CN104609441A - Method for decomposing ammonium chloride by semidry method and reactor - Google Patents
Method for decomposing ammonium chloride by semidry method and reactor Download PDFInfo
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- CN104609441A CN104609441A CN201510002402.XA CN201510002402A CN104609441A CN 104609441 A CN104609441 A CN 104609441A CN 201510002402 A CN201510002402 A CN 201510002402A CN 104609441 A CN104609441 A CN 104609441A
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Abstract
The invention relates to a method for decomposing ammonium chloride by a semidry method. The method comprises the steps of adding reactor powder calcium oxide and ammonium chloride into a reactor, carrying out pressed water spraying on a reactor in a foggy manner, allowing the reactor to react with the water to obtain liquid calcium chloride under the condition of heating and stirring, and after exhausting ammonia, natural cooling and crystallizing liquid calcium chloride to obtain solid calcium chloride dihydrate. At the same time, the invention further relates to a reactor for decomposing ammonium chloride by the semidry method. The reactor is provided with a barrel with a heating device, a twin-screw stirring device arranged in the barrel, and an exhaust outlet formed in the barrel, wherein a spraying filler pipe capable of carrying out pressed spraying of the water in a foggy manner is arranged in the barrel. With the adoption of the technical scheme, ammonium chloride can be decomposed to generate ammonia and calcium chloride dihydrate in an economical even environment-friendly manner.
Description
Technical field
The present invention relates to a kind of decomposition method of ammonium chloride, particularly relate to a kind of method of semidrying decomposing ammonium chloride, meanwhile, the invention still further relates to the reactor of this semidrying decomposing ammonium chloride.
Background technology
Solvay soda process is the main method of soda manufacture, this process is while production soda ash, the ammonium chloride solution of by-product lower concentration, generally take the method adding milk of lime in ammonium chloride solution at present, ammonium chloride is decomposed and generates calcium chloride and ammonia, then steamed by ammonia by ammonia distillation process, ammonia returns soda ash system again, realizes ammonia circulation.But this method can produce the waste solution of calcium chloride that a large amount of concentration is about 10%, causes serious environmental pollution and water resource waste.Producing another commercial run of soda ash is union soda, and the method by ammonium chloride output in solid form from system, thus avoids the environmental pollution that evaporated waste ammonia liquid brings by cold analysis, the process such as to saltout.The main application of solid ammonium chloride is agrochemical, and the ammonium chloride of current more than 95% is mainly as fertilizer application.Due to the acidic fertilizier that ammonium chloride is chloride, the sugariness of melon or fruit type crops can be caused to decline, and mouthfeel is bad, and life-time service ammonium chloride chemical fertilizer can cause soil compaction simultaneously, has therefore occurred that ammonium chloride is excessive, has caused the wasting of resources.
Disclose in patent of invention CN101941719A a kind of with solid ammonium chloride and solid lime carry out non-aqueous reaction realize ammonium chloride decompose novel method, its ultimate principle is: CaO+NH
4cl==CaOHCl+NH
3, the method is except ammonia is produced in decomposition, and its solid product is alkali formula calcium chloride, instead of Calcium dichloride dihydrate, and calcium oxide consumption is large.
Disclose a kind of ammonium chloride in patent of invention CN102838132A and decompose the method for producing ammonia and high calcium chloride concentration, this invention has following 2 deficiencies: 1, reactant can not fully contact, reaction times needed for complete reaction is very long, and speed of reaction is lower, is difficult to realize suitability for industrialized production; 2, water add-on is large, and the most of ammonia generated is only absorbed by the water, and Ammonia recovery rate is low.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides a kind of method of semidrying decomposing ammonium chloride of economic environmental protection.
For achieving the above object, the method of semidrying decomposing ammonium chloride of the present invention, that reactant powder calcium oxide and ammonium chloride are joined in reactor, with mist to reactant pressurization water spray, and under heating and strong stirring state, make reactant and water be obtained by reacting calcium chloride liquid, after discharging ammonia, calcium chloride liquid natural cooling crystallization obtains solid Calcium dichloride dihydrate.
In the system being reactant with ammonium chloride and calcium oxide, by mist to reactant pressurization water spray, the add-on that can control water is on the one hand less, the water that adds and powder calcium oxide can be made on the other hand fully to react, prevent local digestion from causing calcium oxide to be wrapped the appearance of problem, selective oxidation calcium and water carry out digestion reaction and are converted into calcium hydroxide, then calcium hydroxide and ammonium chloride react, generate calcium chloride and water, generate water again with unreacted calcium oxide, ammonium chloride continues reaction, achieve the recycle of water, save water resources, finally obtain calcium chloride liquid and ammonia, the ammonia produced reclaims from venting port in time, because amount of water is less, liquid calcium chloride bulk concentration is higher, high calcium chloride concentration liquid obtains solid Calcium dichloride dihydrate through naturally cooling.Its reaction principle is:
In semidrying reaction process, material viscosity is large, rate of mass transfer is slow, in order to prevent wrapping up between unreacting material and between raw material and product, this reaction need be carried out under heating and strong stirring state, material is sheared fully under strong stirring, avoid parcel and agglomeration, accelerate speed of reaction, ensure that reaction is carried out smoothly.
As the restriction to aforesaid way, the mol ratio of described powder calcium oxide and water is 1.0:1.0 ~ 1.5, and the mol ratio of powder calcium oxide and ammonium chloride is 1.0:1.5 ~ 2.0.
As the further optimization to aforesaid way, the mol ratio of described powder calcium oxide and water is 1.0:1.0 ~ 1.3, and the mol ratio of powder calcium oxide and ammonium chloride is 1.0:1.9 ~ 2.0.
Generation calcium hydroxide is fully reacted in order to enable calcium oxide, obtain the calcium chloride solution of high density, limit the amount of water of adding, the water yield crosses that I haven't seen you for ages generates by product one water calcium chloride and hydroxy chloride calcium, hypervolia can generate by product four water calcium chloride, affects the purity of reaction product; In order to make ammonium chloride decompose completely, limit calcium oxide excessive, to improve the quality of product solid Calcium dichloride dihydrate.
As the restriction to aforesaid way, described reactor interior reaction temperature is 80 DEG C ~ 200 DEG C, and the reaction times is 10 ~ 30min.
As the further optimization to aforesaid way, described reactor interior reaction temperature is 100 DEG C ~ 130 DEG C, and the reaction times is 20 ~ 30min.
Improve temperature of reaction and can make ammonia fast desorption, but temperature is crossed high water vapor steam output and is increased, cause the water that adds can not completely and calcium oxide react, increase energy consumption and the water yield; Temperature is too low, and the desorption rate of ammonia is slack-off, causes ammonium chloride to decompose the time needed completely elongated; Therefore take energy consumption and reaction times into consideration, limit best temperature of reaction and reaction times, can ensure that ammonium chloride decomposes completely and can obtain meeting the product of industrialization production requirements.
As the restriction to aforesaid way, described liquid calcium chloride bulk concentration is not less than 75.5%.
The semidrying decomposing ammonium chloride reaction carried out in reactor of the present invention, owing to reacting the minimizing of the water yield, make product chlorinated calcium solution concentration reach more than 75.5%, utilize the principle of crystallisation by cooling, after high calcium chloride concentration is cooled, directly generate solid Calcium dichloride dihydrate product.
Simultaneously, present invention also offers a kind of reactor for semidrying decomposing ammonium chloride, this reactor has the outer cylinder body with heating unit, be arranged on the twin screw whipping appts in outer cylinder body, and the venting port be arranged in outer cylinder body, being provided with in outer cylinder body can by water with the spray filler pipe of mist pressurization ejection.
For the reactor of semidrying decomposing ammonium chloride, be provided with twin screw whipping appts, under shearing and the broken effect of twin screw strong stirring, material is fully contacted, avoid the calcium chloride generated to be deposited on calcium hydroxide surface with the form of crystallization, ensure that the reaction of calcium oxide, ammonium chloride and water is carried out smoothly; Being provided with can by water with the spray filler pipe of mist pressurization ejection, that water in order to control to add fully can contact with calcium oxide, make to react completely, otherwise remaining calcium oxide can react with ammonium chloride and generate hydroxy chloride calcium, affect the quality product of Calcium dichloride dihydrate on the one hand, on the other hand due to the formation of hydroxy chloride calcium, cause the calcium oxide content deficiency added, reduce ammonium chloride rate of decomposition; Heating unit is to provide reaction heat energy, and venting port is to discharge the ammonia of decomposing ammonium chloride reaction generation in time.
As the restriction to aforesaid way, described spray filler pipe is provided with multiple mouth spray, and adjacent mouth spray spacing is 10cm.
The mouth spray that arranges on spray filler pipe, its spacing can make the water distribution that adds even with 10cm distribution.
As the restriction to aforesaid way, described twin screw whipping appts comprise two parallel and rotate the axis be arranged in outer cylinder body, be vertically fixed on the multiple stirring rod on each axis, the gap between the adjacent stirring rod on same axis is 14mm.
The design in stirring rod angle and gap makes it in high-speed rotation, larger particle can be sheared and smash, and makes the powerful broken and fully mixing of material, avoids the reunion in reaction process and parcel problem, enhance mass transfer effect.
As the restriction to aforesaid way, the mixing speed of described twin screw whipping appts is 70 ~ 100r/min.
Mixing speed can adjust within the scope of 70 ~ 100r/min, and because the viscosity of material is comparatively large, the too low material of rotating speed can not get good mixing and shearing, easily occurs to reunite and parcel phenomenon; The high power consumption that causes of rotating speed increases, and stable equipment operation is deteriorated.
In sum, adopt technical scheme of the present invention, powder calcium oxide and ammonium chloride can be made fully to contact and react, improve speed of reaction, Reaction time shorten, the product obtained directly forms Calcium dichloride dihydrate product without the need to filtering; In addition, the method improves the utilization ratio of water by the mode of spray, reduces amount of water, thus improves ammonium chloride rate of decomposition and ammonia recovery, is a kind of both economical and the method for ammonium chloride decomposition being produced ammonia and Calcium dichloride dihydrate of environmental protection.
Accompanying drawing explanation
Do further to describe in detail to the present invention below in conjunction with the drawings and the specific embodiments:
Fig. 1 is the internal structure schematic diagram under longitudinal view of reactor;
Fig. 2 is the internal structure schematic diagram under the transverse views of reactor;
In figure: 1, reactor; 2, outer cylinder body; 3, twin screw whipping appts; 4, charging opening; 5, filler pipe is sprayed; 6, venting port; 7, discharge port; 8, additional hot jacket; 9, steam inlet pipe; 10, condensating water outlet tube; 11, the first axis; 12, the second axis; 13, stirring rod; 14, the first gear; 15, the second gear; 16, belt pulley.
Embodiment
The method of the semidrying decomposing ammonium chloride that the present invention relates to, adopts the reactor of structure shown in Fig. 1, Fig. 2.Reactor 1 is made up of the twin screw whipping appts 3 of outer cylinder body 2, rotary motion, charging opening 4, spray filler pipe 5, venting port 6 and discharge port 7, outer cylinder body 2 is welded by a bilayer sleeve with additional hot jacket 8, charging opening 4 at the front upper part of outer cylinder body 2, and is communicated with outer cylinder body 2 inside, spray filler pipe 5 penetrates from the side of outer cylinder body 2, spray filler pipe 5 is distributed with multiple mouth sprays of spacing 10cm, venting port 6 in the upper back of outer cylinder body 2, and is communicated with outer cylinder body 2 inside, discharge port 7 at the rear lower of outer cylinder body 2, and is communicated with outer cylinder body 2 inside, additional hot jacket 8 is connected to steam inlet pipe 9 and condensating water outlet tube 10, twin screw whipping appts 3 comprise two parallel and rotate the axis be arranged in outer cylinder body 2, first axis 11, second axis 12, also comprise and be vertically fixed on the first axis 11, multiple stirring rod 13 on second axis 12, spacing between adjacent stirring rod on same axis is 14mm, stirring rod 13 is 2mm with the inwall spacing of outer cylinder body 2, and it is outside in outer cylinder body 2, by intermeshing first gear 14, second gear 15 connects, on the second axis 12 of outer cylinder body 2 outside, be provided with the belt pulley 16 driving with not shown motor and be connected, be connected with motor by belt pulley 16, with the uniform stirring and the reaction that drive twin screw whipping appts 3 to rotate material in realization response device.
Embodiment one
The present embodiment relates to reaction mass impact on the reaction of semidrying decomposing ammonium chloride under different add-on, specific experiment is operating as: at normal temperatures, after powder calcium oxide and ammonium chloride are mixed in the storage tank with stirring, join in reactor 1 and stir under about 80r/min rotating speed, water is added by the mode of spray, after adding, be heated to 130 DEG C, maintain 30min.This slurry cools through normal temperature, directly obtains Calcium dichloride dihydrate solid.The reaction result of each material add-on and correspondence is as shown in the table:
Can be drawn by above-mentioned example, when ammonium chloride add-on reduces, the rate of decomposition of ammonium chloride can be improved, but unreacted calcium oxide content can be made simultaneously higher, affect the purity of product Calcium dichloride dihydrate.
Embodiment two
The present embodiment relates to the impact that reaction conditions reacts semidrying decomposing ammonium chloride, specific experiment is operating as: at normal temperatures, after 13.7kg powder calcium oxide and 24.9kg ammonium chloride are mixed in the storage tank with stirring, join in reactor 1 and stir, 5.7L water is added by the mode of spray, after adding, be heated to certain temperature, maintain certain hour.This slurry cools through normal temperature, directly obtains Calcium dichloride dihydrate solid.The reaction result of reaction conditions and correspondence is as shown in the table:
Can be drawn by above-mentioned example, when rotating speed is less, reaction mass can not be made fully to contact, and then affect the rate of decomposition of ammonium chloride; Time shorter when reacted, ammonium chloride can not decompose completely, affects the purity of product.
Embodiment three
This enforcement relates to the impact that conversion unit reacts semidrying decomposing ammonium chloride.
Embodiment 3.1
At normal temperatures, after 13.7kg powder calcium oxide and 23.5kg ammonium chloride are mixed in the storage tank with stirring, join in reactor 1 and stir under rotating speed 80r/min, 5.0L water is added by the mode of spray, after adding, be heated to 130 DEG C, maintain 30min.This slurry cools through normal temperature, directly obtains Calcium dichloride dihydrate solid.Calcium dichloride dihydrate concentration 95.3%, ammonium chloride rate of decomposition 99.4%.
Embodiment 3.2
At normal temperatures, after 13.7kg powder calcium oxide and 23.5kg ammonium chloride are mixed in the storage tank with stirring, join in common singe screw reaction unit, and directly add 5.0L water, after adding, be heated to 130 DEG C, maintain 30min.This slurry cools through normal temperature, directly obtains Calcium dichloride dihydrate solid.Calcium dichloride dihydrate concentration 75.1%, ammonium chloride rate of decomposition 80.4%.
Can draw from executing example 3.1 and 3.2,1) common response device is insufficient owing to stirring, and reaction mass can not be made fully to contact, reduce the transformation efficiency of ammonium chloride; 2) add water with the form directly added, can not be uniformly distributed, make the oxidized calcium parcel of ammonium chloride, reduce the rate of decomposition of ammonium chloride.
Claims (10)
1. the method for a semidrying decomposing ammonium chloride, it is characterized in that: reactant powder calcium oxide and ammonium chloride are joined in reactor, with mist to reactant pressurization water spray, and under heated and stirred state, reactant and water is made to be obtained by reacting calcium chloride liquid, after discharging ammonia, calcium chloride liquid natural cooling crystallization obtains solid Calcium dichloride dihydrate.
2. the method for semidrying decomposing ammonium chloride according to claim 1, is characterized in that: the mol ratio of powder calcium oxide and water is 1.0:1.0 ~ 1.5, and the mol ratio of powder calcium oxide and ammonium chloride is 1.0:1.5 ~ 2.0.
3. the method for semidrying decomposing ammonium chloride according to claim 2, is characterized in that: the mol ratio of powder calcium oxide and water is 1.0:1.0 ~ 1.3, and the mol ratio of powder calcium oxide and ammonium chloride is 1.0:1.9 ~ 2.0.
4. the method for semidrying decomposing ammonium chloride according to claim 1, is characterized in that: reactor interior reaction temperature is 80 DEG C ~ 200 DEG C, and the reaction times is 10 ~ 30min.
5. the method for semidrying decomposing ammonium chloride according to claim 4, is characterized in that: reactor interior reaction temperature is 100 DEG C ~ 130 DEG C, and the reaction times is 20 ~ 30min.
6. the method for semidrying decomposing ammonium chloride according to claim 1, is characterized in that: described liquid calcium chloride bulk concentration is not less than 75.5%.
7. the reactor of a semidrying decomposing ammonium chloride as claimed in claim 1, there is the outer cylinder body with heating unit, be arranged on the twin screw whipping appts in outer cylinder body, and the venting port be arranged in outer cylinder body, it is characterized in that: being provided with in outer cylinder body can by water with the spray filler pipe of mist pressurization ejection.
8. the reactor of semidrying decomposing ammonium chloride according to claim 7, is characterized in that: described spray filler pipe is provided with multiple mouth spray, and adjacent mouth spray spacing is 10cm.
9. the reactor of semidrying decomposing ammonium chloride according to claim 7, it is characterized in that: described twin screw whipping appts comprise two parallel and rotate the axis be arranged in outer cylinder body, vertically be fixed on the multiple stirring rod on each axis, the gap between the adjacent stirring rod on same axis is 14mm.
10. the reactor of semidrying decomposing ammonium chloride according to claim 7, is characterized in that: the mixing speed of described twin screw whipping appts is 70 ~ 100r/min.
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| CN201510002402.XA CN104609441A (en) | 2015-01-05 | 2015-01-05 | Method for decomposing ammonium chloride by semidry method and reactor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116040672A (en) * | 2023-01-28 | 2023-05-02 | 山东海化集团有限公司 | Method for preparing basic calcium chloride eutectic by ammonia distillation wastewater |
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| CN102838132A (en) * | 2012-09-05 | 2012-12-26 | 河北科技大学 | Method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride |
| CN102976355A (en) * | 2012-10-31 | 2013-03-20 | 四川大学 | Production process for ammonia gas and calcium chloride through utilization of ammonium chloride and carbide slag |
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| JPS52101694A (en) * | 1976-02-24 | 1977-08-25 | Central Glass Co Ltd | Production of calcium chloride solution in ammonia soda process |
| JPS605023A (en) * | 1983-06-22 | 1985-01-11 | Tokuyama Soda Co Ltd | Production of aqueous solution of calcium chloride |
| CN102583438A (en) * | 2012-02-15 | 2012-07-18 | 青岛科技大学 | Process for preparing ammonia by utilizing calcium oxide |
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| CN102838132A (en) * | 2012-09-05 | 2012-12-26 | 河北科技大学 | Method for producing ammonia and high-concentration calcium chloride by decomposing ammonium chloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116040672A (en) * | 2023-01-28 | 2023-05-02 | 山东海化集团有限公司 | Method for preparing basic calcium chloride eutectic by ammonia distillation wastewater |
| CN116040672B (en) * | 2023-01-28 | 2023-06-20 | 山东海化集团有限公司 | Method for preparing basic calcium chloride eutectic by ammonia distillation wastewater |
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Application publication date: 20150513 |