CN109721055B - Preparation method of water-insoluble carbonate - Google Patents
Preparation method of water-insoluble carbonate Download PDFInfo
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Abstract
The invention provides a preparation method of water-insoluble carbonate, belonging to the technical field of inorganic chemical industry and comprising the following steps: (1) dissolving soluble metal salt into an aqueous solution to obtain a metal salt solution; (2) introducing carbon dioxide into the organic amine aqueous solution to generate amine carbonate, mixing the amine carbonate with a metal salt solution, and reacting to generate water-insoluble carbonate and a first organic amine salt solution; (3) adding inorganic base into the first organic amine salt solution, and reacting to generate an inorganic salt solution and organic amine; (4) adding an extractant into the inorganic salt solution to obtain an extractant dissolved with organic amine; (5) adding the acid solution into an extractant dissolved with organic amine to obtain the extractant and a second organic amine salt solution; (6) and (5) taking the second organic amine salt solution and repeating the steps (3) to (5). Organic amine is adopted to absorb carbon dioxide, the carbon dioxide reacts with soluble metal salt solution to prepare carbonate which is insoluble in water, and inorganic base reduces organic amine salt to organic amine, so that the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical industry, and particularly relates to a preparation method of water-insoluble carbonate.
Background
Water-insoluble carbonates are important compounds and are widely used in the chemical industry, the coating industry, new energy, agriculture, medicine, food, and other fields.
The preparation method of the water-insoluble carbonate mainly adopts a precipitation method, firstly, a soluble metal salt solution is prepared, the soluble carbonate is added to generate the water-insoluble carbonate, and then the water-insoluble carbonate is obtained by washing and filtering.
In the prior art, the soluble carbonate used is generally sodium carbonate, 1.77 tons of sodium carbonate are needed to provide one ton of carbonate, and the price of each ton of sodium carbonate is about 1500 yuan, so the production cost is high. Meanwhile, the additive used in the production process can not be recycled, and even can cause environmental pollution.
Disclosure of Invention
In view of the above, the invention provides a method for preparing a water-insoluble carbonate, which comprises absorbing carbon dioxide with organic amine, reacting with a soluble metal salt solution to prepare the water-insoluble carbonate, and reducing organic amine salt to organic amine with one or more of cheap calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide, without using expensive sodium carbonate, wherein the carbon dioxide has low cost and is beneficial to the environment, and the used organic amine can be recovered.
The invention relates to a preparation method of water-insoluble carbonate, which comprises the following steps:
(1) dissolving soluble metal salt in water solution to obtain metal salt solution, wherein the soluble metal salt is one or more of soluble calcium salt, magnesium salt, iron salt, aluminum salt, copper salt, nickel salt, cobalt salt, manganese salt, lithium salt and zinc salt, and can be soluble calcium salt and soluble magnesium salt.
(2) Introducing carbon dioxide into the organic amine aqueous solution to generate amine carbonate, mixing the amine carbonate with the metal salt solution, and reacting to generate water-insoluble carbonate and a first organic amine salt solution, wherein the reaction temperature is 10-110 ℃; the organic amine is one or more of methylamine, ethylamine, propylamine, butylamine, hexylamine and octylamine, the amine can be one or more of monoamine, diamine and triamine, and for example, the organic amine can be diethylamine, trihexylamine and the like; the organic amine is carbonate which can absorb carbon dioxide to generate amine, the carbon dioxide is rich in source, can be carbon dioxide discharged by combustion of fossil fuels such as coal, petroleum and natural gas in factory production, and can also be carbon dioxide discharged in the production process of chemical products such as feed-grade calcium phosphate or carbon dioxide discharged by animal and plant respiration. The carbonate of amine reacts with the metal salt solution to generate water-insoluble carbonate and organic amine salt solution, wherein the water-insoluble carbonate precipitates, solid-liquid separation is carried out through filtration, impurities in the insoluble carbonate solid are removed through washing, washing liquor is mixed with the first organic amine salt solution, and then the next organic amine extraction is carried out.
(3) Adding inorganic base into the first organic amine salt solution obtained in the step (2), reacting to generate an inorganic salt solution and organic amine, separating the organic amine from the inorganic salt solution, recovering the generated organic amine, and applying the recovered organic amine to the step (2) again. Because a small amount of organic amine is still dissolved in the inorganic salt solution, the next extraction is carried out, and the organic amine is completely recovered.
(4) And (4) adding an extractant into the inorganic salt solution obtained in the step (3) to extract organic amine to obtain the extractant dissolved with the organic amine, wherein the reaction temperature is 30-110 ℃. The extractant may be one or more of diethyl ether, acetone, petroleum ether, carbon tetrachloride, carbon disulfide, chloroform, toluene, xylene, octane, heptane, for example diethyl ether.
(5) And (4) adding an acid solution into the extractant dissolved with the organic amine in the step (4) to obtain the extractant and a second organic amine salt solution. The process is back extraction, and when the acid solution is added, the organic amine in the extractant reacts with the acid solution to separate the organic amine from the extractant. The extractant in the step can be returned to the step (4) for use again, and can also be collected for use, so the consumption of the extractant in the whole process is less, and the acid solution can be one or more of hydrochloric acid, nitric acid and sulfuric acid.
(6) And (4) taking the second organic amine salt solution obtained in the step (5) to repeat the steps (3), (4) and (5), and repeating the steps (3), (4) and (5) on the second organic amine salt solution, or directly adding the solution to a production line in the step (3) to continue extracting the organic amine.
The invention has the beneficial effects that: the method adopts organic amine to absorb carbon dioxide, then reacts with soluble metal salt solution to prepare carbonate which is insoluble in water, and finally reduces organic amine salt into organic amine by using one or a mixture of more of calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide which are low in price.
Drawings
Fig. 1 is a scanning electron microscope image of nickel carbonate prepared by the preparation method of the first embodiment of the invention.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Example one
The invention relates to a preparation method of water-insoluble carbonate, which comprises the following steps:
(1) dissolving nickel chloride in water to obtain a nickel chloride solution;
(2) introducing carbon dioxide into an ethylamine aqueous solution to generate amine carbonate, mixing the amine carbonate with a nickel chloride solution, reacting to generate nickel carbonate and an ethylamine hydrochloride solution, wherein the reaction temperature is 10 ℃, filtering, and carrying out solid-liquid separation;
(3) adding calcium hydroxide into the ethylamine hydrochloride solution obtained in the step (2), and reacting to generate a calcium chloride solution and ethylamine;
(4) adding acetone into the calcium chloride solution obtained in the step (3) to extract ethylamine to obtain an extractant dissolved with ethylamine, wherein the temperature during extraction is 30 ℃;
(5) adding a hydrochloric acid solution into the acetone dissolved with ethylamine in the step (4) to obtain acetone and an ethylamine hydrochloride solution;
(6) and (5) taking the ethylamine hydrochloride solution obtained in the step (5), repeating the steps (3), (4) and (5), and fully recovering the ethylamine.
Tests show that the crystallinity and purity of the nickel carbonate prepared by using the diethylamine and the triethylamine are similar to those of the nickel carbonate prepared by using the ethylamine. If sodium carbonate is used for precipitating nickel chloride, 0.89 ton of sodium carbonate is consumed per ton of nickel carbonate, the price of the sodium carbonate per ton is about 1500 yuan, and the raw material cost is 1335 yuan, while carbon dioxide is industrial waste gas, 0.63 ton of calcium hydroxide is required per ton of nickel carbonate, 500 yuan and 315 yuan are required per ton of calcium hydroxide, the loss rate of ethylamine is 0.02, the cost is about 200 yuan, and the total raw material cost is 515 yuan <1335 yuan.
Example two
The invention relates to a preparation method of water-insoluble carbonate, which comprises the following steps:
(1) dissolving a mixed salt of nickel nitrate, aluminum nitrate and manganese nitrate in water to obtain a salt solution of the mixture;
(2) introducing carbon dioxide into an aqueous solution of a mixture of methylamine and triethylamine to generate amine carbonate, mixing the amine carbonate with a salt solution of the mixture, reacting to generate mixed carbonate of nickel, cobalt and aluminum and mixed nitrate of methylamine and triethylamine, wherein the reaction temperature is 60 ℃, filtering, and carrying out solid-liquid separation;
(3) adding calcium oxide into the mixed nitrate of methylamine and triethylamine in the step (2), and reacting to generate a calcium nitrate solution and a mixture of methylamine and triethylamine;
(4) adding diethyl ether into the calcium nitrate solution obtained in the step (3) to extract a mixture of methylamine and triethylamine to obtain an extracting agent in which the mixture of methylamine and triethylamine is dissolved, wherein the temperature during extraction is 80 ℃;
(5) adding a nitric acid solution into the extracting agent dissolved with the mixture of the methylamine and the triethylamine in the step (4) to obtain a nitrate solution of the mixture of the diethyl ether, the methylamine and the triethylamine;
(6) and (4) taking the nitrate solution of the mixture of the methylamine and the triethylamine in the step (5), repeating the steps (3), (4) and (5), and fully recovering the mixture of the methylamine and the triethylamine.
Tests show that the crystallinity and purity of the mixed carbonate of nickel, cobalt and aluminum prepared by using any mixture of monomethylamine, dimethylamine, trimethylamine and ethylamine, diethylamine and triethylamine are similar to those of the mixed carbonate of methylamine and triethylamine.
If sodium carbonate is used for precipitating the mixture of nickel nitrate, aluminum nitrate and manganese nitrate, 0.95 ton of sodium carbonate is consumed per ton of mixed carbonate, the price of the sodium carbonate per ton is about 1500 yuan, and the raw material cost is 1425 yuan, while the method of the invention is used, carbon dioxide is industrial waste gas, 0.5 ton of calcium oxide is required per ton of mixed carbonate, 600 yuan and 300 yuan are required per ton of calcium oxide, the loss rate of the mixture of methylamine and triethylamine is 0.04, the cost is about 500 yuan, and the total raw material cost is 800 yuan <1425 yuan.
EXAMPLE III
The invention relates to a preparation method of water-insoluble carbonate, which comprises the following steps:
(1) dissolving cobalt chloride in water to obtain a cobalt chloride solution;
(2) introducing carbon dioxide into the water solution of propylamine and butylamine to generate carbonate of amine, mixing the carbonate with the cobalt chloride solution, reacting to generate cobalt carbonate, mixed hydrochloride of propylamine and butylamine, wherein the reaction temperature is 110 ℃, filtering, and carrying out solid-liquid separation;
(3) adding magnesium oxide and magnesium hydroxide into the propylamine and butylamine mixed hydrochloride in the step (2) according to the molar ratio of 1:2, and reacting to generate a magnesium chloride solution and a propylamine and butylamine mixture;
(4) adding petroleum ether and acetone into the magnesium chloride solution obtained in the step (3) and mixing according to the molar ratio of 1:3, and then extracting propylamine and butylamine to obtain an extracting agent in which a mixture of propylamine and butylamine is dissolved, wherein the temperature during extraction is 110 ℃;
(5) adding the hydrochloric acid solution into the extracting agent dissolved with the mixture of propylamine and butylamine in the step (4) to obtain a mixture of petroleum ether and acetone, and a mixed hydrochloric acid solution of propylamine and butylamine;
(6) and (4) taking the mixed hydrochloride of the propylamine and the butylamine in the step (5), repeating the steps (3), (4) and (5), and fully recovering the mixture of the propylamine and the butylamine.
The crystallinity and purity of the iron carbonate prepared by using any mixture of propylamine, dipropylamine, tripropylamine and butylamine, dibutylamine and tributylamine are similar to those of the mixture of propylamine and butylamine through tests.
If sodium carbonate is used for precipitating nickel chloride, 0.9 ton of sodium carbonate is consumed per ton of nickel carbonate, the price of the sodium carbonate is about 1500 yuan per ton, and the raw material cost is 1350 yuan, while carbon dioxide is industrial waste gas, 0.6 ton of magnesium oxide and magnesium hydroxide mixture is required per ton of nickel carbonate, 900 yuan per ton of magnesium oxide and magnesium hydroxide mixture is about 540 yuan, the loss rate of the mixture of propylamine and butylamine is 0.03, the cost is about 400 yuan, and the total raw material cost is 940 yuan <1350 yuan by using the method of the invention.
Example four
The invention relates to a preparation method of water-insoluble carbonate, which comprises the following steps:
(1) dissolving lithium sulfate in water to obtain a lithium sulfate solution;
(2) introducing carbon dioxide into the butylamine aqueous solution to generate amine carbonate, mixing the amine carbonate with the lithium sulfate solution, reacting to generate lithium carbonate and butylamine sulfate, wherein the reaction temperature is 35 ℃, filtering, and carrying out solid-liquid separation;
(3) adding magnesium hydroxide into the butylamine sulfate in the step (2), and reacting to generate magnesium sulfate solution and butylamine;
(4) adding heptane into the magnesium sulfate solution in the step (3) to extract butylamine to obtain an extracting agent for dissolving the butylamine, wherein the temperature during extraction is 50 ℃;
(5) adding a sulfuric acid solution into the butylamine-dissolved extracting agent in the step (4) to obtain heptane and butylamine sulfate solution;
(6) and (4) taking the butylamine sulfate solution obtained in the step (5), repeating the steps (3), (4) and (5), and fully recovering butylamine.
If sodium carbonate is used for precipitating lithium sulfate, 1.5 tons of sodium carbonate is consumed for each ton of lithium carbonate, the price of each ton of sodium carbonate is about 1500 yuan, and the raw material cost is 2250 yuan, whereas carbon dioxide is industrial waste gas, 0.8 ton of magnesium hydroxide is needed for each ton of lithium carbonate, 1000 yuan is needed for each ton of magnesium hydroxide, the loss rate of butylamine is 0.01, the cost is about 150 yuan, and the total raw material cost is 950 yuan <2250 yuan.
The preparation process of the fifth to tenth embodiments is the same as that of the third embodiment, and the kinds of the chemical reagents used in the preparation methods of the fifth to tenth embodiments are as follows:
fig. 1 is a scanning electron microscope image of the nickel carbonate prepared in the first embodiment, from which it can be seen that the grain structure of the nickel carbonate is complete and the crystallinity is good, and the grain structures of the carbonate products of the second embodiment to the tenth embodiment are complete, and are similar to the type of fig. 1.
The carbonate solids prepared by the methods of examples one to ten were analyzed for purity and crystallinity.
The detection method of the carbonate purity refers to the method of national standard law carbonate content, 10g of carbonate is weighed, then hydrochloric acid is added to generate carbon dioxide, the carbon dioxide is collected, the content of the carbonate is calculated, and then the content is divided by 10 to obtain the carbonate purity. The results of the measured data are as follows:
in conclusion, the carbonate with the purity of 95.0-99.99% can be prepared, and the production cost of the preparation method is lower than that of the prior art according to the calculation and comparison of the production cost.
The invention has the beneficial effects that: according to the invention, organic amine is adopted to absorb carbon dioxide, then the carbon dioxide reacts with soluble metal salt solution to prepare water-insoluble carbonate, and finally the low-price calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide are used to reduce organic amine salt into organic amine. The process is equivalent to replacing expensive carbonate with carbon dioxide and low-price alkali. If sodium carbonate is used as a precipitator, 1.77 tons of sodium carbonate is required to be added for providing one ton of carbonate, and the price of each ton of sodium carbonate is about 1500 yuan, so the production cost is high. Carbon dioxide is an industrial waste, organic amine and an extracting agent are hardly consumed in the production process, and the production cost of the carbonate which is insoluble in water is low.
The present invention is not limited to the above-described specific embodiments, and various modifications and variations are possible. Any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for preparing a water-insoluble carbonate, which is characterized by comprising the following steps:
(1) dissolving soluble metal salt into an aqueous solution to obtain a metal salt solution;
(2) introducing carbon dioxide into the organic amine aqueous solution to generate amine carbonate, mixing the amine carbonate with the metal salt solution, and reacting to generate water-insoluble carbonate and a first organic amine salt solution; the organic amine is one or more of methylamine, ethylamine, propylamine, butylamine and hexylamine organic substances;
(3) adding inorganic base into the first organic amine salt solution obtained in the step (2) to react to generate an inorganic salt solution and organic amine;
(4) adding an extracting agent into the inorganic salt solution obtained in the step (3) to extract organic amine to obtain an extracting agent dissolved with organic amine;
(5) adding an acid solution into the extractant dissolved with the organic amine in the step (4) to obtain the extractant and a second organic amine salt solution;
(6) and (5) taking the second organic amine salt solution obtained in the step (5), and repeating the steps (3), (4) and (5).
2. The method according to claim 1, wherein the amine is one or more of a monoamine and a diamine.
3. The method according to claim 1, wherein the inorganic base is one or more of calcium oxide, calcium hydroxide, magnesium oxide, and magnesium hydroxide.
4. The method of claim 1, wherein the extractant is one or more selected from the group consisting of diethyl ether, acetone, petroleum ether, carbon tetrachloride, carbon disulfide, chloroform, toluene, xylene, octane, and heptane.
5. The method according to claim 1, wherein the soluble metal salt is one or more selected from the group consisting of soluble calcium salt, magnesium salt, iron salt, aluminum salt, copper salt, nickel salt, cobalt salt, manganese salt, lithium salt, and zinc salt.
6. The method according to claim 1, wherein the acid solution in step (5) is one or more selected from hydrochloric acid, nitric acid, and sulfuric acid.
7. The method for preparing a water-insoluble carbonate according to claim 1, wherein the reaction temperature in the step (2) is 10 to 110 ℃.
8. The method for preparing a water-insoluble carbonate according to claim 1, wherein the reaction temperature in the step (4) is 30 to 110 ℃.
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