阅读说明：本技术 一种复合闭环嫁接式电池级氯化锌的环保制备工艺 (A kind of environment-friendly preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride ) 是由 王建中 于 2019-09-27 设计创作，主要内容包括：本发明提供了一种复合闭环嫁接式电池级氯化锌的制备工艺,针对原料中含有可溶性的钾盐、钠盐、铵盐；在原料加入时,次氧化锌或者锌灰与水搅拌漂洗,使可溶性的盐溶解于水中除去,经压滤机压滤得到无可溶性盐的氧化锌泥,提高了产品产率；并采用复式常压二级除杂提纯工艺技术,根除了生产过程中重金属铅镉等难稳定控制至电池级标准的问题。且本发明技术方案为常温有效反应途径；以及在遂道窑进行坡板浓缩过程中,将产生的水蒸气回收利用,并将尾气热能与烘箱进行热交换,实现了热能回收综合利用,提高了燃料的热能利用率,收到较大经济效益；通过创新复合嫁接融合技术,得到了另一附加值高的碱式碳酸锌产品,大幅度提高了收益。(The present invention provides a kind of preparation processes of compound closed loop grafting formula LITHIUM BATTERY zinc chloride, for sylvite, the sodium salt, ammonium salt containing solubility in raw material；When raw material is added, secondary zinc oxide or zinc gray and water stirring are rinsed, and so that soluble salt is dissolved in the water removing, are obtained the zinc oxide mud of no soluble-salt through filter press filters pressing, improve product yield；And the problem of using compound normal-pressure second level removal of impurities purifying technology, having eradicated the hardly possible such as heavy metal lead cadmium stability contorting to battery grade standard in production process.And technical solution of the present invention is room temperature effecting reaction approach；And carried out in ramp concentration process in tunnel kiln, the vapor of generation is recycled, and exhaust heat-energy and baking oven are subjected to heat exchange, realizes thermal energy recycling comprehensive utilization, improve the heat utilization rate of fuel, receive larger economic benefit；By innovating grafting compound integration technology, the high basic carbonate zinc product of another added value is obtained, income is greatly improved.)

1. a kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride, which comprises the steps of:

Step 1: water and secondary zinc oxide or zinc gray being stirred evenly in stirring pool, mixed liquor is squeezed by filters pressing with pump later Machine generates zinc mud and rinse water after filter press；Water and secondary zinc oxide or the ratio of zinc gray addition are based on parts by weight 2-3:1-2；

Step 2: hydrochloric acid is added in the zinc mud that step 1 obtains, after reaction is sufficiently stirred, sample detection pH value；It is with pH value It is reaction end between 4.4-4.7；Sodium chlorate iron ions are added in reaction tank again；Mixed liquor is squeezed into filter press with pump, By generating cadmia and crude liquor zinci chloridi after filter press；

Step 3: process is carried out to cadmia and rinse water:

Step (1): cadmia being mixed with rinse water, and hydrochloric acid is added in system, later by mixed liquor squeeze into filter press into Row filters pressing obtains useless mud and low concentration acid chlorization zinc solution；

Step (2): in low concentration acid chlorization zinc solution be added secondary zinc oxide in and, adjust pH value between 4.4-4.7, and Hydrogen peroxide is added, oxidation reaction occurs, and remove iron ion；Mixed liquor is squeezed into filter press filters pressing later, obtains a chlorination Zinc solution and iron cement；

Step (3): being added zinc powder in the liquor zinci chloridi that step (2) obtains, and displacement reaction occurs, by lead ion, cadmium Ion removes, and after the reaction was completed, reaction solution is carried out filters pressing, natural filtration filtrate obtains secondary liquor zinci chloridi again later；

Step (4): being added potassium permanganate in secondary liquor zinci chloridi, and oxidation reaction occurs, and removes manganese ion；It is pressed later Filter, carries out natural filtration to filtrate again, obtains liquor zinci chloridi three times, and soda ash solution reaction is added in liquor zinci chloridi three times eventually The pH value of point is 6.7-7.0, and reaction generates basic zinc carbonate；Basic zinc carbonate reaction system is subjected to filters pressing, and in filters pressing It is rinsed in journey, obtains basic zinc carbonate solid；

Step 4: process is carried out to crude liquor zinci chloridi:

Step (1): potassium permanganate is added in the crude liquor zinci chloridi that step 2 obtains, reaction is sufficiently stirred under room temperature, to remove Remove manganese ion, the iron ion in crude liquor zinci chloridi；Mixed liquor is squeezed into filter press later, obtains ferrimanganic mud and four chlorine Change zinc solution；

Step (2): zinc powder and barium chloride being added into four liquor zinci chloridis obtained in step (1), and it is anti-to carry out room temperature displacement It answers, after the reaction was completed, mixed liquor is squeezed into and carries out filters pressing in filter press, obtain lead cadmium mud and five liquor zinci chloridis；And by five Secondary liquor zinci chloridi natural filtration obtains six liquor zinci chloridis；

Step (3): zinc powder being added into six liquor zinci chloridis that step 2 obtains, and carries out room temperature displacement reaction, and reaction is completed Afterwards, mixed liquor is squeezed into and carries out filters pressing, and natural filtration in filter press, obtain seven liquor zinci chloridis；

Step (4): after potassium permanganate is added in seven liquor zinci chloridis obtained in step 3, oxidation reaction is carried out, has been reacted Mixed liquor is squeezed into filters pressing in filter press by Cheng Hou, and filtrate carries out natural filtration again, obtains high-purity purification liquor zinci chloridi；

Step (5): high-purity purification liquor zinci chloridi is delivered to graphite plate tunnel oven, carries out ramp concentration, and through multistage cold But decrease temperature crystalline obtains zinc chloride finished product of the invention.

2. a kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride according to claim 1, which is characterized in that In the step 2, pressure-filtering process rinses zinc mud with small flow water, and the time is about 10 minutes.

3. a kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride according to claim 1, which is characterized in that The ratio that water and secondary zinc oxide or zinc gray are added in the step 1 is based on parts by weight are as follows: 2:1.

4. a kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride according to claim 1, which is characterized in that It with the hydrochloric acid being added in (1) the step of step 3 be concentration is 31% in the step 2；And the hydrochloric acid content added in step 2 The ratio of parts by weight and secondary zinc oxide or zinc gray is 2:3-6.

5. a kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride according to claim 1, which is characterized in that The basic zinc carbonate solid that step (4) obtains in the step 3 passes through oven drying, packs after crushing, obtains product caustic soda formula Zinc carbonate.

6. a kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride according to claim 1, which is characterized in that After potassium permanganate is added in the step of described step 4 (1), solution measurement pH value is taken to react when pH value is less than 4.0 Secondary zinc oxide is added in journey and raises PH, makes pH value control 4.5 or more.

7. a kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride according to claim 1, which is characterized in that In the step of described step 4 (5) in tunnel oven tail gas with the baking of step (4) application in heat-conduction oil heat switch and step 3 Case carries out heat exchange, and by flue gas three-level desulphurization denitration qualified discharge.

8. a kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride according to claim 1, which is characterized in that The gas for being concentrated to get ramp in the step of described step 4 (5) by being condensed into hot water after vapor condensing unit, and Spray liquid alkaline in condensation process, water ph value control will be condensed in 7-7.5, by delivery and step 3 step (1) with zinc Slag mixing, to be rinsed.

Technical field

The invention belongs to zinc chloride preparation technical field, a kind of compound closed loop grafting formula LITHIUM BATTERY zinc chloride is particularly belonged to Environment-friendly preparation process.

Background technique

Zinc chloride is one of staple product of inorganic chemicals industry, its application range is extremely wide.But in the prior art, produce chlorination The production technology of zinc, there is also following defects:

(1) production technology in the prior art, because production zinc chloride primary raw material zinc gray or secondary zinc oxide in there are Soluble sylvite, ammonium salt etc. enters product being concentrated by evaporation link and can crystallize with zinc chloride, so that the zinc chloride master of production contains Measure it is relatively low, be not achieved main content be 98%-99% LITHIUM BATTERY zinc chloride requirement；And it can also contain exceeded iron, manganese, a huge sum of money Belong to lead, cadmium, therefore the product produced is extremely difficult to gold standard: moreover, in the prior art, to main material secondary zinc oxide or zinc The recovery rate of ash is low, and 5% zinc remains in cadmia in process of production, to improve recovery rate, it is necessary to cadmia with greatly The water of amount is rinsed, then zinc chloride is concentrated to get from rinse water, but the chlorination Zn content in rinse water is lower, is being concentrated During rinse water, a large amount of thermal energy is expended, makes that the production cost increases, or cadmia is sold at a low price, for producing chlorine For the enterprise for changing zinc, this some is lower.

(2) in processing step in the prior art: liquor zinci chloridi zincification powder is replaced under the conditions of 60 DEG C and is once removed Heavy metal process procedure, heavy metal lead cadmium tin nickel etc. as present in raw material is complex, and the cadmium displaced is easily again Secondary redissolve enters solution, then has filters pressing to filter link, and the filter cloth of the readily permeable filter press of the heavy metal displaced is molten with zinc chloride Liquid enters subsequent processing, encounters oxidant and dissolves in liquor zinci chloridi again and causes heavy metals exceeding standard in product zinc chloride；

(3) high energy consumption, high pollution；High energy consumption is mainly reflected in: when reacting liquor zinci chloridi iron removal by oxidation, needing will be anti- It answers solution to be heated up to 80 DEG C, zinc dust precipitation heavy metal reaction link is also required to be heated up to 60 DEG C, above-mentioned reaction solution heated up Journey energy consumption is higher；High pollution is mainly reflected in: zinc chloride ramp evaporates in tunnel oven, and tail gas is exhausted directly in atmosphere, larger portion Divide thermal energy to be discharged with tail gas, causes the waste of thermal energy；It is molten in liquor zinci chloridi during having zinc chloride ramp concentration and evaporation again Agent water is vapor through high temperature evaporation, and vapor is discharged in atmosphere through fibreglass epoxy stove-pipe, generates a large amount of white cigarette gases, and companion There is a small amount of HCl gas, causes environmental pollution.

Summary of the invention

A kind of environment-friendly preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride provided by the present invention, improves chlorine to reach Change yield, the quality of zinc, and achievees the purpose that reduce energy consumption simultaneously and protect environment.

A kind of preparation process of compound closed loop grafting formula LITHIUM BATTERY zinc chloride, which comprises the steps of:

Step 1: water and secondary zinc oxide or zinc gray being stirred evenly in stirring pool, mixed liquor is squeezed by pressure with pump later Filter generates zinc mud and rinse water after filter press；The ratio that water and secondary zinc oxide or zinc gray are added is based on parts by weight For 2-3:1-2；

Step 2: hydrochloric acid is added in the zinc mud that step 1 obtains, after reaction is sufficiently stirred, sample detection pH value；With pH value It is reaction end between 4.4-4.7；Sodium chlorate iron ions are added in reaction tank again；Mixed liquor is squeezed into filters pressing with pump Machine, by generating cadmia and crude liquor zinci chloridi after filter press；

Step 3: process is carried out to cadmia and rinse water:

Step (1): cadmia is mixed with rinse water, and hydrochloric acid is added in system, mixed liquor is squeezed into filter press later Interior carry out filters pressing obtains useless mud and low concentration acid chlorization zinc solution；

Step (2): in low concentration acid chlorization zinc solution be added secondary zinc oxide in and, adjust pH value 4.4-4.7 it Between, and hydrogen peroxide is added, oxidation reaction occurs, and remove iron ion；Mixed liquor is squeezed into filter press filters pressing later, is obtained primary Liquor zinci chloridi and iron cement；

Step (3): being added zinc powder in the liquor zinci chloridi that step (2) obtains, and displacement reaction occurs, by lead from Son, cadmium ion remove, and after the reaction was completed, reaction solution are carried out filters pressing, and to obtain secondary zinc chloride molten for natural filtration filtrate again later Liquid；

Step (4): being added potassium permanganate in secondary liquor zinci chloridi, and oxidation reaction occurs, and removes manganese ion；It is laggard Row filters pressing carries out natural filtration to filtrate again, obtains liquor zinci chloridi three times, and it is anti-that soda ash solution is added in liquor zinci chloridi three times The pH value for answering terminal is 6.7-7.0, and reaction generates basic zinc carbonate；Basic zinc carbonate reaction system is subjected to filters pressing, and is being pressed It is rinsed during filter, obtains basic zinc carbonate solid；

Step 4: process is carried out to crude liquor zinci chloridi:

Step (1): potassium permanganate being added in the crude liquor zinci chloridi that step 2 obtains, reaction is sufficiently stirred under room temperature, To remove manganese ion, the iron ion in crude liquor zinci chloridi；Mixed liquor is squeezed into filter press later, obtains ferrimanganic mud and four Secondary liquor zinci chloridi；

Step (2): zinc powder and barium chloride being added into four liquor zinci chloridis obtained in step (1), carry out room temperature and set Reaction is changed, after the reaction was completed, mixed liquor is squeezed into and carries out filters pressing in filter press, obtains lead cadmium mud and five liquor zinci chloridis；And By five liquor zinci chloridi natural filtrations, six liquor zinci chloridis are obtained；

Step (3): zinc powder being added into six liquor zinci chloridis that step 2 obtains, and carries out room temperature displacement reaction, has reacted Mixed liquor is squeezed into and carries out filters pressing in filter press by Cheng Hou, and natural filtration, obtains seven liquor zinci chloridis；

Step (4): after potassium permanganate is added in seven liquor zinci chloridis obtained in step 3, oxidation reaction is carried out, instead After the completion of answering, mixed liquor is squeezed into filters pressing in filter press, filtrate carries out natural filtration again, and it is molten to obtain high-purity purification zinc chloride Liquid；

Step (5): high-purity purification liquor zinci chloridi is delivered to graphite plate tunnel oven, carries out ramp concentration, and through more Grade cooling crystallization, obtains zinc chloride finished product of the invention.

Further, in the step 2, pressure-filtering process rinses zinc mud with small flow water, and the time is about 10 minutes.

Further, the ratio that water and secondary zinc oxide or zinc gray are added in the step 1 is based on parts by weight are as follows: 2: 1。

It further, be concentration is 31% with the hydrochloric acid being added in (1) the step of step 3 in the step 2；And step The parts by weight and secondary zinc oxide of the hydrochloric acid content added in 2 or the ratio of zinc gray are 2:3-6.

Further, the basic zinc carbonate solid that step (4) obtains in the step 3 passes through oven drying, after crushing Packaging, obtains finished product basic zinc carbonate.

Further, after potassium permanganate being added in the step of step 4 (1), solution is taken to measure pH value, it is small in pH value When 4.0, secondary zinc oxide is added during the reaction and raises PH, makes pH value control 4.5 or more.

Further, in the step of step 4 (5) in tunnel oven tail gas with heat-conduction oil heat switch and step 3 The baking oven of middle step (4) application carries out heat exchange, and by flue gas three-level desulphurization denitration qualified discharge.

Further, the gas being concentrated to get ramp in the step of step 4 (5) passes through vapor condensing unit Afterwards, it is condensed into hot water, and sprays liquid alkaline in condensation process, water ph value control will be condensed in 7-7.5, by delivery and step It is mixed in rapid 3 step (1) with cadmia, to be rinsed.

Present invention process the utility model has the advantages that

(1) for sylvite, the sodium salt, ammonium salt containing solubility in raw material；When raw material is added, secondary zinc oxide or zinc gray It stirs and rinses with water, so that soluble salt is dissolved in the water removing, obtain the zinc oxide mud of no soluble-salt through filter press filters pressing, Improve product yield.And in rinse cycle, a part of zinc salt is entered in rinse water, during preparing basic zinc carbonate It is utilized；And using compound normal-pressure second level removal of impurities purifying technology, it is difficult steady heavy metal lead cadmium etc. in production process has been eradicated The problem of fixed control to battery grade standard.

(2) technical solution of the present invention quotes room temperature effecting reaction approach and eliminates tradition in zinc dust precipitation heavy metal link Iron removal by oxidation manganese link in technique needs to be heated up to 60-80 DEG C of reaction condition；

(3) it is carried out in ramp concentration process in tunnel kiln, the vapor of generation is recycled, is added in cadmia, into Row rinse cycle realizes the closed loop cycle production of steam condensate (SC), reaches environmentally friendly environment-friendly production process；And by tail gas Thermal energy and baking oven carry out heat exchange, realize thermal energy recycling comprehensive utilization, improve the heat utilization rate of fuel, receive larger warp Ji benefit；

(4) high energy consumption low concentration liquor zinci chloridi in production link is married again by innovating grafting compound integration technology In basic zinc carbonate production link, by metathesis reaction principle, zinc ion deep processing extraction is carried out, has been obtained another additional It is worth high basic carbonate zinc product, income is greatly improved.

Detailed description of the invention

Fig. 1 is flow chart of the invention.

Specific embodiment

Explanation is further explained to technical solution of the present invention content below by specific embodiment.