation time is concentrated 1 ~ 3.5 times again, the consumption of described hydrolytic polymaleic anhydride solution is 0.25 ~ 1mg in the original seawater of every 1L, and circulation time is concentrated 1 ~ 3.5 times again.
4. the composite scale inhibitor for circulating cooling seawater according to claim 3, it is characterized in that: when composite scale inhibitor is used for circulating cooling seawater scale inhibition, the consumption of described poly-epoxy succinic acid solution is 0.5mg in the original seawater of every 1L, circulation time is concentrated 1 ~ 2.5 times again, the consumption of described hydrolytic polymaleic anhydride solution is 0.5mg in the original seawater of every 1L, and circulation time is concentrated 1 ~ 2.5 times again.
5. the composite scale inhibitor for circulating cooling seawater according to claim 1 and 2, is characterized in that: the initial mass percentage composition of described poly-epoxy succinic acid solution is 30 ~ 50%.
6. the composite scale inhibitor for circulating cooling seawater according to claim 5, is characterized in that: the initial mass percentage composition of described poly-epoxy succinic acid solution is 40%.
7. the composite scale inhibitor for circulating cooling seawater according to claim 1 and 2, is characterized in that: the initial mass percentage composition of described hydrolytic polymaleic anhydride solution is 30 ~ 50%.
8. the composite scale inhibitor for circulating cooling seawater according to claim 7, is characterized in that: the initial mass percentage composition of described hydrolytic polymaleic anhydride solution is 40%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925966A (en) * | 2015-07-06 | 2015-09-23 | 安徽省蓝天能源环保科技有限公司 | Scale and corrosion inhibitor for oil field system |
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|---|---|---|---|---|
| CN101508492A (en) * | 2009-03-10 | 2009-08-19 | 同济大学 | Environment-friendly composite dirt dispersion agent for oil-field flooding treatment |
| CN101767885A (en) * | 2010-01-12 | 2010-07-07 | 张文宇 | Phosphorus-free corrosion and scale inhibitor |
-
2014
- 2014-08-28 CN CN201410432588.8A patent/CN104291454A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508492A (en) * | 2009-03-10 | 2009-08-19 | 同济大学 | Environment-friendly composite dirt dispersion agent for oil-field flooding treatment |
| CN101767885A (en) * | 2010-01-12 | 2010-07-07 | 张文宇 | Phosphorus-free corrosion and scale inhibitor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925966A (en) * | 2015-07-06 | 2015-09-23 | 安徽省蓝天能源环保科技有限公司 | Scale and corrosion inhibitor for oil field system |
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