CN109337650B - Low-corrosiveness snow melt liquid and preparation method thereof - Google Patents
Low-corrosiveness snow melt liquid and preparation method thereof Download PDFInfo
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- CN109337650B CN109337650B CN201811524528.3A CN201811524528A CN109337650B CN 109337650 B CN109337650 B CN 109337650B CN 201811524528 A CN201811524528 A CN 201811524528A CN 109337650 B CN109337650 B CN 109337650B
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Abstract
The invention discloses a preparation method of a low-corrosiveness snow melt liquid, which comprises the following steps: step A: proportioning according to the weight, taking 100kg of mother liquor with the PH value of 1-2, and adding 6-7 kg of calcium hydroxide into the mother liquor to obtain neutral mother liquor with the PH value of 6.5-7.5; and (B) step (B): b, pumping the neutral mother liquor in the step A into a wastewater tank, and standing for a period of time to obtain layered mother liquor; step C: filtering the upper mother liquor in the step B through filter cloth to obtain clear liquid, and adding 500-2000 g of activated carbon into the clear liquid to decolorize to obtain suspension; step D: and C, adding calcium chloride and potassium chloride into the suspension in the step, filtering by a filter cloth, and filtering by a PP cotton filter element machine to obtain clear liquid which is the snow melt. The invention aims to provide a low-corrosiveness snow-melting liquid and a preparation method thereof, wherein mother liquor after gallic acid crystallization is produced from galls is used as a raw material to prepare the low-corrosiveness snow-melting liquid, so that the low-corrosiveness snow-melting liquid has low corrosiveness to steel and low phytotoxicity.
Description
Technical Field
The invention belongs to the technical field of application of snow-melting agents, and particularly relates to a low-corrosiveness snow-melting liquid and a preparation method thereof.
Background
At present, industrial salt is still used for melting snow at home and abroad, and serious harm is brought to pavements, bridges and plants after the industrial salt is melted. It is reported that the use of industrial salt for snow melting in winter in a certain place causes excessive industrial salt in part of road sections and the death of trees and grass on both sides of the road due to excessive use, and the reason is that the soil salt is too high, so that the plants are difficult to absorb water and finally the plants die because the plants cannot absorb water for a long time. In addition, the salt can promote electrochemical corrosion of metal and accelerate corrosion of reinforcing steel bars. With the development of national economy, the highway construction of China is rapidly developed, and the highway traffic volume is increased year by year, so the research of the low-corrosion environment-friendly snow-melting agent is urgent.
According to analysis, the current environment-friendly snow-melting agent for roads is widely studied, and the related raw materials are also many, such as: organic acid potassium salt, papermaking waste liquid and the like are not produced in industry due to insufficient raw material supply, excessive production cost or other pollution; some products on the market are used for reducing the damage to the pavement and the addition of the calcium chloride into the antirust agent, so that the corrosion of the products to the steel bars is reduced, but the cost of the snow-melting agent is greatly increased, and the toxicity of the antirust agent to plants is relatively high, so that the antirust agent is difficult to popularize in a large area.
Galla chinensis is suitable for growing in warm and moist mountainous areas and hills. The main production area of China is concentrated in Guizhou, sichuan, hubei, hunan, shaanxi, yunnan and other 6 provinces, and the Chinese gall yield of the provinces accounts for more than 90 percent of the total national yield. The main ingredient of Galla chinensis is tannic acid, which is the main raw material for extracting gallic acid. However, the production process of nutgall generally generates a large amount of brown yellow waste liquid, and each 1 ton of gallic acid is produced to generate about 4.5 tons of waste liquid, and the waste liquid is mainly mother liquid formed after crystallization, contains about 1.2 percent of gallic acid, about 6 percent of sodium chloride, about 6 percent of glucose, and also contains about 0.3 percent of tannic acid, ellagic acid and the like, and the gallic acid has extremely low toxicity to human bodies, but if the waste liquid is directly discharged, the gallic acid is combined with ferrous ions in water or soil to form black complex, so that water and soil are blackened. It is worth noting that the gallic acid finished product has good application effect in rust prevention of ships, if the production wastewater is used for producing snow-melting liquid, the snow-melting liquid has the function of protecting bridge steel bars from salt corrosion, so how to develop low-corrosion environment-friendly snow-melting liquid by using the mother liquid becomes a technical problem to be solved urgently.
Disclosure of Invention
The invention aims at solving the problems and provides a preparation method of low-corrosiveness snow melt, which comprises the following steps:
step A: proportioning according to the weight, taking 100kg of mother liquor with the pH value of 1-2, adding 6-7 kg of calcium hydroxide into the mother liquor, and neutralizing to obtain neutral mother liquor with the pH value of 6.5-7.5;
and (B) step (B): b, pumping the neutral mother liquor in the step A into a wastewater tank, and standing for a period of time to obtain layered mother liquor;
step C: filtering the upper mother liquor in the step B through filter cloth to obtain clear liquid, and adding 500-2000 g of activated carbon into the clear liquid to decolorize to obtain suspension;
step D: and C, adding calcium chloride and potassium chloride into the suspension in the step, filtering by a filter cloth, and filtering by a PP cotton filter element machine to obtain clear liquid which is the snow melt.
And C, pumping the neutral mother liquor in the step B into a wastewater tank, and standing for more than 30 days.
And further, adding 10-30% of calcium chloride and 5-15% of potassium chloride to the total weight in the step D to obtain a mixed solution of 10-30% of calcium chloride and 5-15% of potassium chloride in the mother solution.
Further, the mesh number of the filter cloth in the step C is 350.
Further, the filtering precision of the PP cotton filter element machine in the step D is 1 micrometer.
The snow melt liquid obtained by the preparation method of the low-corrosiveness snow melt liquid comprises the following components in percentage by weight: 0.2-0.6% of tannic acid, 0.8-1% of gallic acid, 4-6% of glucose, 6-8% of sodium chloride, 5-15% of potassium chloride, 10-30% of calcium chloride and the balance of water.
Further, the composition comprises the following components in percentage by weight: tannic acid 0.25%, gallic acid 0.9%, glucose 4.5%, sodium chloride 7%, potassium chloride 10%, calcium chloride 12.5%, and water in balance.
A method for using low-corrosiveness snow-melting liquid is characterized in that the snow-melting liquid is sucked into a sprinkler, and the snow is melted on a road in a spraying mode along with the movement of the sprinkler.
The invention has the beneficial effects that: the mother liquor after gallic acid crystallization is prepared from gallnut as a raw material, so that the low-corrosiveness snow melt is weak in corrosiveness to steel in roads and bridges, has low toxicity to plants, is low in cost and meets the environmental protection requirement.
1. In the step A, mother liquor after gallic acid crystallization is strongly acidic, calcium hydroxide is added into the mother liquor until the mother liquor is neutralized to neutrality, so that phosphate radicals, sulfate radicals and plasmas are effectively removed, and the sedimentation of organic matters is facilitated.
2. In the step B, the suspension in the mother liquor starts layering under the standing condition, fine particles are coagulated together through interaction to form larger particles, then the larger particles are agglomerated again to form floccules, and the two react together to realize the standing layering of the suspension in the neutral mother liquor, so that the sedimentation of the suspension is realized, and the separation of the suspended large-particle matters in the neutral mother liquor by the filter cloth is facilitated.
3. In the step D, calcium chloride and potassium chloride are added into the supernatant, wherein the calcium chloride is a salt formed by chlorine element and calcium element, has extremely high hygroscopicity, is extremely deliquescent when exposed to air, is favorable for dissolving snow and easily dissolving in water, simultaneously emits a large amount of heat, and is difficult to form ice blocks after the salt is dissolved in snow water due to low solidifying point, so that the snow is favorably discharged, and the potassium chloride is also favorable for the same.
4. In the step D, the filtering by adopting the PP cotton filter element machine is used for removing suspended matters and large particles remained in the mother liquor mixed liquor, ensuring the purity of the finally obtained snow melt liquor and greatly reducing the COD content in the mother liquor.
5. Compared with the solid snow-melting agent, the liquid snow-melting liquid has great advantages in practical application, does not need to be packaged, unpacked, thrown manually, put up and down, and the like, and greatly saves the use cost and reduces the labor intensity.
6. In the invention, tannic acid, gallic acid and the like react with oxides on the surface of iron to form a layer of compact protective film, so that metal is isolated from air, water and salt, electrochemical corrosion of the metal is prevented, and the effect of slowing down corrosion of steel is achieved.
7. The snow melt liquid can be sucked into the sprinkler by a pump, and is sprayed by a sprayer to be uniformly sprayed on the snow surface, so that the effect of rapidly eliminating the snow crystalline state is realized, and the car is prevented from skidding on the snow surface.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Embodiment one:
the preparation method of the low-corrosiveness snow melt liquid comprises the following steps:
step A: taking 100kg of mother liquor with the pH value of 1 after gallic acid is produced by gallnut for crystallization, proportioning according to weight, adding 7kg of calcium hydroxide into the mother liquor, and neutralizing to obtain neutral mother liquor with the pH value of 7.5;
and (B) step (B): b, pumping the neutral mother liquor in the step A into a wastewater tank, and standing for 30 days to obtain layered mother liquor;
step C: filtering the upper mother liquor in the step B through 350-mesh filter cloth to obtain clear liquid, and adding 500g of activated carbon into the clear liquid to obtain suspension;
step D: and C, adding 20% of calcium chloride and 5% of potassium chloride into the suspension in the total weight in the step, filtering by a 350-mesh filter cloth, and filtering by a PP cotton filter element machine with the filtering precision of 1 micrometer to obtain clear liquid which is the snow melt.
The low-corrosiveness snow melt prepared according to the steps comprises the following components in percentage by weight: tannic acid 0.25%, gallic acid 0.9%, glucose 4.5%, sodium chloride 7%, potassium chloride 5%, calcium chloride 26.5%, and water in balance.
Embodiment two:
the preparation method of the low-corrosiveness snow melt liquid comprises the following steps:
step A: taking 100kg of mother liquor with the pH value of 2 after gallic acid is produced by gallnut for crystallization, proportioning according to weight, adding 6kg of calcium hydroxide into the mother liquor, and neutralizing to obtain neutral mother liquor with the pH value of 6.5;
and (B) step (B): b, pumping the neutral mother liquor in the step A into a wastewater tank, and standing for 40 days to obtain layered mother liquor;
step C: filtering the upper mother liquor in the step B through 350-mesh filter cloth to obtain clear liquid, and adding 2000g of active carbon into the clear liquid to obtain suspension;
step D: and C, adding 5% of calcium chloride and 15% of potassium chloride into the suspension in the step, filtering by a 350-mesh filter cloth, and filtering by a PP cotton filter element machine with the filtering precision of 1 micrometer to obtain clear liquid which is the snow melt.
The low-corrosiveness snow melt prepared according to the steps comprises the following components in percentage by weight: tannic acid 0.6%, gallic acid 0.8%, glucose 5%, sodium chloride 6%, potassium chloride 15%, calcium chloride 11%, and water in balance.
Embodiment III:
the preparation method of the low-corrosiveness snow melt liquid comprises the following steps:
step A: taking 100kg of mother liquor with the pH value of 1.4 after gallic acid is produced by gallnut for crystallization, proportioning according to weight, adding 6.5kg of calcium hydroxide into the mother liquor, and neutralizing to obtain neutral mother liquor with the pH value of 7;
and (B) step (B): b, pumping the neutral mother liquor in the step A into a wastewater tank, and standing for 35 days to obtain layered mother liquor;
step C: filtering the upper mother liquor in the step B through 350-mesh filter cloth to obtain clear liquid, and adding 1000g of activated carbon into the clear liquid to obtain suspension;
step D: and C, adding 10% of calcium chloride and 10% of potassium chloride into the suspension in the step, filtering by a 350-mesh filter cloth, and filtering by a PP cotton filter element machine with the filtering precision of 1 micrometer to obtain clear liquid which is the snow melt.
The low-corrosiveness snow melt prepared according to the steps comprises the following components in percentage by weight: tannic acid 0.5%, gallic acid 1%, glucose 5%, sodium chloride 8%, potassium chloride 10%, calcium chloride 16%, and water in balance.
The snow melt prepared by the preparation method is subjected to the following comparative tests:
experiment a: snow melt liquid solidification speed test experiment
In the experimental content, 100 milliliters of saturated sodium chloride solution, 100 milliliters of saturated calcium chloride solution, 100 milliliters of mother liquor calcium chloride saturated solution (namely, only excessive calcium chloride is added to be saturated in the preparation step D), 100 milliliters of mother liquor potassium chloride saturated solution (namely, only excessive potassium chloride is added to be saturated in the preparation step D), 100 milliliters of mother liquor 20 percent calcium chloride+15% potassium chloride solution (namely, 20 percent calcium chloride+15 percent potassium chloride of the total weight is simultaneously added in the preparation step D) are added into conical flasks filled with the solution, then the conical flasks are respectively placed into a freezing chamber with the test temperature of-24 ℃ for experiment, and the time required for starting icing to complete icing in each conical flask is recorded.
Table 1 experiment table for testing solidification speed of snow melt
From the above table 1, it can be seen that the mother liquor, 20% calcium chloride and 15% potassium chloride, has the slowest freezing speed and the strongest freezing resistance at the temperature of-24 ℃.
Experiment B: corrosion speed detection experiment of snow melt on screw steel
The experimental instrument is an FA1004 analytical balance, and the test conditions are normal temperature, static and semi-immersion methods. The experimental method is a weightlessness method, wherein rust and greasy dirt on the surface of the screw-thread steel are removed, and the screw-thread steel is placed in a drying box. Weighing after drying to the accuracy of ten-thousandth gram, respectively adding 600 milliliters of saturated sodium chloride solution, 600 milliliters of saturated calcium chloride solution, 600 milliliters of mother liquor calcium chloride saturated solution (namely, only adding excessive calcium chloride to be saturated in the preparation step D), 600 milliliters of mother liquor potassium chloride saturated solution (namely, only adding excessive potassium chloride to be saturated in the preparation step D), 600 milliliters of mother liquor 20% calcium chloride and 15% potassium chloride solution (namely, simultaneously adding 20% calcium chloride and 15% potassium chloride with the total weight in the preparation step D), respectively placing 3 weighed screw steels in each beaker, and removing rust after the test for weighing again, wherein the experimental results are shown in Table 2:
TABLE 2 comparison of corrosion Rate data of snow melt on threaded Steel
From the above table 2, it can be seen that the mother liquor has a good slow release effect on corrosion of screw-thread steel.
Experiment C: damage test experiment of snow melt liquid on plant
Experiments on the toxicity of the snow melt and the industrial salt to the lawn are carried out in factories of China limited development of the gallnut production industry of Hunan Linong, and the experiment time is as follows: the grass in early spring is very tender in 2017, 3 and 22 days, is sensitive to toxic substances, and has the following experimental contents: the saturated sodium chloride solution, the mother solution, 20% calcium chloride and 15% potassium chloride solution are diluted 10 times, and 1 liter of the solution is sprayed on the lawn with the area of 60CM multiplied by 60CM, and the spraying is carried out once in the morning, noon and supper for 3 times. After 3 days, leaves of the grass sprayed with the sodium chloride solution are curled somewhat, similar to dehydration, the grass sprayed with the mother liquor of 20% calcium chloride and 15% potassium chloride solution has no obvious phenomenon, and has no obvious difference from the surface phenomenon of the lawn which is not tested, and after 2 months, the grass sprayed with the sodium chloride solution has poor rising potential and is yellow. And the grass sprayed with the mother liquor of 20 percent of calcium chloride and 15 percent of potassium chloride has good growth condition. The specific test contents are as follows:
respectively diluting the saturated sodium chloride solution, the mother solution of 20 percent calcium chloride and 15 percent potassium chloride solution by 10 times, spraying 500 milliliters of liquid on 3 rapes with small growth vigor, spraying once in the morning, noon and supper, observing the growth condition of plants, and testing the good growth condition of the rapes sprayed with the mother solution of 20 percent calcium chloride and 15 percent potassium chloride solution, wherein the tip wilt of the 3 rapes sprayed with the sodium chloride solution occurs.
Experiment D: experiment of damage of snow-melting liquid to concrete structure pavement
The comparison was made with a 5-fold dilution of the mother liquor 20% calcium chloride+15% potassium chloride solution (i.e. 20% calcium chloride+15% potassium chloride by total weight was added simultaneously in preparation step D), respectively, a 5-fold dilution of the industrial salt saturated solution:
the test object is 42.5 ordinary Portland cement, the soaking time is 10 days after final setting for 28 days, and after taking out and draining, the test object is subjected to stress test, and the test result is shown in the following table 3:
table 3 comparison of damage test data of snow-melting liquid to concrete structural pavement
It can be seen from table 3 above that the degree of damage to the pavement of the concrete structure by the snow melt is significantly less than the damage procedure caused by direct use of industrial salt.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. The foregoing is merely illustrative of the preferred embodiments of this invention, and it is noted that there is objectively no limit to the specific structure disclosed herein, since numerous modifications, adaptations and variations can be made by those skilled in the art without departing from the principles of the invention, and the above-described features can be combined in any suitable manner; such modifications, variations and combinations, or the direct application of the inventive concepts and aspects to other applications without modification, are contemplated as falling within the scope of the present invention.
Claims (5)
1. The preparation method of the low-corrosiveness snow melt liquid is characterized by comprising the following steps of:
step A: proportioning according to the weight, taking 100kg of mother liquor with the pH value of 1-2, adding 6-7 kg of calcium hydroxide into the mother liquor, and neutralizing to obtain neutral mother liquor with the pH value of 6.5-7.5; wherein the mother solution is waste liquid formed after the crystallization of the produced gallic acid;
and (B) step (B): b, pumping the neutral mother liquor in the step A into a wastewater tank, and standing for a period of time to obtain layered mother liquor;
step C: filtering the upper mother liquor in the step B through filter cloth to obtain clear liquid, and adding 500-2000 g of activated carbon into the clear liquid to decolorize to obtain suspension;
step D: adding calcium chloride and potassium chloride into the suspension in the step C, filtering by a filter cloth, and filtering by a PP cotton filter element machine to obtain clear liquid which is snow melt; the snow melt liquid consists of the following components in percentage by weight: 0.2-0.6% of tannic acid, 0.8-1% of gallic acid, 4-6% of glucose, 6-8% of sodium chloride, 5-15% of potassium chloride, 10-30% of calcium chloride and the balance of water.
2. The method for preparing a low-corrosiveness snow-melting liquid according to claim 1, wherein the neutral mother liquor in the step B is left standing for 30 days or more.
3. The method for preparing a low-corrosiveness snow-melting liquid according to claim 1, wherein the mesh number of the filter cloth in the step C is 350.
4. The method for preparing a low-corrosion snow melt according to claim 1, wherein the filtering precision of the PP cotton filter element machine in the step D is 1 micron.
5. The method for using the snow melt prepared by the preparation method according to claim 1, wherein the snow melt is sucked into a sprinkler, and the snow melt is performed on a road in a spraying manner along with the movement of the sprinkler.
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