CN104726882A - Efficient sulfuric acid pickling corrosion inhibitor and preparation method thereof - Google Patents
Efficient sulfuric acid pickling corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN104726882A CN104726882A CN201510133409.5A CN201510133409A CN104726882A CN 104726882 A CN104726882 A CN 104726882A CN 201510133409 A CN201510133409 A CN 201510133409A CN 104726882 A CN104726882 A CN 104726882A
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- sulfuric acid
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Abstract
The invention provides an efficient sulfuric acid pickling corrosion inhibitor and a preparation method thereof. The sulfuric acid pickling corrosion inhibitor is a combination of thiourea and derivatives of thiourea, imidazoline, quaternary ammonium salt and pure water which are in a mass ratio of (10-20):(10-20):(5-10):(50-75). The invention further provides the preparation method of the efficient sulfuric acid pickling corrosion inhibitor. The four substances are added in a stirrer in sequence according to a certain mass ratio and are mixed and dissolved to obtain the efficient sulfuric acid pickling corrosion inhibitor. The four substances are compounded according to a certain ratio; during the sulfuric acid pickling process, the corrosion inhibitor has better corrosion inhibiting effect on low-carbon steel than any one of the four substances if the four substances are used separately; in addition, the use amount of the corrosion inhibitor is smaller than sulfuric acid pickling corrosion inhibitors available in China and the chemical agent cost of pickling is saved. The efficient sulfuric acid pickling corrosion inhibitor provided by the invention has the advantages of small use amount and high corrosion inhibition effect and can be widely applied to the field of sulfuric acid pickling of industrial equipment.
Description
Technical field
The present invention relates to industrial equipments cleaning field, relate in particular to the development field of restrainer, refer to a kind of efficient sulfuric acid washing inhibiter and preparation method thereof especially.
Background technology
Pickling is widely used in the incrustation scale cleaning of heat-exchange equipment, heat transfer equipment and cooling apparatus etc. in each industrial sector, and particularly the pickling of the heat power equipment (as boiler) of power department is even more important.From socioeconomic angle, the fuel brought because of dirt can be reduced and expend; From the angle of environment protection, decrease exhaust combustion gases and topsoil; From the view of security, the heat power equipment such as boiler and interchanger in use forms all kinds of dirt gradually, and the bad boiler tube local temperature that causes of these dirt heat conduction raises, and reduces the intensity of steel, usually pipe explosion accident occurs, affect boiler operatiopn.Therefore pickling plays very important effect for the boiler operatiopn of power plant.The acid that pickling is commonly used has the mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, thionamic acid, and the organic acid such as citric acid, EDTA.But because acid all has corrosive nature to hardware, especially the corrosion of mineral acid is even more serious, the hydrogen of simultaneously releasing can spread to metal inside, makes to be washed equipment generation hydrogen embrittlement, and a large amount of sour gas of separating out in acid cleaning process, and labor condition can be made to worsen.Therefore to add inhibiter when pickling, to suppress the corrosion of metal in acidic medium, reduce the usage quantity of acid, improve pickling effect, extend the work-ing life of heat power equipment.Not only to consider the molten iron ability of acid during pickling, also should consider the factors such as dirty composition, metal material, method for treating waste liquid.Therefore select the measured inhibiter of a kind of matter to be the important step of pickling, and the corrosion inhibition understanding all kinds of inhibiter better can carry out anticorrosive work.
Sulfuric acid be everlasting pickling large usage quantity metallic substance acid dipping process in do cleaning host and in boiler fouling, calcium cpd content is very low for pickling boiler.Kind is more on the market at present for sulfuric acid washing inhibiter, but the problem that ubiquity corrosion inhibition rate is low.
Summary of the invention
The present invention is directed to above-mentioned Problems existing and deficiency, provide a kind of efficient sulfuric acid washing inhibiter and preparation method thereof, sulfuric acid washing inhibiter is combined by thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water, and the mass ratio of thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water is 10 ~ 20:10 ~ 20:5 ~ 10:50 ~ 75.The invention provides a kind of preparation method of efficient sulfuric acid washing inhibiter, by four kinds of materials according to certain mass ratio to put into successively in stirred vessel stirring and dissolving product of the present invention.In the present invention, four kinds of materials press certain mass than composite use, in sulfuric acid washing process, be obviously better than wherein any one material to the corrosion mitigating effect of soft steel be used alone, and the domestic existing sulfuric acid washing inhibiter usage quantity of amount ratio will be lacked, and can save the reagent cost of pickling.The consumption of the efficient sulfuric acid washing inhibiter in the present invention is few, corrosion inhibition rate is high, can be widely used in the sulfuric acid washing field of industrial equipments.
The technical solution adopted in the present invention is as follows:
The invention provides a kind of efficient sulfuric acid washing inhibiter and preparation method thereof, sulfuric acid washing inhibiter is combined by thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water, and the mass ratio of thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water is 10 ~ 20:10 ~ 20:5 ~ 10:50 ~ 75.
Described efficient sulfuric acid washing inhibiter, it is characterized in that: sulfuric acid washing inhibiter is combined by thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water, and the mass ratio of thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water is 10 ~ 20:10 ~ 20:5 ~ 10:50 ~ 75.
Described efficient sulfuric acid washing inhibiter, is characterized in that: described thiourea process is one or more in methylthiourea (MTU), ethyl thiourea, tolylthiourea (TTU) and chloro-phenyl-thiocarbamide (CPTU).
Described efficient sulfuric acid washing inhibiter, is characterized in that: described tetrahydroglyoxaline is one or more in glyoxal ethyline quinoline, 2-ethyl imidazol(e) quinoline, 2 isopropyl imidazole quinoline.
Described efficient sulfuric acid washing inhibiter, is characterized in that: described quaternary ammonium salt is one or more in Benzylmagnesium chloride quinoline, allyl group chloroquine.
Described efficient sulfuric acid washing inhibiter, is characterized in that: the preparation method that the invention provides a kind of efficient sulfuric acid washing inhibiter, by four kinds of materials according to certain mass ratio to put into successively in stirred vessel stirring and dissolving product of the present invention.
The present invention compared with prior art has the following advantages:
Sulfuric acid washing inhibiter of the present invention is combined by thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water; Thiourea process: in order to synthesize the raw material of the medicines such as Sulphathiazole, methionine(Met) and big porker sheet.As the raw material of dye well dyeing auxiliary, resin and molding powder.Also can be used as the catalyzer of the vulcanization accelerator of rubber, the flotation agent of metalliferous mineral, Tetra hydro Phthalic anhydride processed and fumaric acid, and be used as metal antirusting agent.Thiocarbamide is generally used as restrainer, the application of thiocarbamide corrosion inhibitor in oil field also appears in the newspapers, research data in recent years shows, thiocarbamide is not only used as the main component of compound restrainer, even can be used as the main component of iron and steel inhibiter in brine media; Tetrahydroglyoxaline: tetrahydroglyoxaline is after naphthenic acid and organic polyamine react, through water-soluble, the oil soluble product of modification; Product is applicable to refining equipment, and pressure regulating equipment as usual just pushes up, often push up, subtract top etc., hydrogenation unit, visbreaking unit etc.; Under middle hot conditions, to HCl-H
2s-H
2the corrosion of O system has good restraining effect, particularly has good result to high-sulfur crude oil refining process is anticorrosion, and product performance are better than domestic conventional related products now.
In the present invention, four kinds of materials press certain mass than composite use, in sulfuric acid washing process, be obviously better than wherein any one material to the corrosion mitigating effect of soft steel be used alone, and the domestic existing efficient sulfuric acid washing inhibiter usage quantity of amount ratio will be lacked, and can save the reagent cost of operation.
embodiment
Embodiment 1:
Choose raw material by weight percentage
Methylthiourea 10%,
Glyoxal ethyline quinoline 10%,
Benzylmagnesium chloride quinoline 5%,
All the other are water.
Reverse osmosis produced water, methylthiourea, glyoxal ethyline quinoline, Benzylmagnesium chloride quinoline are added in container in proportion successively, at room temperature stirs 2 ~ 3 hours, obtain product.
Embodiment 2:
Choose raw material by weight percentage
Tolylthiourea 10%,
2-ethyl imidazol(e) quinoline 10%,
Benzylmagnesium chloride quinoline 5%,
All the other are water.
Reverse osmosis produced water, tolylthiourea, 2-ethyl imidazol(e) quinoline, Benzylmagnesium chloride quinoline are added in container in proportion successively, at room temperature stirs 2 ~ 3 hours, obtain product.
Embodiment 3:
Choose raw material by weight percentage
Methylthiourea 15%,
Glyoxal ethyline quinoline 15%,
Allyl group chloroquine 10%,
All the other are water.
Reverse osmosis produced water, tolylthiourea, glyoxal ethyline quinoline, allyl group chloroquine are added in container in proportion successively, at room temperature stirs 2 ~ 3 hours, obtain product.
Embodiment 4:
Choose raw material by weight percentage
Methylthiourea 15%,
Glyoxal ethyline quinoline 15%,
Benzylmagnesium chloride quinoline 5%,
All the other are water.
Reverse osmosis produced water, methylthiourea, glyoxal ethyline quinoline, Benzylmagnesium chloride quinoline are added in container in proportion successively, at room temperature stirs 2 ~ 3 hours, obtain product.
Embodiment 5:
Choose raw material by weight percentage
Methylthiourea 15%,
Glyoxal ethyline quinoline 15%,
Allyl group base chloroquine 5%,
All the other are water.
Reverse osmosis produced water, methylthiourea, glyoxal ethyline quinoline, allyl group base chloroquine are added in container in proportion successively, at room temperature stirs 2 ~ 3 hours, obtain product.
Embodiment 6:
Choose raw material by weight percentage
Tolylthiourea 15%,
2-ethyl imidazol(e) quinoline 15%,
Benzylmagnesium chloride quinoline 8%,
All the other are water.
Reverse osmosis produced water, tolylthiourea, 2-ethyl imidazol(e) quinoline, Benzylmagnesium chloride quinoline are added in container in proportion successively, at room temperature stirs 2 ~ 3 hours, obtain product.
application test and result
one, experimental technique:
Weight-loss method surveys metallic corrosion speed:
(1) solution is joined: with reagent of sulfuric acid and distilled water preparation experiment solution, often kind of solution 800mL, is contained in 1000mL beaker respectively;
(2) sample is ground: specimen surface conditions dictate is homogeneous, bright and clean, needs to carry out surface treatment.Through machining during making sample, also need with emery cloth polishing before test, to meet the requirements of smooth finish.On the surface should without indentation and pit.The condition of surface of parallel sample will be tried one's best unanimously.It is overheated to note during polishing avoiding;
(3) marking code: sample marking, available grade of steel code printing numbering;
(4) take measurements: with length and width, the thick and hole diameter of vernier caliper measurement sample, for calculating exposed surface area.Several position must be measured during measurement, get its mean value;
(5) cleaning is deoiled: eliminated by specimen surface detritus, with the cotton ball wiping of leaching acetone, and removing surface and oil contaminant, then use distilled water flushing, filter paper blots.Then hair dryer drying (attention cold wind is used! ).Sample after cleaning can not be got with hand-held again, need be placed on clean filter paper;
(6) initial weight is claimed: dried sample analytical balance takes initial weight W
0, be accurate to 0.1mg;
(7) immersion test solution: sample puts on plastic cord after weighing immediately, (writes down the immersion time in immersion test solution! ).3 ~ 4 pieces of parallel samples are hung in often kind of testing liquid.Notice that sample can not contact with each other, can not contact with container.Sample immersion depth should be roughly the same.Its upper end should be greater than 2cm apart from liquid level.Observe and record the phenomenon occurred after sample immerses solution;
(8) test period: because the corrosion speed of carbon steel in the sulphuric acid soln of different concns differs greatly, the test period of different system should be determined as the case may be;
(9) corrosion product is removed: the change in specimen surface and solution before taking out sample, should be examined.Take out sample (to record the time! ) observe form and the distribution of specimen surface corrosion product afterwards.Sample is placed on tap water and flows down flushing, brush away loose corrosion product with hairbrush, again observe specimen surface state.Sample is used chemical method membrane removal.Except membrane operations should carry out repeatedly, to reach constant weight (difference of weighing for twice is less than 0.5mg), and by the loss of check sample determination metallic matrix;
(10) heavy after claiming corrosion: with distilled water flushing after membrane removal, removing has become loose corrosion product, and then wiping, drying, weigh with analytical balance.Weight after constant weight is as W heavy after corrosion
1.
two, experimental result:
The corrosion mitigating effect contrast table 1 of embodiment to soft steel in the sulfuric acid washing experiment of 20%
Chemical feeding quantity | Corrosion inhibition rate (carbon steel) | Chemical feeding quantity | Corrosion inhibition rate (carbon steel) | |
Embodiment 1 | 2.5‰ | 98.77% | 3‰ | 98.99% |
Embodiment 2 | 2.5‰ | 99.08% | 3‰ | 99.59% |
Embodiment 3 | 2.5‰ | 99.03% | 3‰ | 99.12% |
Embodiment 4 | 2.5‰ | 98.99% | 3‰ | 98.95% |
Embodiment 5 | 2.5‰ | 99.32% | 3‰ | 99.42% |
Embodiment 6 | 2.5‰ | 99.01% | 3‰ | 99.31% |
Claims (6)
1. the invention provides a kind of efficient sulfuric acid washing inhibiter and preparation method thereof, sulfuric acid washing inhibiter is combined by thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water, and the mass ratio of thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water is 10 ~ 20:10 ~ 20:5 ~ 10:50 ~ 75.
2. efficient sulfuric acid washing inhibiter according to claim 1, it is characterized in that: sulfuric acid washing inhibiter is combined by thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water, and the mass ratio of thiourea process, tetrahydroglyoxaline, quaternary ammonium salt and pure water is 10 ~ 20:10 ~ 20:5 ~ 10:50 ~ 75.
3. efficient sulfuric acid washing inhibiter according to claim 1, is characterized in that: described thiourea process is one or more in methylthiourea (MTU), ethyl thiourea, tolylthiourea (TTU) and chloro-phenyl-thiocarbamide (CPTU).
4. efficient sulfuric acid washing inhibiter according to claim 1, is characterized in that: described tetrahydroglyoxaline is one or more in glyoxal ethyline quinoline, 2-ethyl imidazol(e) quinoline, 2 isopropyl imidazole quinoline.
5. efficient sulfuric acid washing inhibiter according to claim 1, is characterized in that: described quaternary ammonium salt is one or more in Benzylmagnesium chloride quinoline, allyl group chloroquine.
6. efficient sulfuric acid washing inhibiter according to claim 1, it is characterized in that: the preparation method that the invention provides a kind of efficient sulfuric acid washing inhibiter, by four kinds of materials according to certain mass ratio to put into successively in stirred vessel stirring and dissolving product of the present invention.
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Cited By (6)
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CN104988518A (en) * | 2015-07-30 | 2015-10-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Hot rolling pickling corrosion inhibitor and pickling method by using the same |
CN104988520A (en) * | 2015-07-30 | 2015-10-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Corrosion inhibitor composition, and method for pickling by using corrosion inhibitor composition |
CN105002509A (en) * | 2015-07-30 | 2015-10-28 | 攀钢集团攀枝花钢铁研究院有限公司 | Corrosion inhibitor for pickling solution and pickling method adopting same |
CN105040007A (en) * | 2015-07-30 | 2015-11-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Acid adding inhibiter and method for acid pickling through acid adding inhibiter |
CN105132929A (en) * | 2015-09-24 | 2015-12-09 | 威海翔宇环保科技股份有限公司 | Chlorohydric acid pickling corrosion inhibitor and preparation method thereof |
CN114456786A (en) * | 2018-09-18 | 2022-05-10 | 陕西信业科技开发有限公司 | Corrosion inhibitor for deep well oil gas gathering and transportation and preparation method thereof |
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Cited By (8)
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CN104988518A (en) * | 2015-07-30 | 2015-10-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Hot rolling pickling corrosion inhibitor and pickling method by using the same |
CN104988520A (en) * | 2015-07-30 | 2015-10-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Corrosion inhibitor composition, and method for pickling by using corrosion inhibitor composition |
CN105002509A (en) * | 2015-07-30 | 2015-10-28 | 攀钢集团攀枝花钢铁研究院有限公司 | Corrosion inhibitor for pickling solution and pickling method adopting same |
CN105040007A (en) * | 2015-07-30 | 2015-11-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Acid adding inhibiter and method for acid pickling through acid adding inhibiter |
CN105040007B (en) * | 2015-07-30 | 2018-03-30 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method that addition carries out pickling with corrosion inhibiter and with addition in the acid with corrosion inhibiter in acid |
CN105132929A (en) * | 2015-09-24 | 2015-12-09 | 威海翔宇环保科技股份有限公司 | Chlorohydric acid pickling corrosion inhibitor and preparation method thereof |
CN105132929B (en) * | 2015-09-24 | 2018-04-17 | 威海翔宇环保科技股份有限公司 | A kind of hydrochloric acid pickling corrosion inhibitor and preparation method thereof |
CN114456786A (en) * | 2018-09-18 | 2022-05-10 | 陕西信业科技开发有限公司 | Corrosion inhibitor for deep well oil gas gathering and transportation and preparation method thereof |
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Application publication date: 20150624 |