CN111187099A - Preparation method of calcium nitrate-containing secondary element water-soluble fertilizer liquid product - Google Patents
Preparation method of calcium nitrate-containing secondary element water-soluble fertilizer liquid product Download PDFInfo
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Abstract
A preparation method of a calcium nitrate-containing medium element water-soluble fertilizer liquid product is characterized by comprising the following sequential steps of ⒈ adding a small amount of clear water into a reactor to serve as a base solution, adding deplating waste nitric acid and 20-25% of lime milk in a parallel flow mode, keeping the pH value of reaction liquid to be 5-7, stopping feeding after a set volume is reached, ⒉ taking 10-20 ml of reaction slurry and filtering, dropwise adding 0.1ml of heavy metal capture agent into filtrate, continuously adding the deplating waste nitric acid and the heavy metal capture agent into the reactor according to the proportion of 1000: 2(V/V) if black precipitates are generated, ⒊ repeating the step 2 until the filtrate has no black precipitates, filtering the slurry to obtain a calcium nitrate crude solution, ⒋ adding activated carbon into the calcium nitrate crude solution to remove organic impurities, filtering, and evaporating and concentrating the calcium nitrate solution to a specific gravity of 1.28-1.45, and cooling to the room temperature to obtain the medium element water-soluble fertilizer liquid product with the calcium nitrate content of 100-160 g/l.
Description
The technical field is as follows:
the invention relates to a preparation method of a calcium nitrate-containing secondary element water-soluble fertilizer liquid product, belonging to the technical field of producing liquid fertilizers by utilizing industrial wastes in the surface treatment industry.
Background art:
the deplating is a process in the production process of the surface treatment industry, and the deplating waste nitric acid is waste liquid generated by selectively dissolving metal copper, nickel and tin covered on a base material by a nitric acid type deplating agent under the condition of ensuring that the base material is not eroded. For example, the copper-stripping waste nitric acid contains 20-40% of nitric acid and 50-130 g/L of copper, the nickel-stripping waste nitric acid contains 20-40% of nitric acid and 5-50 g/L of nickel, and the tin-stripping waste nitric acid contains 20-30% of nitric acid, 50-150 g/L of tin, 1-20 g/L of copper and 5-20 g/L of iron.
For deplating waste nitric acid, the most common pretreatment method is an acid-base neutralization method, namely, alkaline materials such as ammonia water, ammonium carbonate, ammonium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, lime and the like are adopted to neutralize free nitric acid in waste liquid, and copper, nickel and tin ions in the waste liquid are precipitated; obtaining mud cakes containing heavy metal compounds through filter pressing, and selling the mud cakes to downstream metal smelting factories to refine copper, nickel and tin, or continuously producing products such as metastannic acid, tin dioxide, sodium stannate and the like. The related patent technologies comprise CN104986892A, CN101497458B, CN101984097A, CN102766883B, CN1211503C, CN103482688A, CN105330080B, CN105460972B, CN101532096B, CN102086073B, CN101948133B and the like.
However, these patent technologies are mostly confused about the actual orientation of the sodium nitrate, ammonium nitrate or calcium nitrate solution generated during the neutralization process, or have poor operability. For example, CN102766883B waited for a process of returning a sodium nitrate solution to a tin stripping production line after supplementing nitric acid and a small amount of additives, but accumulation of sodium salts in tin stripping water would affect the tin stripping effect, and finally, another path for excess sodium nitrate solution was required. In addition, CN102775197B proposes a concept of processing an ammonium nitrate solution into a fertilizer-grade ammonium nitrate concentrated solution; however, the nitrogen content of the ammonium nitrate concentrated solution is low, and the use willingness of downstream fertilizer plants is not high. The schemes of processing the calcium nitrate solution into the solid calcium nitrate tetrahydrate product and the scheme of processing the sodium nitrate solution into the solid sodium nitrate product, which are respectively introduced in CN103408164B and CN102086073B, and the scheme of processing the sodium nitrate solution into the solid sodium nitrate product, which is introduced in CN105460972B, have higher practicability; however, solid sodium nitrate and solid calcium nitrate are listed in the book of easily exploding dangerous chemicals (2017), and related enterprises have great difficulty in handling safety production licenses.
On the other hand, the liquid fertilizer is applied later in large scale in China, but has the advantages of low production cost, high fertilizer efficiency, high fertilizer utilization rate, suitability for water and fertilizer integration, outstanding environmental benefit and the like, and is developed rapidly in recent years. Wherein, the 'water soluble fertilizer with medium elements' (NY 2266) -2012 mentions the technical index of the liquid product of the water soluble fertilizer with medium elements, and the content of calcium or calcium and magnesium in the liquid is required to be not less than 100 g/L.
Calcium is one of indispensable medium elements of crops, and mainly plays roles in stabilizing cell walls and cell membranes, activating specific enzyme activity, promoting growth of young roots, stems and leaves, delaying crop aging and the like in crops. Wherein, the vegetables are calcium-loving crops, the calcium absorption of the radish and the tomato is 10 times higher than that of the wheat and the rice, and the calcium absorption of the cabbage is 25 times higher than that of the wheat. In China, the phenomenon of calcium deficiency in the planting process of fruits and vegetables is common, especially in the south. The lack of calcium in crops can cause the growth failure of terminal buds and the top of root systems, and in severe cases, the growth points are necrotic, and the root systems become black and rot. The navel rot of tomatoes and sweet peppers, the dry heart of Chinese cabbages, the scorched leaf of lettuce and cabbage, the bitter pox and pox leaf of apples, the fruit cracking of litchis, cherries and oranges and the like are common calcium deficiency physiological diseases on fruits and vegetables, and the yield and the quality of the fruits and vegetables are seriously influenced. The reason for the lack of calcium in crops is that the soil in south China is generally lack of calcium, but most of fertilizers supplied in the market mainly comprise high-concentration nitrogen, phosphorus and potassium elements, and medium elements and trace elements are not supplemented in a targeted manner, so that the nutrient supply is unbalanced. Secondly, excessive use of nitrogen fertilizer, drought, salt and alkali and the like can affect the absorption of calcium by crops.
The calcium nitrate is a water-soluble nitrogen-calcium compound fertilizer, and has the characteristics of quickly supplementing calcium and nitrogen although the price is low. The calcium nitrate is suitable for various soils, and has better application effect on the southern acid soil which is lack of calcium; can be applied by basal application, topdressing, irrigation and foliage spraying, and can also be used as nutrient solution for soilless culture. In addition, calcium nitrate is most suitable for application to crops such as beet, potato, barley, hemp, citrus, and longan. The stress resistance of the fruits and vegetables can be enhanced and the precocity can be promoted by applying calcium nitrate to the fruits and vegetables; the hardness of the fruit is increased, and fruit cracking and spots are prevented; meanwhile, the plant diseases caused by infection of certain bacteria and fungi can be relieved, and the storage stability and the quality guarantee period of the fruits are increased.
The invention content is as follows:
the invention aims to provide a method for producing a safe and effective secondary element water-soluble fertilizer liquid product, namely a preparation method of a secondary element water-soluble fertilizer liquid product containing calcium nitrate.
The purpose of the invention is realized as follows:
a: preparing reaction slurry: adding clear bottoming water into a reactor as a base solution, simultaneously adding deplating waste nitric acid and 20-25% lime milk in a parallel flow mode, adjusting the flow rate of the deplating waste nitric acid and the lime milk to maintain the pH value of the reaction solution to be 5-7, and stopping feeding after the reaction solution reaches a set volume;
b: taking 10-20 ml of the reaction slurry obtained in the step A, filtering the reaction slurry by using filter paper, and adding 0.1ml of heavy metal capture agent into the filtrate by using a dropper; when black precipitates are generated, returning filter mud and filtrate into the reactor, and adding a heavy metal capture agent into the reactor according to the proportion of deplating waste nitric acid to the heavy metal capture agent which is 1000 to 2V/V;
c: repeating the step B until no black precipitate exists in the filtrate, and filtering the slurry to obtain a yellowish crude calcium nitrate solution;
d: removing organic impurities: c, adding active carbon into the coarse calcium nitrate solution obtained in the step C by stirring to remove polycyclic aromatic hydrocarbon organic impurities, wherein the addition amount of the active carbon is 0.1-0.5% W/W of the coarse calcium nitrate solution, and filtering to obtain a clear and transparent calcium nitrate solution;
e: carrying out evaporation concentration on the calcium nitrate solution by adopting a reduced-pressure low-temperature evaporation technology with the evaporation temperature of 38-50 ℃; and stopping evaporation when the specific gravity of the calcium nitrate concentrated solution reaches 1.28-1.45, and cooling to room temperature to obtain a secondary element water-soluble fertilizer liquid product with the calcium content of 100-160 g/L.
In a preferred scheme, the deplating waste nitric acid used in the step A is tin deplating waste nitric acid.
In a preferred scheme, the deplating waste nitric acid used in the step A is deplating waste nitric acid.
In a preferred scheme, the deplating waste nitric acid used in the step A is nickel-deplating waste nitric acid.
In a preferred scheme, the heavy metal trapping agent adopted in the step B is 15% sodium trithiocyanate solution TMT-15.
In a preferable scheme, the heavy metal trapping agent adopted in the step B is 20% sodium dimethyldithiocarbamate solution DTC-20.
The invention can effectively realize the complete reclamation of copper, nickel, tin and nitrate nitrogen in the deplating waste nitric acid. The process is safe and efficient, and the obtained calcium nitrate concentrated solution completely meets the agricultural industry standard 'secondary element water-soluble fertilizer' (NY 2266-: wherein the content of calcium (Ca) is more than or equal to 100g/L, the content of water-insoluble substances is less than or equal to 50g/L, the pH (1:250 times dilution) is 3.0-9.0, the content of mercury (Hg) is less than or equal to 5mg/Kg, the content of arsenic (As) is less than or equal to 10mg/Kg, the content of cadmium (Cd) is less than or equal to 10mg/Kg, the content of lead (Pb) is less than or equal to 50mg/Kg, and the content of chromium (Cr) is less than or equal to 50mg/Kg, and the calcium (Ca) can be directly applied to agricultural. The parallel flow feeding mode adopted by the invention can eliminate NOx waste gas pollution in the positive addition or reverse addition neutralization process of lime and deplating waste nitric acid and improve the production operation environment; the application of the heavy metal trapping agent can ensure that the heavy metal content of the calcium nitrate solution is far lower than the standard requirement of a medium element water-soluble fertilizer product. The application of the activated carbon is beneficial to eliminating the doubt that the public harms the human health and the ecological environment by the durable organic pollutants of Polycyclic Aromatic Hydrocarbons (PAHs) through a food chain in the planting process of the calcium nitrate concentrated solution of the crops; the calcium nitrate solution is concentrated by adopting a low-temperature evaporation technology, so that the problem of scaling of the calcium nitrate solution in an evaporator can be remarkably solved.
The specific implementation mode is as follows:
example 1:
firstly, taking a 3L three-neck flask, adding 200 ml of clear water for bottoming, and inserting a pH meter below the liquid level; then, 1 liter of measuring cylinder is respectively used for containing 1.0 liter of tin-stripping waste nitric acid a and 25 percent of lime milk, and the tin-stripping waste nitric acid a and the lime milk are respectively connected with the flask through two peristaltic pumps and hoses. Starting stirring, starting a peristaltic pump, and simultaneously injecting the tin-stripping waste nitric acid a and the lime milk into clear water for neutralization and precipitation reaction; the flow rate of the tin-stripping waste nitric acid a is fixed to be 25 ml/min, and the flow rate of the lime milk is adjusted to ensure that the pH value of the reaction liquid is 5-7. When the addition of 1 liter of tin-stripping waste nitric acid a is finished, the addition of lime milk is stopped, but stirring is continued.
Then, 20ml of the reaction slurry obtained by the above treatment is taken, filtered by filter paper, 0.1ml of heavy metal trapping agent, in this example, 15% sodium trithiocyanate solution TMT-15 is added into the filtrate by a dropper, and black precipitate is generated; pouring the filter mud and the filtrate into the flask, adding the tin-stripping waste nitric acid and the heavy metal capture agent into TMT-15 according to a ratio of 1000: 2(V/V), namely measuring 2.0 ml of TMT-15, adding the measured TMT-15 into the slurry of the flask, and stirring for 5 minutes; taking 20ml of reaction slurry again, filtering with filter paper, adding 0.1ml of TMT-15 into the filtrate by using a dropper, and generating no black precipitate; the mud and filtrate were poured back into the flask and stirring was stopped. The slurry in the flask was suction filtered to obtain a yellowish crude solution of calcium nitrate of 2093 g.
Subsequently, the crude calcium nitrate solution was poured into a 2 l beaker, 10 g (0.48% W/W) of powdered activated carbon was added with stirring, and after 5 minutes the reaction was suction filtered to give a colorless and transparent calcium nitrate solution.
The main component contents of the calcium nitrate solution are shown in table 1. The calcium nitrate solution is put into a rotary evaporator evaporation flask with the specification of 5 liters, evaporation is carried out at 38 ℃, the evaporation is stopped when calibrated scales are reached, and the solution is cooled to 30 ℃ to obtain 1152 g of calcium nitrate concentrated solution with the specific gravity of 1.284 (the content of main components is shown in table 1), and the calcium nitrate concentrated solution can be directly applied to agricultural production as a medium element water-soluble fertilizer liquid product.
TABLE 1 main Components and contents of calcium nitrate concentrates prepared using spent nitric acid from tin stripping
Example 2:
firstly, 0.5m tap water3Adding into a container with a volume of 5m3Respectively starting an industrial on-line pH meter and a stirring slurry, then starting a tin-stripping waste nitric acid b and a 25% lime milk feeding pump, and simultaneously injecting the tin-stripping waste nitric acid b and the lime milk into the reaction kettle I for neutralization and precipitation reaction; the flow of the fixed tin-stripping waste nitric acid b is 1m3Adjusting the flow rate of lime milk to ensure that the pH value of the reaction liquid is 5-7; when 2m3And after the feeding of the tin-stripping waste nitric acid b is finished, closing a tin-stripping waste nitric acid and lime milk feeding pump, and continuously stirring.
Then, 20ml of reaction slurry is taken, filtered by filter paper, 0.1ml of heavy metal trapping agent, which is 20% sodium dimethyldithiocarbamate solution DTC-20 in the embodiment, is added into the filtrate by a dropper, and black precipitate is generated; pouring the filter mud and the filtrate into a reaction kettle I, adding the tin-stripping waste nitric acid and the heavy metal capture agent into DTC-20 according to a ratio of 1000: 2(V/V), namely measuring 4.0L of DTC-20, adding the mixture into the slurry, and stirring for 5 minutes. Taking 20ml of reaction slurry for the second time, filtering by using filter paper, adding 0.1ml of DTC-20 into the filtrate, and generating black precipitate; pouring the filter mud and the filtrate into the reaction kettle I again, adding the tin-stripping waste nitric acid and the heavy metal capture agent into DTC-20 according to a ratio of 1000: 2(V/V), namely measuring 4.0L of DTC-20, adding the mixture into the slurry, and stirring for 5 minutes. And (3) taking 20ml of reaction slurry for the third time, filtering the reaction slurry by using filter paper, adding 0.1ml of DTC-20 into the filtrate, pouring the filter mud and the filtrate into the reaction kettle when no black precipitate is generated, and stopping stirring. The slurry was press-filtered with a filter press to obtain 3228 kg of a yellowish crude calcium nitrate solution.
Subsequently, the crude calcium nitrate solution was transferred in its entirety by 5m35 kg of activated carbon (0.15% W/W) is added into the reaction kettle II under stirring, and after 5 minutes, the reactant is subjected to pressure filtration to obtain a colorless and transparent calcium nitrate solution.
The main component contents of the calcium nitrate solution are shown in Table 2. 233 kg of calcium nitrate solution is taken, injected into low-temperature evaporation equipment with the evaporation capacity of 110 kg/h in batches, and evaporated and concentrated at the temperature of 48-50 ℃, and finally, 128 kg of evaporated condensate water and 97 kg of calcium nitrate concentrated solution with the specific gravity of 1.396 are obtained (the main component content is shown in table 2).
TABLE 2 main components and contents of calcium nitrate concentrate prepared by using tin-stripping waste nitric acid
Example 3:
firstly, taking a 3L three-neck flask, adding 200 ml of clear water for bottoming, and inserting a pH meter below the liquid level; then, 1 liter of measuring cylinder is used for containing 1.0 liter of copper-removing waste nitric acid c and 25 percent of lime milk respectively, and the copper-removing waste nitric acid c and the lime milk are respectively connected with the flask through two peristaltic pumps and hoses. Starting stirring, starting a peristaltic pump, and simultaneously injecting the copper-removing waste nitric acid c and the lime milk into clear water for neutralization and precipitation reaction; and (3) fixing the flow rate of the copper-removing waste nitric acid c to be 25 ml/min, and adjusting the flow rate of lime milk to ensure that the pH value of the reaction liquid is 5-7. When the addition of 1 liter of copper-withdrawing waste nitric acid A is finished, the addition of lime milk is stopped, but stirring is continued.
Then, 20ml of reaction slurry is taken out and filtered by filter paper, 0.1ml of heavy metal trapping agent, which is 20% sodium dimethyldithiocarbamate solution DTC-20 in the embodiment, is added into the filtrate, and black precipitate is generated; pouring the filter mud and the filtrate into the flask, adding the copper-removing waste nitric acid and the heavy metal capture agent into DTC-20 according to a ratio of 1000: 2(V/V), namely measuring 2.0 ml of DTC-20, adding the mixture into the slurry, and stirring for 5 minutes. Taking 20ml of reaction slurry again, filtering with filter paper, adding 0.1ml of DTC-20 into the filtrate, and generating no black precipitate; the mud and filtrate were poured back into the flask and stirring was stopped. The slurry was filtered by suction to give 2125 g of a yellowish crude calcium nitrate solution.
Subsequently, the crude calcium nitrate solution was poured into a 5 l beaker, 8 g of activated carbon (0.38% W/W) was added with stirring, and after 5 minutes the reaction was filtered with suction to give a colorless and transparent calcium nitrate solution.
The main component contents of the calcium nitrate solution are shown in Table 3. The calcium nitrate solution was put into a 5-liter rotary evaporator evaporation flask, and evaporated at 45 ℃ until the scale was calibrated, and cooled to 30 ℃ to obtain 1294 g of a calcium nitrate concentrated solution having a specific gravity of 1.454 (the contents of the main components are shown in table 3).
TABLE 3 main components and contents of calcium nitrate concentrates prepared using copper depleted spent nitric acid
Example 4:
firstly, 0.4m tap water3Adding into a container with a volume of 5m3Respectively starting an industrial on-line pH meter and a stirring slurry, then starting a copper-removing waste nitric acid d and a 20% lime milk feeding pump, and simultaneously injecting the copper-removing waste nitric acid d and the lime milk into the reaction kettle I for neutralization and precipitation reaction; the flow of the fixed copper-removing waste nitric acid d is 1m3Adjusting the flow rate of lime milk to ensure that the pH value of the reaction liquid is 5-7; when 2m3And after the feeding of the copper-removing waste nitric acid d is finished, closing the copper-removing waste nitric acid d and the lime milk feeding pump, and continuously stirring.
Then, 20ml of reaction slurry is taken, filtered by filter paper, and 0.1ml of heavy metal trapping agent, in this example, 15% sodium trithiocyanate solution TMT-15, is added into the filtrate, and black precipitate is generated; pouring the filter mud and the filtrate into a reaction kettle I, adding the copper-removing waste nitric acid and the heavy metal capture agent into TMT-15 according to a ratio of 1000: 2(V/V), namely measuring 4.0L of TMT-15, adding the mixture into the slurry, and stirring for 5 minutes. Taking 20ml of reaction slurry for the second time, filtering by using filter paper, adding 0.1ml of TMT-15 into the filtrate, and generating black precipitate; pouring the filter mud and the filtrate into the reaction kettle I again, adding the copper-removing waste nitric acid and the heavy metal capture agent into TMT-15 according to a ratio of 1000: 2(V/V), namely weighing 4.0 liters of TMT-15, adding the mixture into the slurry, and stirring for 5 minutes. And (3) taking 20ml of reaction slurry for the third time, filtering by using filter paper, adding 0.1ml of TMT-15 into the filtrate, pouring the filter mud and the filtrate into the reaction kettle when no black precipitate is generated, and stopping stirring. And (4) carrying out pressure filtration on the slurry by using a filter press to obtain 4396 kg of yellowish crude calcium nitrate solution.
Subsequently, the crude calcium nitrate solution was transferred in its entirety by 5m3And (3) adding 15 kg of 0.34% W/W of activated carbon into the reaction kettle II under stirring, and carrying out pressure filtration on the reactant after 5 minutes to obtain a colorless and transparent calcium nitrate solution.
The main component contents of the calcium nitrate solution are shown in Table 4. Injecting 250 kg of calcium nitrate solution into low-temperature evaporation equipment with the evaporation capacity of being nominally 110 kg/h in batches, and carrying out evaporation concentration at 38-40 ℃ to finally obtain 151 kg of evaporation condensate water and 89 kg of calcium nitrate concentrated solution with the specific gravity of 1.430 (the content of main components is shown in Table 4).
TABLE 4 main components and contents of calcium nitrate concentrates prepared using copper depleted spent nitric acid
Example 5:
firstly, taking a 3L three-neck flask, adding 200 ml of clear water for bottoming, and inserting a pH meter below the liquid level; then, 1 liter of measuring cylinder is used for containing 1.0 liter of nickel-removing waste nitric acid e and 25 percent of lime milk respectively, and the nickel-removing waste nitric acid e and the lime milk are respectively connected with the flask through two peristaltic pumps and hoses. Starting stirring, starting a peristaltic pump, and simultaneously injecting the nickel-removing waste nitric acid e and the lime milk into clear water for neutralization and precipitation reaction; and (3) fixing the flow rate of the nickel-removing waste nitric acid e to be 25 ml/min, and adjusting the flow rate of lime milk to ensure that the pH value of the reaction liquid is 5-7. When the addition of the 1 liter of nickel-withdrawing waste nitric acid e is finished, the addition of the lime milk is stopped, but the stirring is continued.
Then, 20ml of the reaction slurry obtained by the above treatment is taken, filtered by filter paper, and 0.1ml of heavy metal trapping agent, which is 15% sodium trithiocyanate solution TMT-15 in the embodiment, is added into the filtrate, and black precipitate is generated; pouring the filter mud and the filtrate into the flask, adding the nickel-removing waste nitric acid and the heavy metal capture agent into TMT-15 according to a ratio of 1000: 2(V/V), namely measuring 2.0 ml of TMT-15, adding the TMT-15 into the slurry of the flask, and stirring for 5 minutes; taking 20ml of reaction slurry for the second time, filtering by using filter paper, adding 0.1ml of TMT-15 into the filtrate, and generating black precipitate; pouring the filter mud and the filtrate into the flask again, adding the nickel-removing waste nitric acid and the heavy metal capture agent into TMT-15 according to a ratio of 1000: 2(V/V), namely measuring 2.0 ml of TMT-15, adding the mixture into the slurry, and stirring for 5 minutes; and taking 20ml of reaction slurry for the third time, filtering the reaction slurry by using filter paper, adding 0.1ml of TMT-15 into the filtrate, pouring the filter mud and the filtrate into the flask when no black precipitate is generated, and stopping stirring. The slurry in the flask was suction filtered to give 2253 g of a yellowish crude calcium nitrate solution.
Subsequently, the crude calcium nitrate solution was poured into a 2 l beaker and 5 g (0.22% W/W) of powdered activated carbon was added with stirring, and after 5 minutes the reaction was filtered with suction to give a colorless and transparent calcium nitrate solution.
The main component contents of the calcium nitrate solution are shown in Table 5. The calcium nitrate solution was put into a 5-liter rotary evaporator evaporation flask, and evaporated at 50 ℃ until the scale was marked, and cooled to 30 ℃ to obtain 1650 g of a calcium nitrate concentrated solution with a specific gravity of 1.348 (the contents of the main components are shown in Table 5).
TABLE 5 main Components and contents of calcium nitrate concentrates prepared using spent nitric acid from nickel stripping
Example 6:
firstly, 0.4m tap water3Adding into a container with a volume of 5m3Respectively starting an industrial on-line pH meter and a stirring slurry, then starting a nickel-removing waste nitric acid f and a 20% lime milk feeding pump, and simultaneously injecting the nickel-removing waste nitric acid f and the lime milk into the reaction kettle I for going onAnd a precipitation reaction; flow of fixed nickel-removing waste nitric acid f is 1m3Adjusting the flow rate of lime milk to ensure that the pH value of the reaction liquid is 5-7; when 2m3And after the feeding of the nickel-removing waste nitric acid f is finished, closing the nickel-removing waste nitric acid and lime milk feeding pump, and continuously stirring.
Then, 20ml of reaction slurry is taken out and filtered by filter paper, 0.1ml of heavy metal trapping agent is added into the filtrate, in the embodiment, the heavy metal trapping agent is 20% sodium dimethyldithiocarbamate solution DTC-20, and black precipitate is generated; and pouring the filter mud and the filtrate into a reaction kettle I, adding the nickel-removing waste nitric acid and the heavy metal capture agent into DTC-20 according to the ratio of 1000: 2(V/V), namely measuring 4.0L of DTC-20, adding the mixture into the slurry, and stirring for 5 minutes. Taking 20ml of reaction slurry for the second time, filtering by using filter paper, adding 0.1ml of DTC-20 into the filtrate, and generating black precipitate; pouring the filter mud and the filtrate into the reaction kettle I again, adding the nickel-removing waste nitric acid and the heavy metal capture agent into DTC-20 according to the ratio of 1000: 2(V/V), namely measuring 4.0L of DTC-20, adding the mixture into the slurry, and stirring for 5 minutes. And (3) taking 20ml of reaction slurry for the third time, filtering the reaction slurry by using filter paper, adding 0.1ml of DTC-20 into the filtrate, pouring the filter mud and the filtrate into the reaction kettle when no black precipitate is generated, and stopping stirring. The slurry was filter-pressed with a filter press to obtain 4658 kg of a yellowish crude calcium nitrate solution.
Subsequently, the crude calcium nitrate solution was transferred in its entirety by 5m315 kg of activated carbon (0.32% W/W) is added into the reaction kettle II under stirring, and after 5 minutes, the reactant is subjected to pressure filtration to obtain a colorless and transparent calcium nitrate solution.
The main component contents of the calcium nitrate solution are shown in Table 6. 240 kg of calcium nitrate solution is taken, injected into low-temperature evaporation equipment with the evaporation capacity of being nominally 110 kg/h in batches, and evaporated and concentrated at 44-46 ℃, and finally 125 kg of evaporated condensate water and 107 kg of calcium nitrate concentrated solution with the specific gravity of 1.374 are obtained (the main component content is shown in table 6).
TABLE 6 main components and contents of calcium nitrate concentrate prepared by using nickel-removed waste nitric acid
Claims (6)
1. A preparation method of a calcium nitrate-containing secondary element water-soluble fertilizer liquid product comprises the following steps:
a: preparing reaction slurry: adding clear bottoming water into a reactor as a base solution, simultaneously adding deplating waste nitric acid and 20-25% lime milk in a parallel flow mode, adjusting the flow rate of the deplating waste nitric acid and the lime milk to maintain the pH value of the reaction solution to be 5-7, and stopping feeding after the reaction solution reaches a set volume;
b: taking 10-20 ml of the reaction slurry obtained in the step A, filtering the reaction slurry by using filter paper, and adding 0.1ml of heavy metal capture agent into the filtrate by using a dropper; when black precipitates are generated, returning filter mud and filtrate into the reactor, and adding a heavy metal capture agent into the reactor according to the proportion of deplating waste nitric acid to the heavy metal capture agent which is 1000 to 2V/V;
c: repeating the step B until no black precipitate exists in the filtrate, and filtering the slurry to obtain a yellowish crude calcium nitrate solution;
d: removing organic impurities: c, adding active carbon into the coarse calcium nitrate solution obtained in the step C by stirring to remove polycyclic aromatic hydrocarbon organic impurities, wherein the addition amount of the active carbon is 0.1-0.5% W/W of the coarse calcium nitrate solution, and filtering to obtain a clear and transparent calcium nitrate solution;
e: carrying out evaporation concentration on the calcium nitrate solution by adopting a reduced-pressure low-temperature evaporation technology with the evaporation temperature of 38-50 ℃; and stopping evaporation when the specific gravity of the calcium nitrate concentrated solution reaches 1.28-1.45, and cooling to room temperature to obtain a secondary element water-soluble fertilizer liquid product with the calcium content of 100-160 g/L.
2. The method for producing a secondary element water-soluble fertilizer liquid product containing calcium nitrate according to claim 1, wherein the deplating waste nitric acid used in the step a is a tin-deplating waste nitric acid.
3. The method for producing a secondary element water-soluble fertilizer liquid product containing calcium nitrate according to claim 1, wherein the deplating waste nitric acid used in the step a is deplating waste nitric acid.
4. The method for producing a secondary element water-soluble fertilizer liquid product containing calcium nitrate according to claim 1, wherein the deplating waste nitric acid used in the step a is a nickel-deplating waste nitric acid.
5. The process for preparing a secondary element water-soluble fertilizer liquid product containing calcium nitrate as claimed in claim 1, wherein the heavy metal scavenger used in step B is 15% sodium tripolyphosphate solution TMT-15.
6. The process for preparing a secondary element water-soluble fertilizer liquid product containing calcium nitrate as claimed in claim 1, characterized in that the heavy metal scavenger used in step B is 20% sodium dimethyldithiocarbamate solution DTC-20.
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|---|---|---|---|---|
| CN112790074A (en) * | 2021-01-13 | 2021-05-14 | 广西壮族自治区农业科学院 | Method for planting pineapples by using astragalus sinicus organic fertilizer |
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