阅读说明：本技术 一种自动配料方法及其应用的三元前驱体生产方法 (A kind of ternary precursor production method of automatic blending method and its application ) 是由 李喜 张军 李鹏飞 首卫文 丘吉祥 李剑锐 于 2019-07-12 设计创作，主要内容包括：本发明提供了一种自动配料方法及其应用的三元前驱体生产方法。该自动配料方法包括如下步骤：原料分别溶解,进行比重测定,DCS根据测定值及设定所需配的比重进行相应计算得出需补水的重量进行自动补水,配制得到设定比重的原料液；将三种原料液加入配料装置,根据所需配制金属盐液的配比及浓度,通过DCS控制三种原料液和水的加入质量,搅拌均匀,控制温度即得到设定配比的金属盐溶液。本发明的自动配料方法对每种原料进行单独溶解,原料主含量及杂质含量的波动及相对误差较小,根据原料液的比重控制质量百分数,控制更加精准,稳定,无需负压管道输送,减少能耗,最大限度的提高配料的精确性及稳定性。(The present invention provides a kind of ternary precursor production methods of automatic blending method and its application.The automatic blending method includes the following steps: that raw material dissolves respectively, carries out gravity test, and the specific gravity that DCS matches according to needed for measured value and setting, which be accordingly calculated, needs the weight of moisturizing to be automatically replenished, and prepares and obtains the material liquid of setting specific gravity；Proportioner is added in three kinds of material liquids, according to required preparing metal saline solution with when concentration, the addition quality of three kinds of material liquids and water is controlled by DCS, is stirred evenly, control temperature is to obtain the metal salt solution of setting proportion.Automatic blending method of the invention individually dissolves every kind of raw material, the fluctuation of the main content of raw material and impurity content and relative error are smaller, according to the specific gravity control mass percent of material liquid, it controls more accurate, stablize, it is conveyed without negative-pressure pipeline, reduces energy consumption, improve the accuracy and stability of ingredient to greatest extent.)

1. a kind of automatic blending method, which comprises the steps of:

S1. raw material dissolves respectively: cobaltous sulfate, manganese sulfate, nickel sulfate being dissolved in water, gravity test is carried out, measured value is inputted The specific gravity that DCS, DCS match according to needed for measured value and setting, which be accordingly calculated, needs the weight of moisturizing to be automatically replenished, It prepares and obtains the material liquid of setting specific gravity；

S2. preparing metal salting liquid: being added proportioners for three kinds of material liquids by raw material conveying device, golden according to required preparations Belong to stirring evenly with when concentration by the addition quality of DCS control three kinds of material liquids and water for saline solution, control temperature to obtain the final product To the metal salt solution of setting proportion.

2. automatic blending method as described in claim 1, which is characterized in that the inducer of the raw material conveying device is provided with out Regulating device is spent, the bottom of the proportioner is provided with weighing equipment, the opening adjusting device and weighing equipment and DCS electricity Connection, controls the addition quality of three kinds of material liquids and water.

3. automatic blending method as claimed in claim 2, which is characterized in that described when quality is added close to target in material liquid DCS controls aperture regulation to 10%.

4. automatic blending method as claimed in claim 3, which is characterized in that be provided with temperature control system in the proportioner System, controls the temperature of metal salt solution.

5. automatic blending method as claimed in claim 4, which is characterized in that the material liquid delivery pump of raw material conveying device is frequency conversion Pump.

6. automatic blending method as claimed in claim 5, which is characterized in that the pipeline of raw material conveying device is removed equipped with filter Magnetic device.

7. automatic blending method as claimed in claim 6, which is characterized in that setting in the dissolver that the raw material dissolves respectively There are weighing system, online densimeter, temperature control system and liquidometer.

8. automatic blending method as described in claim 1, which is characterized in that the cobaltous sulfate, manganese sulfate and nickel sulfate raw material are logical It crosses the lower hopper with moving knife and stationary knife to be crushed, dissolving tank dissolution is added by vibrating screen after being crushed.

9. automatic blending method as claimed in claim 8, which is characterized in that the cobaltous sulfate, manganese sulfate, nickel sulfate raw material are broken Broken advance row carries out pivot cellulose content and impurity content detection, and control acceptable material enters lower hopper.

10. a kind of production method of ternary precursor, which comprises the steps of: use the claims 1~9 Any one the method preparing metal salting liquid is pumped to reaction kettle after filtering metal salt solution, prepare after stablizing reaction Obtain ternary precursor product.

Technical field

The present invention relates to ternary precursor preparation technical fields, more particularly, to a kind of automatic blending method and its answer Ternary precursor production method.

Background technique

Metal saline solution is formulated with following two method in ternary precursor production at present.One is by manually will centainly weigh The nickel sulfate, cobaltous sulfate, manganese sulfate for measuring proportion are added to material-compound tank, are mixed after adding a certain amount of pure water, so ICP is carried out afterwards and chemistry titration detection, host element squeeze into storage tank, unqualified progress with when concentration after the acceptability limit of control Feed supplement is until qualified.Another kind is to be evacuated to nickel sulfate, cobaltous sulfate, manganese sulfate raw material after measuring chute again using pipe conveying equipment Spiral blanking is carried out to preparing tank, pure water is controlled by ball valve and preparing tank is added, then carries out sample detection after being stirred mixing, Enter storage tank after qualification.Existing preparation method has the disadvantage that (1) nickel sulfate, cobaltous sulfate and manganese sulfate raw material are solid knot Brilliant particle, Manual material feeding large labor intensity, easy contact toxicity dust, the degree of automation are low；(2) mode conveyed with negative-pressure pipeline Nickel sulfate, cobaltous sulfate, manganese sulfate raw material are evacuated to measuring chute, energy consumption is high, and each raw material easily agglomerates, and especially cobaltous sulfate easily agglomerates, Not only feed intake inconvenience, and is easy plugging and causes to block measuring secondary agglomeration inside feed bin, causes to feed intake unsmooth, prolong significantly Working hour is missed；(3) three kinds of raw materials not only have an agglomeration, and simultaneously because containing compared with multi-crystallization water, by raw material producer technique and The influence of the factors such as stability, the storage transportation and storage of process, host element, the crystallization water and outside moisture inevitably will appear Certain fluctuation；(4) nickel sulfate, cobaltous sulfate, manganese sulfate raw material supplied materials batch are typically small, and the host element and impurity of each batch Content has a certain difference, and causes each ingredient not only to carry out calculating and opens charger sheet, and due to every kind of raw material itself Content error, the ratio and concentration of wiring solution-forming Ni:Co:Mn have certain fluctuation, influence the accuracy of ingredient, especially match When making nickelic metal saline solution, since Co, Mn of needs are relatively fewer, and when feeding intake, since manganese sulfate has particle tiny Easily hike up etc. characteristics, have certain influence to the accuracy of weight, cobaltous sulfate humidity it is big it is easy to hang leans on, there are the hidden of the built-in material of pipeline Suffer from, so each element proportion can be caused larger fluctuation occur.(5) the entire blending process period is long, every batch of need 4 hours with On, every batch of metal saline solution nickel content carries out titration detection, cobalt manganese element carries out ICP detection, and time-consuming needs 3 hours or more, it leads Cause the ingredient whole cycle time it is very long, efficiency is relatively low, restrict producing line overall throughput, if you need to by after ingredient metal saline solution proportion and Concentration controls in smaller range, and such method is difficult to realize substantially, and needs frequent progress feed supplement, seriously restricts production capacity. (6) in production metal saline solution it is most important with when concentration, concentration and proportion will affect the technique and its stabilization of reaction process Property, the stability of metal saline solution matched between when batch is most important to the consistency of ternary precursor, and fluctuation will lead to greatly whole The consistency of the indexs such as a process and the main content of final products is poor.And the consistency of presoma directly will mix lithium from ternary precursor Start to affect the process stability and final finished consistency that ternary material produces.In conclusion the shortcomings that entire ingredient, is Using crystal raw material feed intake inconvenience, large labor intensity, time-consuming for entire blending process, detection time is long, metal salt between batch There is certain fluctuation in the pivot cellulose content and concentration of liquid, if you need to eliminate these fluctuations, need to carry out frequent feed supplement and detection, this A little disadvantages leverage production efficiency, the stability of process control and the consistency for being finally made into ternary material finished product.It is existing Technology CN108088730A discloses a kind of accurate dosing method of ternary precursor metal salt solution, the main still needle of this method Influence to temperature using the flow volume of the mass flowmenter measurement metal salt solution of Coriolis force principle, then carries out phase It closes temperature correction and metal salt solution density and final accurately metal ion mass flow is calculated in concentration of metal ions, disappear In addition to temperature is influenced to improve the accuracy of measurement, but the precision of the instrument only has 0.15%, and needs to acquire different time Measurement quality, the data of density and temperature of section carry out similar volume further according to temperature and correct to obtain density, further according to concentration With the linear relationship of density (linear relationship degree with solution purity and temperature in relation to) obtain the concentration of metal saline solution, finally again The metal concentration accumulated.The calculating detection variable of whole process is more, to the accuracy of instrument and process, accuracy and steady Qualitative requirement is high, and system relative error is larger, and obtained metal saline solution proportion and concentration will have biggish fluctuation range, and match It just can be used after needing to carry out host element detection after good, otherwise risk is high, and the disclosure technology is not to the mistake of whole system Difference is analyzed, and is analyzed the influence fluctuation range with when concentration of metal saline solution.The disclosure technology is for above-mentioned The operational issues such as the agglomeration problems mentioned, metal salt caused by the batches error problems such as material crystal water, raw material impurity content are molten The accuracy and stability problem of liquid concentration do not provide relevant solution, and technical problem need further to solve.

Summary of the invention

The technical problem to be solved by the present invention is to overcome the accurate of the metal salt solution of existing ternary precursor material preparation Property and stability defect and deficiency, provide a kind of automatic blending method, the metal saline solution of this method, which is prepared, realizes automation, subtracts Few manually-operated difficulty, and blending process realization can be made to be precisely controlled, the concentration and host element content ratio wave of metal saline solution It moves minimum, ICP detection is carried out to metal saline solution without every batch of and is monitored with precipitation method titration detection, ingredient is improved The overall efficiency of process and the stability of quality can be saved in real time in ingredient data DCS log, are met enterprise two and are changed fusion The requirement of system, while reducing personal injury of the process to environment and personnel.

Another object of the present invention is to provide a kind of ternary precursor production methods.

Above-mentioned purpose of the present invention is achieved through the following technical solutions:

A kind of automatic blending method, includes the following steps:

S1. raw material dissolves respectively: cobaltous sulfate, manganese sulfate, nickel sulfate being dissolved in water, gravity test is carried out, by measured value DCS is inputted, the specific gravity that DCS matches according to needed for measured value and setting, which be accordingly calculated, needs the weight of moisturizing to be mended automatically Water is prepared and obtains the material liquid of setting specific gravity；

S2. preparing metal salting liquid: three kinds of material liquids are added by proportioners by raw material conveying device, are matched according to required Being stirred evenly with when concentration by the addition quality of DCS control three kinds of material liquids and water for metal saline solution processed, controls temperature Obtain the metal salt solution of setting proportion.

Automatic blending method provided by the invention, every kind of raw material is individually dissolved, due to main content mass fraction Decline, material liquid quality increase, and the fluctuation of main content and impurity content and relative error will reduce, simultaneously because disappearing after dissolution In addition to the crystallization water and moisture water content error, impurity content error is only existed, corresponding error is further reduced.

The sulfate starting material of LITHIUM BATTERY, in addition to the sulfate of host element, remaining impurity content is considerably less (< 0.03%), batch Fluctuation range between secondary is less than 0.015%, and after being dissolved into solution, the value is less than 0.007%, so the synthermal item of the impurity content The variation of caused volume, weight and density almost can be ignored under part, and it is molten that solution may be considered single sulfate Liquid.According under certain temperature, nickel sulfate, cobaltous sulfate, manganese sulfate solution have a correspondence under different quality percent concentration Specific gravity, since concentration and specific gravity are there are higher linear relationship, i.e. (wherein Y is concentration to Y=aX+b, and X is specific gravity, and a, b are normal Number), the every reduction 0.0001g/ml of specific gravity is known that according to this relationship, mass percent reduces 0.0001a accordingly, according to meter It calculates, the every decline 0.0001g/ml of nickel sulfate solution specific gravity, the percentage for needing to be added water is 0.03917%, can according to this relationship When acquiring gravity reduction 0.0001*N (g/ml) to write formula with DCS configuration, needs to be added how many water, can pass through Online densimeter, high-precision densimeter, differential pressure levelmeter, temperature transmitter, weighing system and steam pipe coil temperature control system carry out The specific gravity control of material liquid obtains the material liquid of required certain temperature and concentration, to obtain the raw material of aimed quality percentage Liquid.

Since the maximum fluctuation value of the main content of raw material is 0.3%, so it is theoretical that calculated value is first added when preparation raw material liquid The 99.7% of required water after stirring certain time into solution, controls temperature, 0.1 DEG C of temperature accuracy, selects high precision specific gravity Meter (precision 0.0001g/mL) detects gravity, calculates according to data are practical, the sulphur under certain temperature and specific gravity The sour every decline 0.0001g/mL of nickel solution specific gravity, the percentage for needing to be added water is 0.03917%, since the precision of densitometer is 0.0001g/mL, thus error caused by densitometer cause dilution dissolve after pivot cellulose content error be 0.0036%, the mistake Difference will be much smaller than all errors for the route that fed intake originally, and detection time is short, meets control and requires.

According to required preparing metal saline solution with when concentration, pass through the temperature and addition of three kinds of material liquids of control, pure water The weight of material-compound tank, so that it may the metal salt solution strictly matched, by the temperature for controlling metal salt solution, so that it may supervise It controls its specific gravity and obtains certain density metal salt solution, improve the accuracy and stability of ingredient to greatest extent, make to react The whole system control of section is more stable, and homogeneity of product improves.

Preferably, the inducer of the raw material conveying device is provided with opening adjusting device, the bottom of the proportioner It is provided with weighing equipment, the opening adjusting device and weighing equipment are electrically connected with DCS, control the addition of three kinds of material liquids and water Quality.

Opening adjusting device is preferably electric control valve, and three kinds of material liquids are added separately to by what is set than column weight In material-compound tank, the weight of whole process controls weight, material-compound tank material liquid import on pipeline by the weighing equipment of ingredient pot bottom Electric control valve at end controls flow, and electric control valve can automatically adjust open position, be delayed when close to target weight Slow accurate addition, so as not to it is excessive, realize that material liquid is precisely added in material-compound tank by setting ratio weight, whole process is controlled automatically System.

Preferably, when quality is added close to target in material liquid, the DCS controls aperture regulation to 10%.

Preferably, it is provided with temperature control system in the proportioner, controls the temperature of metal salt solution.Material liquid adds After entering, the regular hour is stirred for get the metal saline solution of certain proportion and concentration is arrived, the temperature of saline solution passes through material-compound tank Interior steam(-)coil is controlled, and online densimeter can show the specific gravity of metal saline solution, may be set in a certain range It is interior to be used as monitoring, it serves as warning.

Preferably, the material liquid delivery pump of raw material conveying device is variable frequency pump.Material liquid delivery pump is variable frequency pump, Ke Yigen According to the degree of closeness frequency conversion of setting target weight, it is ensured that the weight being added accurately is controlled.

Preferably, the pipeline of raw material conveying device is equipped with filter and removes magnetic device.

Preferably, weighing system, online densimeter, temperature control are provided in the dissolver that the raw material dissolves respectively System and liquidometer.It, can be molten with real-time display according to on-line densimeter, weight, online liquid level difference gauge combination DCS process control The liquid level and volume of liquid, online temperature transmitter can control program by real-time monitoring and DCS and carry out temperature control.

Preferably, the cobaltous sulfate, manganese sulfate and nickel sulfate raw material are carried out brokenly by the lower hopper with moving knife and stationary knife It is broken, dissolving tank dissolution is added by vibrating screen after being crushed.Since cobaltous sulfate, nickel sulfate, manganese sulfate have agglomeration problems, especially The agglomeration of cobaltous sulfate, hard and bulk are not easy to feed intake, now by cobaltous sulfate agglomeration can by the lower hopper with moving knife and stationary knife into Using dissolving tank is directly added into after vibrating screen after row is broken, the difficult problem that feeds intake can solve in this way, while not needing negative pressure Pipeline reduces energy consumption, facilitates operation.

Preferably, the cobaltous sulfate, manganese sulfate, nickel sulfate raw material contain in broken advance row progress pivot cellulose content and impurity Amount detection, control acceptable material enter lower hopper.

First qualified nickel sulfate, cobaltous sulfate, the manganese sulfate crystal raw material of buying back are sampled and are detected, Nickel sulfate, cobaltous sulfate, manganese sulfate dissolution automatic control program, typing host element content data, group are established in DCS ingredient interface respectively State program is calculated according to the mass percent of the mass percentage content of host element, the weight of addition and the required material liquid of setting The pure water amount being added needed for out.

The accuracy of whole process is, the accuracy of online densimeter, raw material impurity content (basic supplied materials impurity contains Measure lower), the uniformity of the control of process temperature, stirring.

It is the weight, volume and specific gravity that can also fix each ingredient in preparing metal salting liquid, these three amounts are one by one Corresponding amount exceeds error range, is then sampled detection if cannot correspond.

A kind of production method of ternary precursor includes the following steps: using above method preparing metal salting liquid, will be golden Belong to pumping value reaction kettle after salting liquid filters, ternary precursor product is prepared after stablizing reaction.The material liquid prepared is beaten Enter transfer storage tank, there is the stirring of steam pipe coil band in storage tank, makes the concentration of metal saline solution certain by the temperature for controlling certain In range, the discharge nozzle of transfer storage tank is provided centainly to the metering pump of each reaction kettle than the metal saline solution of column and concentration.

Compared with prior art, the beneficial effects of the present invention are:

(1) automatic blending method of the invention individually dissolves every kind of raw material, the main content of raw material and impurity content Fluctuation and relative error are smaller.

(2) automatic blending method of the invention passes through the linear relationship of mass concentration and specific gravity, online progress material liquid Specific gravity control obtains the material liquid of aimed quality percentage, and control is more accurate, stablizes.

(3) raw material of the invention passes through stringent Quality Detection, and dissolving tank dissolution is added by vibrating screen after being crushed, solves The problems such as agglomeration, moisture and impurity content fluctuate does not need negative-pressure pipeline conveying, reduces energy consumption, facilitate operation.

(4) uniformity of control and the stirring of temperature improves to greatest extent in metal salt solution process for preparation of the invention The accuracy and stability of ingredient control the whole system of conversion zone more stable, and homogeneity of product improves.

(5) automatic blending method of the invention and ternary precursor production method whole process can be produced in enormous quantities, raw It is higher to produce efficiency, full-automation production does not need to carry out cumbersome calculating every time.

Specific embodiment

The present invention is further illustrated With reference to embodiment, but embodiment the present invention is not done it is any The restriction of form.Unless otherwise indicated, source chemicals used in the embodiment of the present invention are the source chemicals routinely bought.