CN115490256A - Method for producing foamed calcium chloride by using ammonium chloride - Google Patents
Method for producing foamed calcium chloride by using ammonium chloride Download PDFInfo
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- CN115490256A CN115490256A CN202211178611.6A CN202211178611A CN115490256A CN 115490256 A CN115490256 A CN 115490256A CN 202211178611 A CN202211178611 A CN 202211178611A CN 115490256 A CN115490256 A CN 115490256A
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- ammonium chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/26—Carbonates or bicarbonates of ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention discloses a method for producing foamed calcium chloride by using ammonium chloride. Mixing solid ammonium chloride and/or an ammonium chloride solution with a calcium carbonate material, heating to 250-650 ℃ for reaction to obtain foamed calcium chloride solid and gas containing carbon dioxide and ammonia gas. The method can obtain high-quality foamed calcium chloride with high porosity and large specific surface area, has the advantages of simple preparation process, convenient operation and low energy consumption, obviously reduces the investment cost of production equipment, is economical and efficient, saves energy, protects environment and effectively solves the problems in the prior art.
Description
Technical Field
The invention relates to a method for producing foamed calcium chloride, in particular to a method for producing foamed calcium chloride by using ammonium chloride, and belongs to the field of chemical metallurgy.
Background
Calcium chloride is divided into liquid calcium chloride and solid calcium chloride. The liquid calcium chloride is an aqueous solution of calcium chloride, and CaCl in the liquid calcium chloride product is generally 2 The content of (B) is 12-40 wt%. If the content of calcium chloride is too high, the solution is too viscous, the temperature is reduced, the solution is solidified, and the problems of difficult transportation, unloading, use and the like exist. The solid calcium chloride product can be divided into three types of tablets, spheres, powder and the like, and the solid calcium chloride product comprises calcium chloride dihydrate or anhydrous calcium chloride. Calcium chloride (CaCl) in calcium chloride dihydrate 2 ) The content of (A) is generally 72-78 wt%, and the calcium chloride (CaCl) in the anhydrous calcium chloride 2 ) In an amount ofIs 90 to 95 weight percent.
The calcium chloride is applied to salt water, road ice melting agent, drying agent and the like used by refrigeration equipment. The calcium chloride and the hydrate and solution thereof have important application values in the aspects of food manufacture, building materials, medicine, biology and the like. The anhydrous calcium chloride is a dehydrating agent and a drying agent commonly used in industrial production and laboratories, is mainly used for drying gas, petroleum, organic solvents, snow removing agents and the like, is used as a raw material for preparing metal calcium and various calcium salts in inorganic industry, and is also used as a sizing agent, a water purifying agent, an antifreezing agent, a food preservative and a pavement cleaning agent for textiles. Adding CaCl 2 ·6H 2 O with ice at a ratio of 1.44:1, which is used as a refrigerant in the laboratory and is also an important refrigerant in the refrigeration industry, a low temperature of-54.9 ℃ can be obtained.
The preparation of calcium chloride is generally that calcium carbonate (limestone) reacts with hydrochloric acid, or lime (calcium oxide or calcium hydroxide) reacts with ammonium chloride solution to obtain calcium chloride solution, the calcium chloride solution is purified and impurity-removed, and then is evaporated and concentrated until the content of calcium chloride is 27-42%, so as to obtain liquid calcium chloride product; evaporating and concentrating the purified calcium chloride solution to 172-174 ℃, cooling and crystallizing, drying and dehydrating the crystal at 200-240 ℃ to obtain a calcium chloride dihydrate product; the calcium chloride dihydrate is dried and dehydrated at 260-300 ℃ to obtain the anhydrous calcium chloride product. Generally, the production process of the existing calcium chloride product is complicated, the operation parameters are strict, and the energy consumption is high.
Disclosure of Invention
Aiming at the defects of complex process, complex operation, high cost, high energy consumption and the like in the existing calcium chloride production technology, the invention aims to provide the method for producing the foamed calcium chloride by utilizing the ammonium chloride, the method can obtain the foamed calcium chloride powder with high porosity and large specific surface area, has stronger adsorbability and water absorbability compared with the existing blocky or granular anhydrous calcium chloride, and has the advantages of simple process, convenient operation, low energy consumption, economy, high efficiency, energy conservation, environmental protection and the like, can effectively solve the problems in the prior art, and is suitable for industrial production.
In order to achieve the technical purpose, the invention provides a method for producing foamed calcium chloride by utilizing ammonium chloride, which comprises the steps of mixing solid ammonium chloride and/or ammonium chloride solution with calcium carbonate materials, heating to 250-650 ℃ for reaction to obtain foamed calcium chloride solid and gas containing carbon dioxide and ammonia gas.
Ammonium chloride in the present invention is used not only as a raw material but also as a foaming agent. Heating ammonium chloride and calcium carbonate to react to produce calcium chloride, carbon dioxide, ammonia gas and water vapor, absorbing the water vapor by the calcium chloride to soften the jelly at the reaction temperature, blowing the jelly into foam by the carbon dioxide and the ammonia gas produced by the reaction, and simultaneously continuously evaporating the moisture in the system to obtain the foam-shaped anhydrous calcium chloride.
The basic reaction principle involved in the process is as follows:
2NH 4 Cl+CaCO 3 ＝Δ＝CaCl 2 +2NH 3 ↑+CO 2 ↑+H 2 O↑ (1)
2NH 3 +CO 2 +H 2 O＝(NH 4 ) 2 CO 3 (2)
NH 3 +CO 2 +H 2 O＝NH 4 HCO 3 (3)
in the heating reaction process, part of ammonium chloride is heated and sublimated, condensed and collected through a flue to obtain ammonium chloride solid, and the ammonium chloride solid is returned to be used as a raw material for recycling.
In a further preferred embodiment, the reaction temperature is 350 to 525 ℃. In the reaction process, the reaction temperature needs to be controlled in a proper range to obtain the foamed calcium chloride. If the reaction temperature is too low, the ammonium chloride can be incompletely decomposed, so that the whole reaction is incomplete and the reaction efficiency is low; if the reaction temperature is too high, the produced foamed calcium chloride collapses and sinters to form compact calcium chloride lumps.
As a preferred embodiment, the gas containing carbon dioxide and ammonia is absorbed by water to obtain ammonium carbonate. The CO generated during the above reaction 2 And NH 3 Through multi-stage countercurrent water absorptionSaturated crystallization to separate out ammonium carbonate; or, to a CO-containing atmosphere 2 And NH 3 Introducing CO into the gas 2 And control of CO 2 And NH 3 The molar ratio of 1:1, and supersaturation crystallization to separate out ammonium bicarbonate through multistage countercurrent water absorption.
As a preferred scheme, the calcium carbonate material comprises at least one of natural mineral powder containing calcium carbonate, heavy calcium carbonate, light calcium carbonate, calcium carbonate reagent and artificial calcium carbonate material. The calcium carbonate material is further preferably calcium carbonate material powder with the granularity of less than 250 meshes.
Preferably, the concentration of the ammonium chloride solution is 250 to 850g/L.
As a preferable scheme, the molar ratio of the ammonium chloride in the solid ammonium chloride and/or ammonium chloride solution to the calcium carbonate in the calcium carbonate material is 2-2.5.
In a preferred embodiment, the reaction time is 0.5 to 3.5 hours.
As a preferred embodiment, the foamed calcium chloride has a porosity>85 percent and the bulk density is less than 0.35g/mL. Anhydrous calcium chloride (CaCl) in the foamed calcium chloride 2 ) In an amount of>95％。
Compared with the prior art, the invention has the following advantages and effects:
(1) Simple process, convenient operation, less equipment investment and less energy consumption than 1/3 of the traditional process, and the obtained foam calcium chloride contains anhydrous calcium chloride (CaCl) 2 ) In an amount of>95 percent, high product purity, low production cost, energy conservation and environmental protection, can effectively solve the technical defects of the existing production process, and is suitable for industrial production.
(2) Ammonium chloride is skillfully used as a raw material and a foaming agent, no new impurity is introduced, the prepared calcium chloride foam is a new calcium chloride product, the porosity is high, the specific surface area is large, the bulk density of the calcium chloride foam powder is only 0.26-0.38 g/mL, and the bulk density of granular anhydrous calcium chloride is 0.75-0.87 g/mL, so the calcium chloride foam has stronger adsorbability and water absorbability than massive or granular anhydrous calcium chloride.
(3) The prepared foamed calcium chloride product has an ultra-fast dissolving speed in water, and can be mixed with water to prepare liquid calcium chloride for use at present, so that the packaging and transportation cost of the liquid calcium chloride product is greatly saved.
(4) The method takes ammonium chloride as a raw material to produce foamed calcium chloride, and produces a byproduct ammonium carbonate fertilizer which is popular with crops, so that an ideal comprehensive utilization method is found for the ammonium chloride, three wastes are not generated in the comprehensive utilization process, and the method is economical, efficient, energy-saving and environment-friendly.
(5) The method has good adaptability to calcium carbonate raw materials, can fully utilize different calcium carbonate-containing materials, is favorable for resource recycling, and can be used as an effective way for separating and recycling valuable metal elements.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate the invention but not to limit it further.
Example 1
Taking 110g of analytically pure ammonium chloride reagent and 100g of calcium carbonate reagent, grinding, uniformly mixing, adding into a ceramic bowl with a cover, putting into a muffle furnace, heating, keeping the temperature at 350 ℃ for 2.5h, cooling to obtain 110.85g of foamed calcium chloride with the porosity of 91%, wherein the obtained foamed calcium chloride reaches the quality standard specified by a food additive, namely calcium chloride (GB 1886.45-2016).
Example 2
Uniformly mixing 95.3% calcium carbonate limestone powder with particle size of 1250 meshes and ammonium chloride powder according to a mass ratio of 1:1, adding into an external heating type rotary kiln, keeping the temperature of 525 ℃ for 0.5h, cooling foamed calcium chloride porous powder from the head of the kiln, packaging and selling the cooled foamed calcium chloride porous powder serving as a drying agent, and obtaining anhydrous calcium chloride (CaCl) in the obtained powder 2 ) The content of (A) is 96.1%, the bulk density is 0.28-0.33 g/mL, and after the flue gas discharged from the kiln tail is settled, a proper amount of CO is blown in 2 Cooling for three-stage countercurrent absorption to obtain the ammonium bicarbonate agricultural fertilizer, collecting smoke dust obtained by flue gas sedimentation, and returning to the batching.
Example 3
100g of phosphogypsum with calcium sulfate content of 89.5% is taken and added into 100mL of water, 50mL of concentrated ammonia water is added while stirring, 60g of ammonium bicarbonate is added, stirring and primary transformation are carried out for 1h at room temperature, 85.6g of phosphogypsum primary transformation slag (artificial calcium carbonate material) with water content of 35% and primary transformation liquid thereof are obtained through filtering, 62g of ammonium chloride is added into the obtained primary transformation slag and is stirred uniformly to obtain pasty material (the ammonium chloride is dissolved by water carried in the primary transformation slag), the obtained pasty material is placed into a muffle furnace to be heated and secondarily transformed, the temperature is kept at 450 ℃ for 1h to obtain secondary transformation material containing foamed calcium chloride, the secondary transformation material is cooled and added with 100mL of water to be dissolved, filtered and washed to obtain 132mL of calcium chloride solution with the concentration of 36.91% and the pH of 7.86 and 10.15g of dissolved residue, the dissolved residue is used for separating and recovering valuable elements in the calcium chloride, the calcium chloride solution and the transformed solution are stirred with the transformed solution to precipitate and precipitate to separate and recover the ammonium chloride, and the secondary transformation is recycled.
Comparative example 1
Taking 110g of analytically pure ammonium chloride reagent and 100g of calcium carbonate reagent, grinding, uniformly mixing, adding into a ceramic bowl with a cover, putting into a muffle furnace, heating, keeping the temperature at 150 ℃ for 2.5h, cooling to obtain a mixed material with 25.8% of calcium chloride content, wherein the mixed material also contains a large amount of unreacted calcium carbonate and ammonium chloride, and the ammonium chloride starts to decompose when heated to 100 ℃, but can be completely decomposed when heated to 337.8 ℃.
Comparative example 2
Grinding 110g of analytically pure ammonium chloride reagent and 100g of calcium carbonate reagent, uniformly mixing, adding into a ceramic bowl with a cover, putting into a muffle furnace, heating, keeping the temperature at 700 ℃ for 0.5h, and cooling to obtain a compact blocky calcium chloride material, wherein the melting point of calcium chloride is 772 ℃, and when the temperature is increased to above 650 ℃, the foamed calcium chloride begins to soften and collapse until the temperature is seriously collapsed and sintered at 700 ℃.
Claims (7)
1. A method for producing foamed calcium chloride by using ammonium chloride is characterized by comprising the following steps: mixing solid ammonium chloride and/or ammonium chloride solution with calcium carbonate material, heating to 250-650 deg.C, and reacting to obtain foamed calcium chloride solid and gas containing carbon dioxide and ammonia gas.
2. The method for producing foamed calcium chloride by using ammonium chloride as claimed in claim 1, characterized in that: the calcium carbonate material comprises at least one of natural mineral powder containing calcium carbonate, heavy calcium carbonate, light calcium carbonate, a calcium carbonate reagent and an artificial calcium carbonate material.
3. The method for producing foamed calcium chloride by using ammonium chloride as claimed in claim 1, wherein the method comprises the following steps: the concentration of the ammonium chloride solution is 250-850 g/L.
4. A method for producing foamed calcium chloride from ammonium chloride according to any one of claims 1 to 3, wherein: the molar ratio of the ammonium chloride in the solid ammonium chloride and/or ammonium chloride solution to the calcium carbonate in the calcium carbonate material is (2-2.5).
5. The method for producing foamed calcium chloride by using ammonium chloride as claimed in claim 1, wherein the method comprises the following steps: the reaction time is 0.5-3.5 h.
6. The method for producing foamed calcium chloride by using ammonium chloride as claimed in claim 1, wherein the method comprises the following steps: the porosity of the foamed calcium chloride is more than 85%, and the bulk density is less than 0.35g/mL.
7. The method for producing foamed calcium chloride by using ammonium chloride as claimed in claim 1, wherein the method comprises the following steps: and absorbing the gas containing the carbon dioxide and the ammonia gas by water to obtain ammonium carbonate salt.
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| CN202211178611.6A CN115490256A (en) | 2022-09-27 | 2022-09-27 | Method for producing foamed calcium chloride by using ammonium chloride |
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| CN202211178611.6A CN115490256A (en) | 2022-09-27 | 2022-09-27 | Method for producing foamed calcium chloride by using ammonium chloride |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD223428A1 (en) * | 1984-04-13 | 1985-06-12 | Kali Veb K | PROCESS FOR PREPARING CALCIUM CHLORIDE GRANULATE |
| CN107522219A (en) * | 2017-09-19 | 2017-12-29 | 临海市利民化工有限公司 | A kind of preparation method of industrial calcium chloride |
| CN111592014A (en) * | 2020-06-05 | 2020-08-28 | 周仕飞 | Method and system device for preparing potassium sulfate, calcium carbonate and ammonium chloride from phosphogypsum |
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2022
- 2022-09-27 CN CN202211178611.6A patent/CN115490256A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD223428A1 (en) * | 1984-04-13 | 1985-06-12 | Kali Veb K | PROCESS FOR PREPARING CALCIUM CHLORIDE GRANULATE |
| CN107522219A (en) * | 2017-09-19 | 2017-12-29 | 临海市利民化工有限公司 | A kind of preparation method of industrial calcium chloride |
| CN111592014A (en) * | 2020-06-05 | 2020-08-28 | 周仕飞 | Method and system device for preparing potassium sulfate, calcium carbonate and ammonium chloride from phosphogypsum |
Non-Patent Citations (2)
| Title |
|---|
| 李全超等: ""氯化焙烧法制备无水氯化钙的工艺研究"", 《无机盐工业》, vol. 48, no. 10, pages 36 - 39 * |
| 杨荫森等: "《石油工业劳动卫生与职业性危害》", vol. 1, 人民卫生出版社, pages: 309 * |
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