阅读说明：本技术 低温不凝固的无磷缓蚀阻垢剂及其制备方法、阻垢方法 (Low-temperature non-solidification phosphorus-free corrosion and scale inhibitor, preparation method thereof and scale inhibition method ) 是由 钟毅轩 黄学森 于 2021-10-11 设计创作，主要内容包括：本发明涉及钢铁企业冲渣水系统缓蚀阻垢处理领域,提供一种低温不凝固的无磷缓蚀阻垢剂及其制备方法,用于解决传统阻垢剂在低温下易冻结的问题。本发明提供的低温不凝固的无磷缓蚀阻垢剂,包括：聚天冬氨酸20～40%,聚环氧琥珀酸20～40%,水解聚马来酸酐10～30%,水10～30%。无需额外加入防冻剂即可耐-20℃极端天气,运输储存的方便,降低了生产成本；该低温不凝固的无磷缓蚀阻垢剂采用了无磷配方,相较于有机磷系阻垢剂,二次污染少,安全环保无污染。(The invention relates to the field of corrosion and scale inhibition treatment of slag flushing water systems of iron and steel enterprises, and provides a low-temperature non-solidification phosphorus-free corrosion and scale inhibitor and a preparation method thereof, which are used for solving the problem that the traditional scale inhibitor is easy to freeze at low temperature. The invention provides a low-temperature non-solidified phosphorus-free corrosion and scale inhibitor, which comprises the following components in percentage by weight: 20-40% of polyaspartic acid, 20-40% of polyepoxysuccinic acid, 10-30% of hydrolyzed polymaleic anhydride and 10-30% of water. The weather can be endured at the extreme temperature of-20 ℃ without adding an additional antifreezing agent, the transportation and the storage are convenient, and the production cost is reduced; compared with an organic phosphorus scale inhibitor, the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor adopts a phosphorus-free formula, has less secondary pollution, is safe and environment-friendly, and has no pollution.)

1. A low-temperature non-solidification phosphorus-free corrosion and scale inhibitor is characterized by comprising the following components: 20-40% of polyaspartic acid, 20-40% of polyepoxysuccinic acid, 10-30% of hydrolyzed polymaleic anhydride and 10-30% of water.

2. The low-temperature non-solidifying phosphorus-free corrosion and scale inhibitor according to claim 1, comprising: 30-40% of polyaspartic acid, 30-40% of polyepoxysuccinic acid, 20-30% of hydrolyzed polymaleic anhydride and 20-30% of water.

3. The low-temperature non-setting phosphorus-free corrosion and scale inhibitor according to claim 1, comprising: 30% of polyaspartic acid, 30% of polyepoxysuccinic acid, 20% of hydrolyzed polymaleic anhydride and 20% of water.

4. A preparation method of a low-temperature non-solidification phosphorus-free corrosion and scale inhibitor is characterized by comprising the following steps:

uniformly mixing 20-40% of polyaspartic acid, 20-40% of polyepoxysuccinic acid, 10-30% of hydrolyzed polymaleic anhydride and 10-30% of water to obtain the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor.

5. A method of scale inhibition, comprising:

the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor as defined in any one of claims 1 to 3 is added into a target system, wherein the content of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the target system is 10-30 mg/L.

6. The scale inhibition method according to claim 5, wherein the content of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the target system is 15-20 mg/L.

7. The scale inhibition method according to claim 5, wherein the content of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the target system is 20 mg/L.

Technical Field

The invention relates to the field of corrosion and scale inhibition treatment of slag flushing water systems of iron and steel enterprises, in particular to a low-temperature non-solidification phosphorus-free corrosion and scale inhibitor.

Background

The blast furnace slag flushing water is a byproduct generated in blast furnace ironmaking, and is mainly used for manufacturing building materials after processing. Due to the development of comprehensive utilization of blast furnace slag, the blast furnace slag is mostly made into water granulated slag through water quenching, and becomes a raw material for manufacturing building materials such as slag cement or slag bricks. It can also be used for manufacturing slag wool, cast stone, expanded balls and the like. The blast furnace slag flushing water is used as a low-temperature waste heat source, has the characteristics of stable temperature and large flow, and how to make the slag flushing water exert the benefit of waste heat utilization is also a research subject gradually.

At present, the blast furnace slag flushing water is mainly used for providing heating in winter by directly utilizing sensible heat, the utilization mode is simple in technology and low in modification cost, but serious problems exist: (1) the heating is only suitable for northern cities in winter, and is not needed in summer, and southern cities do not need heating all the year round; (2) the slag flushing water contains a large amount of impurities, and is easy to block after entering a pipe network, and a heat supply pipe network system is huge and has high cleaning difficulty.

Most of scale inhibitors on the market at present are organic phosphorus scale inhibitors, phosphate scale is easily generated in a slag flushing water system by a phosphorus-containing formula, secondary pollution is easily caused to water, the green environmental protection requirement is not met, the scale inhibitors are very easy to freeze in winter in northern China, the scale inhibitors cannot be poured out, and the cost is increased due to the addition of an additional antifreeze. In order to solve the problems that a slag flushing system is seriously scaled and the scale inhibitor cannot be transported and stored in winter in the north, the phosphorus-free scale inhibitor suitable for low-temperature transportation and storage is required to be developed.

Disclosure of Invention

The invention solves the technical problem that the traditional scale inhibitor is easy to freeze at low temperature, and provides a low-temperature non-solidification phosphorus-free corrosion and scale inhibitor, a preparation method thereof and a scale inhibition method.

In order to solve the technical problems, the technical scheme provided by the invention is as follows:

a low-temperature non-solidification phosphorus-free corrosion and scale inhibitor comprises: 20-40% of polyaspartic acid, 20-40% of polyepoxysuccinic acid, 10-30% of hydrolyzed polymaleic anhydride and 10-30% of water.

The polyaspartic acid, the polyepoxysuccinic acid and the hydrolyzed maleic anhydride are compounded, so that a certain synergistic effect is achieved, and the system scaling can be effectively reduced.

The weather can be endured at the extreme temperature of-20 ℃ without adding an additional antifreezing agent, the transportation and the storage are convenient, and the production cost is reduced; compared with an organic phosphorus scale inhibitor, the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor adopts a phosphorus-free formula, has less secondary pollution, is safe and environment-friendly, and has no pollution.

The polyaspartic acid can chelate polyvalent metal ions such as calcium, magnesium, copper, iron and the like, particularly can change the crystal structure of calcium salt to form soft scale, can be used in the fields of water treatment such as industrial circulating water, boiler water, reverse osmosis water, oil field water, seawater desalination and the like, and has good performance in systems with high hardness, high alkalinity, high pH value and high concentration multiple.

Partial active groups in the polyepoxysuccinic acid have certain chelating force on scale-forming cations, and have a chelating effect, so that partial scale-forming cations can be blocked, the reaction of the scale-forming cations and anions can be inhibited, and scaling can be prevented.

The hydrolyzed maleic anhydride is a low molecular weight polyelectrolyte, generally has a relative molecular weight of 400-800, is non-toxic, easily soluble in water, high in chemical stability and thermal stability, and has a decomposition temperature of over 330 ℃. There is a clear solubility limiting effect at high temperatures (< 350 ℃) and high pH. HPMA is suitable for use in alkaline water or in combination with other medicines. The hydrolyzed maleic anhydride still has good scale inhibition and dispersion effects on carbonate at the temperature of below 300 ℃, and the scale inhibition time can reach 100 h. The hydrolyzed maleic anhydride has excellent scale inhibition performance and high temperature resistance, so the hydrolyzed maleic anhydride is widely used in flash evaporation devices for seawater desalination, low-pressure boilers, steam locomotives, crude oil dehydration, water and oil delivery pipelines and industrial circulating cooling water. In addition, the hydrolyzed maleic anhydride has a certain corrosion inhibition effect, and the compounding effect with the zinc salt is better.

Preferably, the method comprises the following steps: 30-40% of polyaspartic acid, 30-40% of polyepoxysuccinic acid, 20-30% of hydrolyzed polymaleic anhydride and 20-30% of water.

Preferably, the method comprises the following steps: 30% of polyaspartic acid, 30% of polyepoxysuccinic acid, 20% of hydrolyzed polymaleic anhydride and 20% of water.

A preparation method of a low-temperature non-solidification phosphorus-free corrosion and scale inhibitor comprises the following steps:

uniformly mixing 20-40% of polyaspartic acid, 20-40% of polyepoxysuccinic acid, 10-30% of hydrolyzed polymaleic anhydride and 10-30% of water to obtain the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor.

A method of scale inhibition comprising:

the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is added into a target system, wherein the content of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the target system is 10-30 mg/L.

Preferably, the content of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the target system is 15-20 mg/L.

Preferably, the content of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the target system is 20 mg/L.

Compared with the prior art, the invention has the beneficial effects that: the weather can be endured at the extreme temperature of-20 ℃ without adding an additional antifreezing agent, the transportation and the storage are convenient, and the production cost is reduced; compared with an organic phosphorus scale inhibitor, the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor adopts a phosphorus-free formula, has less secondary pollution, is safe and environment-friendly, and has no pollution.

Detailed Description

The following examples are further illustrative of the present invention and are not intended to be limiting thereof.

Example 1

A low-temperature non-solidification phosphorus-free corrosion and scale inhibitor comprises: 30% of polyaspartic acid, 30% of polyepoxysuccinic acid, 20% of hydrolyzed polymaleic anhydride and 20% of water.

Uniformly mixing polyaspartic acid, polyepoxysuccinic acid, hydrolyzed polymaleic anhydride and water to obtain the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor.

The polyaspartic acid, the polyepoxysuccinic acid and the hydrolyzed maleic anhydride are compounded, so that a certain synergistic effect is achieved, and the system scaling can be effectively reduced.

The product can resist the inconvenience of transportation and storage caused by extreme weather of 20 ℃ below zero without adding an additional antifreezing agent, so that the production cost is reduced; compared with an organic phosphorus scale inhibitor, the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor adopts a phosphorus-free formula, has less secondary pollution, is safe and environment-friendly, and has no pollution.

The low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the embodiment is added into a cleaned system for circulation, and the adding amount of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is 15 mg/L.

Example 2

A low-temperature non-solidification phosphorus-free corrosion and scale inhibitor comprises: 30% of polyaspartic acid, 20% of hydrolyzed polymaleic anhydride and 50% of water.

Uniformly mixing the polyaspartic acid, hydrolyzed polymaleic anhydride and water to obtain the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor.

The low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the embodiment is added into a cleaned system for circulation, and the adding amount of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is 15 mg/L.

Example 3

A low-temperature non-solidification phosphorus-free corrosion and scale inhibitor comprises: 30% of polyepoxysuccinic acid, 20% of hydrolyzed polymaleic anhydride and 50% of water.

Uniformly mixing polyepoxysuccinic acid, hydrolyzed polymaleic anhydride and water to obtain the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor.

The low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the embodiment is added into a cleaned system for circulation, and the adding amount of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is 15 mg/L.

Example 4

A low-temperature non-solidification phosphorus-free corrosion and scale inhibitor comprises: 30% of polyaspartic acid, 30% of polyepoxysuccinic acid and 40% of water.

Uniformly mixing the polyaspartic acid, the polyepoxysuccinic acid and water to obtain the low-temperature non-solidification phosphorus-free corrosion and scale inhibitor.

The low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the embodiment is added into a cleaned system for circulation, and the adding amount of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is 15 mg/L.

Example 5

A method of scale inhibition comprising:

and cleaning pipelines in the system to remove scale and scale.

Pretreating the pipeline by using a corrosion inhibitor;

the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the embodiment 1 is added into a system for circulation, and the adding amount of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is 15 mg/L.

The preparation method of the corrosion inhibitor comprises the following steps:

preparing a precursor solution, wherein: 81% of absolute ethyl alcohol, 18% of n-butyl titanate and 1% of diethanolamine, weighing the above medicaments in proportion, uniformly mixing, and stirring for 2 hours to obtain a precursor solution;

and (3) mixing the precursor solution with a 95% alcohol solution according to a volume ratio of 1:1, stirring for 30min, adding DMF and benzoic acid to ensure that the mass fraction of DMF is 0.4% and the mass fraction of benzoic acid is 0.1%, and uniformly mixing to obtain the corrosion inhibitor.

The cleaning comprises the following steps:

and (3) adjusting the pH value in the system to be 1-2 by using dilute hydrochloric acid, circulating for 10-20 times, and discharging circulating water. And cleaning the pipeline in the system for 1-2 times by using clear water, for example, the clear water can be used as circulating water and circulated for 1-2 times. And after cleaning, replacing clear water for pretreatment.

The pretreatment comprises the following steps:

adding the corrosion inhibitor into clear water, and circulating for 10-20 times, wherein the mass fraction of the corrosion inhibitor is 5% after the corrosion inhibitor is added.

Example 6

A method of scale inhibition comprising:

and cleaning pipelines in the system to remove scale and scale.

Pretreating the pipeline by using a corrosion inhibitor;

and (2) adding the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the embodiment 2 into a system for circulation, wherein the adding amount of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is 15 mg/L.

The preparation method of the corrosion inhibitor comprises the following steps:

preparing a precursor solution, wherein: 81% of absolute ethyl alcohol, 18% of n-butyl titanate and 1% of diethanolamine, weighing the above medicaments in proportion, uniformly mixing, and stirring for 2 hours to obtain a precursor solution;

and (3) mixing the precursor solution with a 95% alcohol solution according to a volume ratio of 1:1, stirring for 30min, adding DMF and benzoic acid to ensure that the mass fraction of DMF is 0.4% and the mass fraction of benzoic acid is 0.1%, and uniformly mixing to obtain the corrosion inhibitor.

The cleaning comprises the following steps:

and (3) adjusting the pH value in the system to be 1-2 by using dilute hydrochloric acid, circulating for 10-20 times, and discharging circulating water. And cleaning the pipeline in the system for 1-2 times by using clear water, for example, the clear water can be used as circulating water and circulated for 1-2 times. And after cleaning, replacing clear water for pretreatment.

The pretreatment comprises the following steps:

adding the corrosion inhibitor into clear water, and circulating for 10-20 times, wherein the mass fraction of the corrosion inhibitor is 5% after the corrosion inhibitor is added.

Example 7

A method of scale inhibition comprising:

and cleaning pipelines in the system to remove scale and scale.

Pretreating the pipeline by using a corrosion inhibitor;

and (3) adding the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the embodiment 3 into a system for circulation, wherein the adding amount of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is 15 mg/L.

The preparation method of the corrosion inhibitor comprises the following steps:

preparing a precursor solution, wherein: 81% of absolute ethyl alcohol, 18% of n-butyl titanate and 1% of diethanolamine, weighing the above medicaments in proportion, uniformly mixing, and stirring for 2 hours to obtain a precursor solution;

and (3) mixing the precursor solution with a 95% alcohol solution according to a volume ratio of 1:1, stirring for 30min, adding DMF and benzoic acid to ensure that the mass fraction of DMF is 0.4% and the mass fraction of benzoic acid is 0.1%, and uniformly mixing to obtain the corrosion inhibitor.

The cleaning comprises the following steps:

and (3) adjusting the pH value in the system to be 1-2 by using dilute hydrochloric acid, circulating for 10-20 times, and discharging circulating water. And cleaning the pipeline in the system for 1-2 times by using clear water, for example, the clear water can be used as circulating water and circulated for 1-2 times. And after cleaning, replacing clear water for pretreatment.

The pretreatment comprises the following steps:

adding the corrosion inhibitor into clear water, and circulating for 10-20 times, wherein the mass fraction of the corrosion inhibitor is 5% after the corrosion inhibitor is added.

Example 8

A method of scale inhibition comprising:

and cleaning pipelines in the system to remove scale and scale.

Pretreating the pipeline by using a corrosion inhibitor;

and (3) adding the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor in the embodiment 4 into a system for circulation, wherein the adding amount of the low-temperature non-solidified phosphorus-free corrosion and scale inhibitor is 15 mg/L.

The preparation method of the corrosion inhibitor comprises the following steps:

preparing a precursor solution, wherein: 81% of absolute ethyl alcohol, 18% of n-butyl titanate and 1% of diethanolamine, weighing the above medicaments in proportion, uniformly mixing, and stirring for 2 hours to obtain a precursor solution;

and (3) mixing the precursor solution with a 95% alcohol solution according to a volume ratio of 1:1, stirring for 30min, adding DMF and benzoic acid to ensure that the mass fraction of DMF is 0.4% and the mass fraction of benzoic acid is 0.1%, and uniformly mixing to obtain the corrosion inhibitor.

The cleaning comprises the following steps:

and (3) adjusting the pH value in the system to be 1-2 by using dilute hydrochloric acid, circulating for 10-20 times, and discharging circulating water. And cleaning the pipeline in the system for 1-2 times by using clear water, for example, the clear water can be used as circulating water and circulated for 1-2 times. And after cleaning, replacing clear water for pretreatment.

The pretreatment comprises the following steps:

adding the corrosion inhibitor into clear water, and circulating for 10-20 times, wherein the mass fraction of the corrosion inhibitor is 5% after the corrosion inhibitor is added.

Comparative example 1

Water was used as a comparison.

Examples of the experiments

Slag flushing water system of certain iron and steel plant: circulating water amount: 2400m carrying out fruit thinning/hr; water retention amount: 1500m thin section; water replenishing quantity: 1500m thin year/day; water temperature: 80 ℃; daily treatment slag amount: 3000T (water consumption 0.5m for each ton of dregs); the make-up water includes: high salt water, industrial water and reuse water. The hardness of the flushing slag water is as follows: 3700 mg/L; alkalinity: 55 mg/L; pH: 6.5-7.

Imitating the slag flushing water system, a pilot reactor is established: circulating water amount: 2.4 m/hr; water retention amount: carrying out fruit bearing and fruit bearing at 1.5 m; water replenishing quantity: carrying out bearing and carrying out bearing; water temperature: 80 ℃; daily treatment slag amount: 30T (water consumption 0.5m for each ton of dregs); the make-up water includes: high salt water, industrial water and reuse water. The hardness of the flushing slag water is as follows: 3700 mg/L; alkalinity: 55 mg/L; pH: 6.5-7.

The pilot-scale system tests the turbidity of circulating water after 10 days of circulation by using the phosphorus-free low-temperature non-solidification phosphorus-free corrosion and scale inhibitor formula and the corresponding scale inhibition method of the embodiments 1 to 8 and the comparative example 1.

	Turbidity of water
		Example 1	4.3NTU
Example 2	6.8NTU
		Example 3	7.1NTU
Example 4	7.5NTU
		Example 5	2.4NTU
Example 6	5.7NTU
		Example 7	6.2NTU
Example 8	6.5NTU
		Comparative example 1	8.3NTU

It can be seen that the scale inhibitors of examples 1 and 5 can effectively prevent the generation of scale.

By adopting the low-temperature non-solidification phosphorus-free corrosion and scale inhibitor formula and the corresponding scale inhibition method of the embodiments 1-8 and the comparative example 1, a pilot-scale system is operated outdoors in winter, and the turbidity of circulating water is tested after 10 days of circulation.

	Turbidity of water
		Example 1	4.8NTU
Example 2	7.8NTU
		Example 3	8.2NTU
Example 4	8.9NTU
		Example 5	3.6NTU
Example 6	6.8NTU
		Example 7	7.4NTU
Example 8	8.5NTU
		Comparative example 1	9.7NTU

It can be seen that the scale inhibitors of examples 1 and 5 are effective in preventing scale from being produced even under low temperature conditions.

The scale inhibitor and the scale inhibition method in the embodiment 1 are used for the slag flushing water system of a certain steel plant to operate for three months, and the nozzle, the pipeline and the water flow channel only have slight scale, so that the normal operation is not influenced, and the metal pipeline is not obviously corroded.

The above detailed description is specific to possible embodiments of the present invention, and the above embodiments are not intended to limit the scope of the present invention, and all equivalent implementations or modifications that do not depart from the scope of the present invention should be included in the present claims.