CN102838132A - Method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride - Google Patents
Method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride Download PDFInfo
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 162
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 81
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 title claims abstract description 64
- 239000001110 calcium chloride Substances 0.000 title claims abstract description 54
- 229910001628 calcium chloride Inorganic materials 0.000 title claims abstract description 54
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011575 calcium Substances 0.000 claims abstract description 42
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000002144 chemical decomposition reaction Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 229960002713 calcium chloride Drugs 0.000 description 37
- 229960005069 calcium Drugs 0.000 description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 235000011116 calcium hydroxide Nutrition 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCUJUFDOQOJLBE-UHFFFAOYSA-N [Cl].[Ca] Chemical compound [Cl].[Ca] UCUJUFDOQOJLBE-UHFFFAOYSA-N 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 2
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 238000009621 Solvay process Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明属于化工技术领域，具体涉及一种氯化铵分解生产氨和高浓度氯化钙的方法。The invention belongs to the technical field of chemical industry, and in particular relates to a method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride.
背景技术 Background technique
目前，工业生产纯碱的方法包括联碱法和氨碱法。联碱法生产纯碱的同时副产固体氯化铵，由于氯化铵属生理酸性和含氯肥料，作为农用化肥时受到了较多的限制。同时该方法对于氨来讲是一个开放的体系，因此需要配套建设合成氨装置以补充氨的消耗。氨碱法生产过程中，将反应生成的大约含10-15%的氯化铵溶液采用石灰乳进行蒸氨，生成的氨循环用于纯碱生产。At present, the methods of industrial production of soda ash include combined soda method and ammonia soda method. Soda ash is produced by combined soda ash by-product solid ammonium chloride at the same time, because ammonium chloride is a physiologically acidic and chlorine-containing fertilizer, it is subject to more restrictions when used as an agricultural chemical fertilizer. At the same time, this method is an open system for ammonia, so it is necessary to build a synthetic ammonia plant to supplement the consumption of ammonia. In the production process of ammonia-soda method, the ammonium chloride solution containing about 10-15% produced by the reaction is used to distill ammonia with milk of lime, and the generated ammonia is recycled for soda ash production.
Ca(OH)2+2NH4Cl=CaCl2+NH3↑+2H2OCa(OH) 2 +2NH 4 Cl=CaCl 2 +NH 3 ↑+2H 2 O
由于该反应过程属于低浓度下进行的溶液反应，因此还副产含低于10%氯化钙的废液需要排放。每生产1吨纯碱约排放8～10m3废液,废液中同时还含有NaCl和泥渣及生烧物质。这些废液的排放造成了严重的污染和水资源浪费。另外，由于浓度很低，蒸氨过程所需的能耗很高。为了提高蒸氨过程的溶液浓度，日本专利特公平03-062649公开了一种干法加灰蒸氨技术，采用（干灰）生石灰代替石灰乳以减少水的加入，取得了较好的效果。但是由于其浓度提高的幅度并不大，节能效果不是太明显，得到的氯化钙溶液的浓度为19%，废液排放量仍很大。本发明公开了一种在高浓度下进行蒸氨反应的方法，即采用高浓度的氯化铵溶液与含钙碱性物质进行反应，在生产氨回用制碱过程的同时，直接得到固体氯化钙产品，以达到节能减排的效果。Since the reaction process is a solution reaction carried out at a low concentration, the by-product waste liquid containing less than 10% calcium chloride needs to be discharged. For each ton of soda ash produced, about 8 to 10 m 3 of waste liquid is discharged, and the waste liquid also contains NaCl, sludge and burnt substances. The discharge of these waste liquids has caused serious pollution and waste of water resources. In addition, due to the low concentration, the energy consumption required for the ammonia distillation process is high. In order to increase the concentration of the solution in the process of ammonia distillation, Japanese Patent Publication No. 03-062649 discloses a dry ashing ammonia distillation technology, which uses (dry ash) quicklime instead of milk of lime to reduce the addition of water and achieves better results. But because the range of its concentration increase is not large, the energy-saving effect is not too obvious, the concentration of the obtained calcium chloride solution is 19%, and the discharge of waste liquid is still very large. The invention discloses a method for distilling ammonia at high concentration, that is, using high-concentration ammonium chloride solution to react with calcium-containing alkaline substances, and directly obtaining solid chlorine while producing ammonia for reuse in the alkali-making process. Calcium products to achieve the effect of energy saving and emission reduction.
随着物料浓度的提高，氯化铵与氢氧化钙的化学反应会发生本质的变化。日本专利特公平03-062649指出，当反应浓度提高后，会在氢氧化钙的表面生成CaCl·Ca(OH)2·nH2O硬壳而阻碍进一步的反应。中国发明专利CN101941719A中公开了一种以固体氯化铵和固体石灰进行非水反应实现氯化铵分解的新方法，该方法除分解生产氨以外，其固体产物为碱式氯化钙，而不是氯化钙。另外，在高反应物浓度下，生成的溶液产物的浓度和粘度也随之增大，给进一步的除杂也带来了较大的困难。As the concentration of the material increases, the chemical reaction between ammonium chloride and calcium hydroxide will undergo an essential change. Japanese Patent Publication No. 03-062649 points out that when the reaction concentration increases, a hard shell of CaCl·Ca(OH) 2 ·nH 2 O will be formed on the surface of calcium hydroxide to hinder further reaction. Disclosed in the Chinese invention patent CN101941719A is a new method of carrying out non-aqueous reaction with solid ammonium chloride and solid lime to realize the decomposition of ammonium chloride. In addition to decomposing and producing ammonia, the solid product of this method is basic calcium chloride instead of calcium chloride. In addition, at high reactant concentrations, the concentration and viscosity of the resulting solution products also increase, which brings great difficulties to further impurity removal.
发明内容 Contents of the invention
本发明为解决现在技术中的问题，实现节能减排，本发明提供了一种新的氯化铵分解生产氨气和高浓度氯化钙的方法。将氯化铵与氧化钙或氢氧化钙在高浓度的溶液中进行反应，然后经热过滤、冷却可得到高浓度氯化钙或者二水氯化钙固体产品。In order to solve the problems in the current technology and realize energy saving and emission reduction, the invention provides a new method for producing ammonia gas and high-concentration calcium chloride by decomposing ammonium chloride. React ammonium chloride with calcium oxide or calcium hydroxide in a high-concentration solution, then heat-filter and cool to obtain a high-concentration calcium chloride or calcium chloride dihydrate solid product.
本发明采用以下技术方案予以实现：The present invention adopts following technical scheme to realize:
本发明一种氯化铵分解生产氨和高浓度氯化钙的方法,它包括以下步骤：A method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride of the present invention, it comprises the following steps:
将含钙碱性物质、氯化铵和水按照配比加入带有加热和搅拌装置的反应器中，升温进行化学分解反应，使氯化铵分解释放出氨气，溶液经过热过滤器进行过滤除去固体杂质，然后进入冷却成形器进行冷却和成形，得到高浓度或固体的氯化钙；所述含钙碱性物质与氯化铵的摩尔比为1.0:1.8～1.0:2.5；含钙碱性物质与水的摩尔比为1.0:2.0～1.0:5.0。Add calcium-containing alkaline substances, ammonium chloride and water into the reactor with heating and stirring device according to the ratio, raise the temperature to carry out chemical decomposition reaction, make ammonium chloride decompose and release ammonia gas, and the solution is filtered through a hot filter Remove solid impurities, and then enter the cooling shaper for cooling and forming to obtain high-concentration or solid calcium chloride; the molar ratio of the calcium-containing alkaline substance to ammonium chloride is 1.0:1.8～1.0:2.5; the calcium-containing alkali The molar ratio of active substance to water is 1.0:2.0～1.0:5.0.
优选的，所述的一种氯化铵分解生产氨和高浓度氯化钙的方法,它具体包括以下步骤：将含钙碱性物质、氯化铵和水按照配比加入带有加热和搅拌装置的反应器1中，升温进行化学分解反应，反应温度为60～160℃，反应时间是0.1～2.0小时，使氯化铵分解释放出氨气，溶液经过热过滤器2进行过滤除去固体杂质，热过滤温度为60～110℃，然后进入冷却成形器3进行冷却和成形，得到高浓度或固体的氯化钙；所述含钙碱性物质与氯化铵的摩尔比为1.0:1.5～1.0:2.0，含钙碱性物质与水的摩尔比为1.0:2.5～1.0:4.0。Preferably, the method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride specifically includes the following steps: adding calcium-containing alkaline substances, ammonium chloride and water according to the ratio and heating and stirring In the reactor 1 of the device, the temperature is raised to carry out chemical decomposition reaction, the reaction temperature is 60-160°C, and the reaction time is 0.1-2.0 hours, so that the ammonium chloride is decomposed to release ammonia gas, and the solution is filtered through the thermal filter 2 to remove solid impurities , the hot filtration temperature is 60～110 ℃, then enters the cooling forming device 3 for cooling and forming to obtain high-concentration or solid calcium chloride; the molar ratio of the calcium-containing alkaline substance to ammonium chloride is 1.0:1.5～ 1.0:2.0, the molar ratio of calcium-containing alkaline substance to water is 1.0:2.5～1.0:4.0.
所述含钙碱性物质为氧化钙或/和氢氧化钙。The calcium-containing alkaline substance is calcium oxide or/and calcium hydroxide.
所述反应温度为90～120℃。The reaction temperature is 90-120°C.
所述反应时间是0.2～0.8小时。The reaction time is 0.2-0.8 hours.
所述热过滤温度为70～90℃。The temperature of the hot filtration is 70-90°C.
进一步优选的，所述的一种氯化铵分解生产氨和高浓度氯化钙的方法,它具体包括以下步骤：Further preferably, described a kind of ammonium chloride decomposes the method for producing ammonia and high-concentration calcium chloride, and it specifically comprises the following steps:
将含钙碱性物质、氯化铵和水按照配比加入带有加热和搅拌装置的反应器中，升温进行化学分解反应，反应温度为100～115℃，反应时间是0.2～0.5小时，使氯化铵分解释放出氨气，溶液经过热过滤器2进行过滤除去固体杂质，热过滤温度为80～90℃，然后进入冷却成形器3进行冷却和成形，得到高浓度或固体的氯化钙;所述含钙碱性物质与氯化铵的摩尔比为1.0:1.7～1.0:2.0，含钙碱性物质与水的摩尔比为1.0:3.0～1.0:3.5。Add calcium-containing alkaline substances, ammonium chloride and water into the reactor with heating and stirring device according to the proportion, raise the temperature to carry out chemical decomposition reaction, the reaction temperature is 100-115°C, and the reaction time is 0.2-0.5 hours, so that Ammonium chloride decomposes to release ammonia gas, the solution is filtered through a hot filter 2 to remove solid impurities, the temperature of the hot filter is 80-90°C, and then enters the cooling former 3 for cooling and forming to obtain high-concentration or solid calcium chloride ; The molar ratio of the calcium-containing alkaline substance to ammonium chloride is 1.0:1.7 to 1.0:2.0, and the molar ratio of the calcium-containing alkaline substance to water is 1.0:3.0 to 1.0:3.5.
所述的一种氯化铵分解生产氨和高浓度氯化钙的方法,最佳优选方案为，它包括以下具体步骤：Described a kind of ammonium chloride decomposes the method for producing ammonia and high-concentration calcium chloride, and the most preferred scheme is, and it comprises the following concrete steps:
将氧化钙5.6kg，氯化铵10.2kg、水5.4kg加入到带有加热和搅拌的反应器中，然后开启加热和搅拌，升温至110℃，发生化学分解反应,释放出氨气，生成氯化钙，维持0.4小时，然后将反应后的物料经过热过滤器2在80℃进行热过滤，滤液为氯化钙溶液，经冷却成形器3将溶液冷却成形，得到氯化钙固体产品。Add 5.6kg of calcium oxide, 10.2kg of ammonium chloride, and 5.4kg of water into the reactor with heating and stirring, then turn on the heating and stirring, raise the temperature to 110°C, a chemical decomposition reaction occurs, release ammonia gas, and generate chlorine Calcium, maintain for 0.4 hours, then pass the reacted material through the hot filter 2 for hot filtration at 80°C, the filtrate is a calcium chloride solution, and the solution is cooled and formed by the cooling former 3 to obtain a calcium chloride solid product.
上述的一种氯化铵分解生产氨和高浓度氯化钙的方法中,所述反应器包括卧式外筒体、旋转转动的内搅拌器、加料口、加水口、出氨口和液体出料口；其中卧式外筒体由一个带有外加热套双层套管焊接而成；所述加料口和加水口在卧式外筒体的前上部，并与外筒体内壁相接；所述出氨口在卧式外筒体的后上部，并与外筒体内壁相接；所述液体出料口在卧式外筒体的后下部，并与外筒体内壁相接；所述外加热套的上部接有蒸汽进口管，外加热套的另一侧下部接有冷凝水出口管；所述内搅拌器由中轴、搅拌桨叶和刮板构成；搅拌桨叶焊接在中轴上，刮板焊接在搅拌桨叶的末端，刮板与外筒体的内壁间距为2-3mm；所述内搅拌器的中轴穿过外筒体端面的中心位置，并通过动密封与外筒体的端面相连；所述内搅拌器通过皮带轮与电机相连，以带动内搅拌器旋转实现反应器内物料的均匀搅拌和反应。In the above-mentioned method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride, the reactor includes a horizontal outer cylinder, a rotating inner stirrer, a feed inlet, a water inlet, an ammonia outlet, and a liquid outlet. Material inlet; wherein the horizontal outer cylinder is welded by a double-layer casing with an external heating jacket; the feed inlet and water inlet are at the front upper part of the horizontal outer cylinder and are connected to the inner wall of the outer cylinder; The ammonia outlet is at the rear upper part of the horizontal outer cylinder and is connected with the inner wall of the outer cylinder; the liquid outlet is at the rear lower part of the horizontal outer cylinder and is connected with the inner wall of the outer cylinder; The upper part of the outer heating jacket is connected with a steam inlet pipe, and the lower part of the other side of the outer heating jacket is connected with a condensate outlet pipe; the inner stirrer is composed of a central shaft, a stirring blade and a scraper; the stirring blade is welded in the middle On the shaft, the scraper is welded to the end of the stirring blade, and the distance between the scraper and the inner wall of the outer cylinder is 2-3mm; the central axis of the inner agitator passes through the center of the end surface of the outer cylinder, and is connected to The end faces of the outer cylinder are connected; the inner agitator is connected with the motor through a pulley to drive the inner agitator to rotate to achieve uniform stirring and reaction of the materials in the reactor.
为了在制碱工业中实现本发明公开的方法，需要经过技改将现有的氨碱法制碱过程改为联碱法制碱，以联碱工艺副产固体氯化铵代替氨碱工艺副产的低浓度氯化铵溶液作为本发明所述方法的原料。本发明公开的方法同样适用于其他需要将氯化铵进行分解得到氨和氯化钙的场合。In order to realize the method disclosed by the present invention in the soda-making industry, it is necessary to change the existing ammonia-soda method soda-making process into the combined soda method through technical transformation, and replace the by-product of the ammonia-soda process with solid ammonium chloride by-product of the combined soda process Low-concentration ammonium chloride solution is used as the raw material of the method of the present invention. The method disclosed in the present invention is also applicable to other occasions where ammonium chloride needs to be decomposed to obtain ammonia and calcium chloride.
本发明与现有技术相比具有以下显著的优点：Compared with the prior art, the present invention has the following significant advantages:
与现有的工业上制碱生产中蒸氨过程相比，本发明提供的方法具有反应物浓度高，溶液中游离氨容易释放，反应易彻底的特点，因此过程能耗低得多，排放废液大幅度减少，可实现制碱过程的可持续发展。Compared with the ammonia distillation process in the existing industrial alkali production, the method provided by the invention has the characteristics of high reactant concentration, easy release of free ammonia in the solution, and easy and thorough reaction, so the energy consumption of the process is much lower, and the waste discharge The liquid is greatly reduced, which can realize the sustainable development of the alkali making process.
附图说明 Description of drawings
图1为本发明工艺流程图。Fig. 1 is process flow chart of the present invention.
图2为反应器1的结构示意图。FIG. 2 is a schematic structural view of the reactor 1.
图中各部件说明：Description of each part in the figure:
1、反应器；2、热过滤器；3、冷却成形器；4、含钙碱性化合物；5、氯化铵，6、水；7、氨气；8、高浓度氯化钙或固体氯化钙；9、卧式外筒体；10、内搅拌器；11、加料口；12、加水口；13、出氨口；14、液体出料口；15、外加热套；16、中轴；17、搅拌桨叶；18、刮板；19、皮带轮；20、加热蒸汽进口；21、冷凝水出口。1. Reactor; 2. Thermal filter; 3. Cooling former; 4. Calcium-containing basic compound; 5. Ammonium chloride, 6. Water; 7. Ammonia gas; 8. High concentration calcium chloride or solid chlorine Calcium; 9. Horizontal outer cylinder; 10. Internal agitator; 11. Feed inlet; 12. Water inlet; 13. Ammonia outlet; 14. Liquid outlet; 15. External heating jacket; 16. Central axis ; 17. Stirring blades; 18. Scraper; 19. Pulley; 20. Heating steam inlet; 21. Condensed water outlet.
具体实施方式 Detailed ways
下面结合附图对本发明作进一步的详细说明。The present invention will be further described in detail below in conjunction with the accompanying drawings.
参见图1，本发明工艺过程为：Referring to Fig. 1, technological process of the present invention is:
将含钙碱性化合物4、氯化铵5、水6按配比加入到带有加热和搅拌的反应器1中，然后开启加热和搅拌，升温，发生化学分解反应,释放出氨气7，生成氯化钙。然后将反应后的物料经过热过滤器2进行热过滤，滤液为氯化钙溶液，然后经冷却成形器3将溶液冷却成形，可得到高浓度氯化钙或固体氯化钙8。参见图1、图2。Add the calcium-containing basic compound 4, ammonium chloride 5, and water 6 into the reactor 1 with heating and stirring according to the proportion, then turn on the heating and stirring, raise the temperature, and a chemical decomposition reaction occurs, releasing ammonia gas 7 to form calcium chloride. Then the reacted material is hot filtered through the hot filter 2, and the filtrate is a calcium chloride solution, and then the solution is cooled and shaped by the cooling former 3, and high-concentration calcium chloride or solid calcium chloride 8 can be obtained. See Figure 1 and Figure 2.
本发明一种氯化铵分解生产氨和高浓度氯化钙的方法,它包括以下步骤：A method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride of the present invention, it comprises the following steps:
将含钙碱性物质、氯化铵和水按照配比加入带有加热和搅拌装置的反应器1中，升温进行化学分解反应，使氯化铵分解释放出氨气，溶液经过热过滤器2进行过滤除去固体杂质，然后进入冷却成形器3进行冷却和成形，得到高浓度或固体的氯化钙；所述含钙碱性物质与氯化铵的摩尔比为1.0:1.8～1.0:2.5；含钙碱性物质与水的摩尔比为1.0:2.0～1.0:5.0。Add calcium-containing alkaline substances, ammonium chloride and water into the reactor 1 with a heating and stirring device according to the proportion, raise the temperature to carry out chemical decomposition reaction, make the ammonium chloride decompose and release ammonia gas, and the solution passes through the hot filter 2 Filter to remove solid impurities, then enter the cooling former 3 for cooling and forming to obtain high-concentration or solid calcium chloride; the molar ratio of the calcium-containing alkaline substance to ammonium chloride is 1.0:1.8 to 1.0:2.5; The molar ratio of the calcium-containing alkaline substance to water is 1.0:2.0 to 1.0:5.0.
优选的，所述的一种氯化铵分解生产氨和高浓度氯化钙的方法,它具体包括以下步骤：将含钙碱性物质、氯化铵和水按照配比加入带有加热和搅拌装置的反应器1中，升温进行化学分解反应，反应温度为60～160℃，反应时间是0.1～2.0小时，使氯化铵分解释放出氨气，溶液经过热过滤器2进行过滤除去固体杂质，热过滤温度为60～110℃，然后进入冷却成形器3进行冷却和成形，得到高浓度或固体的氯化钙；所述含钙碱性物质与氯化铵的摩尔比为1.0:1.5～1.0:2.0，含钙碱性物质与水的摩尔比为1.0:2.5～1.0:4.0。Preferably, the method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride specifically includes the following steps: adding calcium-containing alkaline substances, ammonium chloride and water according to the ratio and heating and stirring In the reactor 1 of the device, the temperature is raised to carry out chemical decomposition reaction, the reaction temperature is 60-160°C, and the reaction time is 0.1-2.0 hours, so that the ammonium chloride is decomposed to release ammonia gas, and the solution is filtered through the thermal filter 2 to remove solid impurities , the hot filtration temperature is 60～110 ℃, then enters the cooling forming device 3 for cooling and forming to obtain high-concentration or solid calcium chloride; the molar ratio of the calcium-containing alkaline substance to ammonium chloride is 1.0:1.5～ 1.0:2.0, the molar ratio of calcium-containing alkaline substance to water is 1.0:2.5～1.0:4.0.
所述含钙碱性物质为氧化钙或/和氢氧化钙，所述反应温度为90～120℃，所述反应时间是0.2～0.8小时，所述热过滤温度为70～90℃。The calcium-containing alkaline substance is calcium oxide or/and calcium hydroxide, the reaction temperature is 90-120°C, the reaction time is 0.2-0.8 hours, and the hot filtration temperature is 70-90°C.
所述的一种氯化铵分解生产氨和高浓度氯化钙的方法，它具体包括以下步骤：Described a kind of ammonium chloride decomposes the method for producing ammonia and high-concentration calcium chloride, and it specifically comprises the following steps:
将含钙碱性物质、氯化铵和水按照配比加入带有加热和搅拌装置的反应器1中，升温进行化学分解反应，反应温度为100～115℃，反应时间是0.2～0.5小时，使氯化铵分解释放出氨气，溶液经过热过滤器2进行过滤除去固体杂质，热过滤温度为80～90℃，然后进入冷却成形器3进行冷却和成形，得到高浓度或固体的氯化钙;所述含钙碱性物质与氯化铵的摩尔比为1.0:1.7～1.0:2.0，含钙碱性物质与水的摩尔比为1.0:3.0～1.0:3.5。Add calcium-containing alkaline substances, ammonium chloride and water into reactor 1 with a heating and stirring device according to the ratio, and raise the temperature to carry out chemical decomposition reaction. The reaction temperature is 100-115°C, and the reaction time is 0.2-0.5 hours. The ammonium chloride is decomposed to release ammonia gas, and the solution is filtered through a hot filter 2 to remove solid impurities. The temperature of the hot filter is 80-90°C, and then enters the cooling former 3 for cooling and forming to obtain high-concentration or solid chloride Calcium; the molar ratio of the calcium-containing alkaline substance to ammonium chloride is 1.0:1.7-1.0:2.0, and the molar ratio of the calcium-containing alkaline substance to water is 1.0:3.0-1.0:3.5.
上述的一种氯化铵分解生产氨和高浓度氯化钙的方法中，所述反应器1包括卧式外筒体9、旋转转动的内搅拌器10、加料口11、加水口12、出氨口13和液体出料口14；其中卧式外筒体9由一个带有外加热套15双层套管焊接而成；所述加料口11和加水口12在卧式外筒体9的前上部，并与外筒体内壁相接；所述出氨口13在卧式外筒体9的后上部，并与外筒体内壁相接；所述液体出料口14在卧式外筒体9的后下部，并与外筒体内壁相接；所述外加热套15的上部接有蒸汽进口管20，外加热套15的另一侧下部接有冷凝水出口管21；所述内搅拌器10由中轴16、搅拌桨叶17和刮板18构成；搅拌桨叶17焊接在中轴16上，刮板18焊接在搅拌桨叶17的末端，刮板18与外筒体9的内壁间距为2-3mm；所述内搅拌器10的中轴16穿过外筒体端面的中心位置，并通过动密封与外筒体9的端面相连；所述内搅拌器10通过皮带轮19与电机相连，以带动内搅拌器旋转实现反应器内物料的均匀搅拌和反应。In the above-mentioned method for decomposing ammonium chloride to produce ammonia and high-concentration calcium chloride, the reactor 1 includes a horizontal outer cylinder 9, a rotating internal stirrer 10, a feed port 11, a water feed port 12, an outlet Ammonia port 13 and liquid discharge port 14; wherein the horizontal outer cylinder body 9 is welded by a double-layer casing with an outer heating jacket 15; The front upper part is in contact with the inner wall of the outer cylinder; the ammonia outlet 13 is in the rear upper part of the horizontal outer cylinder 9 and is in contact with the inner wall of the outer cylinder; the liquid outlet 14 is in the horizontal outer cylinder The rear lower part of the body 9 is connected with the inner wall of the outer cylinder; the upper part of the outer heating jacket 15 is connected with a steam inlet pipe 20, and the lower part of the other side of the outer heating jacket 15 is connected with a condensed water outlet pipe 21; Stirrer 10 is made of central shaft 16, stirring paddle 17 and scraper 18; Stirring paddle 17 is welded on the central shaft 16, and scraper 18 is welded on the end of stirring paddle 17, and scraper 18 and outer cylinder 9 The inner wall spacing is 2-3mm; the central axis 16 of the inner agitator 10 passes through the center of the end surface of the outer cylinder body, and is connected with the end surface of the outer cylinder body 9 through a dynamic seal; The motor is connected to drive the inner stirrer to rotate to realize the uniform stirring and reaction of the materials in the reactor.
实施例1：Example 1:
将氢氧化钙7.4kg，氯化铵8.6kg、水5.4kg（含钙碱性物质、氯化铵和水按摩尔比1.0:1.6:3.0）加入带有加热和搅拌的反应器1中，然后开启加热和搅拌。升温至90℃，发生化学分解反应，释放出氨气，生成氯化钙。维持0.3小时，取样分析，氯化铵分解率为93.7%。然后将反应后的物料经过热过滤器2在60℃进行热过滤，滤液为氯化钙溶液，取样分析，氯化钙的质量分数为63.1%。Add 7.4kg of calcium hydroxide, 8.6kg of ammonium chloride, and 5.4kg of water (the molar ratio of calcium-based substances, ammonium chloride and water to water is 1.0:1.6:3.0) into reactor 1 with heating and stirring, and then Turn on heat and stir. When the temperature is raised to 90°C, a chemical decomposition reaction occurs, ammonia gas is released, and calcium chloride is generated. Maintained for 0.3 hours, sampling and analysis showed that the ammonium chloride decomposition rate was 93.7%. Then, the reacted material was thermally filtered through the hot filter 2 at 60° C., and the filtrate was a calcium chloride solution. Sample analysis showed that the mass fraction of calcium chloride was 63.1%.
实施例2：Example 2:
将氧化钙5.6kg，氯化铵10.2kg、水5.4kg（含钙碱性物质、氯化铵和水按摩尔比1.0:1.9:3.0）加入带有加热和搅拌的反应器1中，然后开启加热和搅拌。升温至110℃，发生化学分解反应,释放出氨气，生成氯化钙。维持0.4小时，取样分析，氯化铵分解率为97.7%。然后将反应后的物料经过热过滤器2在80℃进行热过滤，滤液为氯化钙溶液，取样分析，氯化钙的质量分数为81.3%。经冷却成形器3将溶液冷却成形可得到氯化钙固体产品。Add 5.6kg of calcium oxide, 10.2kg of ammonium chloride, and 5.4kg of water (the molar ratio of calcium-based substances, ammonium chloride and water is 1.0:1.9:3.0) into reactor 1 with heating and stirring, and then open Heat and stir. When the temperature rises to 110°C, a chemical decomposition reaction occurs, ammonia gas is released, and calcium chloride is generated. Maintained for 0.4 hours, sampling and analysis showed that the ammonium chloride decomposition rate was 97.7%. Then the reacted material was filtered through a hot filter 2 at 80° C., and the filtrate was a calcium chloride solution. Sample analysis showed that the mass fraction of calcium chloride was 81.3%. The solution is cooled and shaped by the cooling former 3 to obtain a calcium chloride solid product.
实施例3：Example 3:
将氢氧化钙7.4kg，氯化铵10.7kg、水4.5kg（含钙碱性物质、氯化铵和水按摩尔比1.0:2.0:2.5）加入带有加热和搅拌的反应器中，然后开启加热和搅拌。升温至120℃，发生化学分解反应,释放出氨气，生成氯化钙。维持0.5小时，取样分析，氯化铵分解率为98.4%。然后将反应后的物料经过热过滤器2在90℃进行热过滤，滤液为氯化钙溶液，取样分析，氯化钙的质量分数为74%。经冷却成形器3将溶液冷却成形可得到二水氯化钙固体产品。Add 7.4kg of calcium hydroxide, 10.7kg of ammonium chloride, and 4.5kg of water (the molar ratio of calcium-based substances, ammonium chloride and water is 1.0:2.0:2.5) into the reactor with heating and stirring, and then open Heat and stir. When the temperature is raised to 120°C, a chemical decomposition reaction occurs, ammonia gas is released, and calcium chloride is generated. Maintain 0.5 hours, sampling analysis, ammonium chloride decomposition rate of 98.4%. Then the reacted material was thermally filtered through the hot filter 2 at 90° C., and the filtrate was a calcium chloride solution. Sample analysis showed that the mass fraction of calcium chloride was 74%. The solution is cooled and shaped by the cooling shaper 3 to obtain the calcium chloride dihydrate solid product.
实施例4：Example 4:
将氢氧化钙7.4kg，氯化铵8.0kg、水7.2kg（含钙碱性物质、氯化铵和水按摩尔比1.0:1.5:4.0）加入带有加热和搅拌的反应器中，然后开启加热和搅拌。升温至100℃，发生化学分解反应,释放出氨气，生成氯化钙。维持0.8小时，取样分析，氯化铵分解率为99.0%。然后将反应后的物料经过热过滤器2在60℃进行热过滤，滤液为氯化钙溶液，取样分析，氯化钙的质量分数为44%。Add 7.4kg of calcium hydroxide, 8.0kg of ammonium chloride, and 7.2kg of water (the molar ratio of calcium-based substances, ammonium chloride and water is 1.0:1.5:4.0) into the reactor with heating and stirring, and then open Heat and stir. When the temperature is raised to 100°C, a chemical decomposition reaction occurs, ammonia gas is released, and calcium chloride is generated. Maintained for 0.8 hours, sampling and analysis showed that the ammonium chloride decomposition rate was 99.0%. Then the reacted material was thermally filtered through the hot filter 2 at 60° C., and the filtrate was a calcium chloride solution. Sample analysis showed that the mass fraction of calcium chloride was 44%.
实施例5：Example 5:
将氢氧化钙7.4kg，氯化铵10.2kg、水9.0kg（含钙碱性物质、氯化铵和水按摩尔比1.0:1.9:5.0）加入带有加热和搅拌的反应器中，然后开启加热和搅拌。升温至100℃，发生化学分解反应,释放出氨气，生成氯化钙。维持0.8小时，取样分析，氯化铵分解率为99.3%。然后将反应后的物料经过热过滤器2在60℃进行热过滤，滤液为氯化钙溶液，取样分析，氯化钙的质量分数为31%。Add 7.4kg of calcium hydroxide, 10.2kg of ammonium chloride, and 9.0kg of water (the molar ratio of calcium-based substances, ammonium chloride and water is 1.0:1.9:5.0) into the reactor with heating and stirring, and then open Heat and stir. When the temperature is raised to 100°C, a chemical decomposition reaction occurs, ammonia gas is released, and calcium chloride is generated. Maintain 0.8 hours, sampling analysis, ammonium chloride decomposition rate of 99.3%. Then the reacted material was thermally filtered through the hot filter 2 at 60° C., and the filtrate was a calcium chloride solution. Sample analysis showed that the mass fraction of calcium chloride was 31%.
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| CN104192861A (en) * | 2014-08-22 | 2014-12-10 | 江苏德邦化学工业集团有限公司 | Method for recycling ammonia byproduct calcium chloride solution in decomposition of ammonium chloride generated during combined-soda process |
| CN104609441A (en) * | 2015-01-05 | 2015-05-13 | 河北科技大学 | Method for decomposing ammonium chloride by semidry method and reactor |
| WO2022259116A1 (en) * | 2021-06-07 | 2022-12-15 | United Arab Emirates University | A method for ammonia recovery from contaminated water including solvay effluent and aqueous solutions |
| JP7637168B2 (en) | 2023-02-13 | 2025-02-27 | 木村化工機株式会社 | Ammonia recovery method and ammonia recovery apparatus |
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