CN105740605B - A kind of zinc hydrometallurgy copper removal process production status appraisal procedure - Google Patents

A kind of zinc hydrometallurgy copper removal process production status appraisal procedure Download PDF

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CN105740605B
CN105740605B CN201610044941.4A CN201610044941A CN105740605B CN 105740605 B CN105740605 B CN 105740605B CN 201610044941 A CN201610044941 A CN 201610044941A CN 105740605 B CN105740605 B CN 105740605B
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orp
dorp
copper removal
state
copper
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CN105740605A (en
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朱红求
张斌
阳春华
张凤雪
李勇刚
桂卫华
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Central South University
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Abstract

The invention discloses a kind of zinc hydrometallurgy copper removal process production status appraisal procedures, the mechanism model that zinc hydrometallurgy is purified to copper removal process is combined with oxidation-reduction potential (ORP), the appraisal procedure of the copper removal process production status based on ORP and ORP change rates is established according to fuzzy control theory, fuzzy rule base is established based on industry park plan data, assessed value, the production status of online evaluation copper removal process are asked using gravity model appoach defuzzification.The technology of the present invention has directive significance to the addition of zinc powder, to reach the target of steady production.

Description

A kind of zinc hydrometallurgy copper removal process production status appraisal procedure
Technical field
The invention belongs to zinc hydrometallurgy copper removal process control technology fields, are related to a kind of zinc hydrometallurgy copper removal process production work Condition appraisal procedure.
Background technology
First process of the copper removal process as zinc hydrometallurgy purification process is one of the key link of purification production, right Purge outlet solution qualification rate, electrolytic zinc quality play an important roll.The process in two concatenated successive reaction stirred tanks, Zinc powder is persistently added, it is dense to retain regulation for the impurity copper ion extra in sulfate precipitate zinc solution in the form of cuprous oxide, elemental copper The activator that the copper ion of degree is reacted as follow-up workshop section.
Since copper removal process production environment is complicated and there is high temperature highly corrosive, copper ion concentration to be difficult to monitor on-line. To differentiate operating mode and adjusting zinc powder, operator often estimates copper ion concentration according to ORP.However, between ORP and copper ion concentration The hysteresis quality of uncertainty and long flow reactor causes artificial experience estimation larger with actual condition gap, and zinc powder is adjusted Precision is unstable, causes the problems such as outlet copper ion qualification rate is low, zinc powder waste rate is high.For this phenomenon, analyzes ORP and go out Relationship between mouth copper ion, variations of the research ORP in large-scale reactor influence copper removal operating mode, establish the assessment of copper removal operating mode Model, the assessment rule of production status is established according to fuzzy theory, foundation is provided for zinc powder adjusting, for stabilization of export copper ion Concentration improves outlet solution qualification rate, reduces zinc consumption amount and is extremely important.
Invention content
It is an object of the invention to be assessed in real time production status during copper removal, avoid because cannot accurately judge Production status causes next step zinc powder to add wrong problem, provides a kind of assessment side of zinc hydrometallurgy copper removal process production status Method.
A kind of zinc hydrometallurgy copper removal process production status appraisal procedure, comprises the steps of:
Step 1:Mutual indepedent principle, material balance principle and Arrhenius establishing equations based on chemical reaction and oxygen Change the related copper removal process reaction dynamic models of reduction potential ORP:
Wherein, t is current time;C0It is reactor inlet copper ion concentration;CtIt is t moment copper ion concentration;eorpIt is oxygen Change reduction potential value;p1, p2, q1, q2, A1, A2It is parameter to be identified, the C based on industry spot acquisition0, Ct, eorpValue identification obtains ?;
Step 2:The dynamic model established according to step 1 is excessively high, stable, too low by copper ion concentration as defined in industrial production State is converted to corresponding oxidation reduction potential value eorp, it is then based on fuzzy control theory structure ORP and ORP change rates Membership function under dORP different conditions;
【Relationship between step 1 and step 2 is from concentration C to ORP value eorpConversion, in the industry, outlet copper from Sub- concentration will be stablized in 0.2g/L to 0.4g/L, and copper ion concentration is converted into the value of ORP based on the dynamic model in step 1 Afterwards, the assessment of next step can just be carried out;】
Step 3:The assessment copper removal process fuzzy rule based on ORP and dORP is created according to the membership function that step 2 obtains, The assessed value g of production status is obtained to the online defuzzification of sampled point using gravity model appoach again.
The membership function built in the step 2 under ORP and ORP change rate dORP different conditions is as follows:
Step 2.1:ORP and dORP are described using trapezoidal membership function, the common version of trapezoidal membership function is:
Wherein,It represents x and is subordinate to angle value under jth kind state;
When i=1, x represents the value of ORP, and j=1,2,3 indicate mistake the low state L, stable state S of ORP and excessively high shape respectively State H;
When i=2, x represents the value of dORP, and j=1,2,3 indicate the negative state N, nought state Z and positive status P of dORP respectively;
A, b, c, d are parameter to be calculated;
Step 2.2:The dynamic analog pattern built according to step 1 is dense by the copper removal procedure exit copper ion in stable state Degree is converted to ORP:
【The requirement of copper removal procedure exit copper ion concentration is stable state between 0.2g/L and 0.4g/L, and copper ion wave It moves and stablizes the most between 0.25g/L to 0.35g/L;
The ORP upper limits are set according to actual industrial process as 100mV, lower limit 0mV.According to copper removal process control period Δ T= 10min andIf variation is stable state to ORP between 40mV and 70mV in 10min, and in 47.5mV Stablize the most to being fluctuated between 62.5mV.】
Step 2.3:ORP and dORP trapezoidal membership functions expression formula and step 2.2 in conjunction with obtained by step 2.1 obtain steady Determine the corresponding ORP of copper removal procedure exit copper ion concentration of state, obtains ORP to be calculated in step 2.1 and dORP and be subordinate to letter Number parameter is as follows:
The following matrix table of assessment copper removal process fuzzy rule based on ORP and dORP:
Fuzzy rule matrix table
Wherein, reactiveness uses copper ion concentration too low VL, low L, relatively low ML, normal S, higher MH, high H and mistake respectively High VH is indicated.
Advantageous effect
The present invention is to coexist the mutual indepedent principle of chemical reaction, based on material balance principle and Arrhenius equations, The copper removal process reaction dynamic model based on oxidation-reduction potential ORP is created, and according to fuzzy control theory, it is proposed that a kind of To copper removal process production status appraisal procedure, avoid because caused by can not accurately judging production status zinc powder addition it is excessive or Very few problem;The reactiveness of copper removal process in current reactor is assessed according to the instantaneous value of ORP and Trend value, to right Guidance is played the role of in the addition of next step zinc powder, and to correct zinc powder additive amount, zinc powder continued to add in artificial unreasonable setting Zinc powder waste, deficient addition cause the problems such as outgoing quality is unstable, product qualification rate is relatively low caused by adding.
Using the zinc hydrometallurgy copper removal process production status appraisal procedure of the present invention, it can accurately assess copper removal process and work as Preceding production status.Compared to artificial qualitative estimation production status, this method assesses accuracy height, and can be according to assessed value pair Next production status is predicted have directive significance to the addition of zinc powder, so that copper ion concentration fluctuation in outlet is reduced, reach The target of steady production.
The features such as present invention has calculating quick and easy, and production status assessment is accurate, is suitable for zinc hydrometallurgy copper removal mistake The assessment of journey production status to copper removal process steady production, improves product quality, reduces cost and be of great significance.
Description of the drawings
Fig. 1 ORP membership function relationships;
Fig. 2 dORP membership function relationships;
Fig. 3 Cu ion concentrations and assessed value contrast schematic diagram.
Specific implementation mode
For a better understanding of the technical solution of the present invention, making to embodiments of the present invention below in conjunction with Figure of description It further describes.
The first step establishes the copper removal process reaction dynamic model based on oxidation-reduction potential ORP.
Copper removal process includes two main redox reactions:Copper precipitation reaction and comproportionation reaction.Both reactions are all Meet single order kinetics equation:
ri=-kiC (1)
Wherein ri, (i=1,2) is the reaction rate of i-th of main reaction, and C is copper ion concentration, ki, (i=1,2) is i-th The rate constant of a main reaction.
Copper removal process reaction dynamic model is established according to single order kinetics equation, specially:
Step 1.1:According to the mutual indepedent principle and material balance principle that chemical reaction coexists, copper removal process cobalt ions is dense Degree rate of change is represented by:
Step 1.2:According to Arrhenius equations:It may determine that reaction rate constant and activation It can Ea,iIt is related.Wherein, AiFor parameter to be identified, R is gas constant, and T is absolute temperature.
Step 1.3:Mutual indepedent principle is reacted according to parallel pole, the reaction in step 2 can mutually share electrode potential Form mixed potential, and the rate that mixed potential is reacted by influencing electron transfer rate come determining electrode.And mixed potential Wired sexual intercourse between oxidation-reduction potential ORP:emix=peorp-q.In conjunction with formula (2), then between copper ion concentration and ORP Mathematical relationship be represented by:
Wherein, p1, p2, q1, q2A1, A2It is parameter to be identified, C0It is determined by reaction process with t.
The foundation of copper removal process dynamic model finishes.
Second step, blurring ORP and ORP rate of changes (dORP), and build membership function.
According to the first step obtain dynamic model, can be converted between ORP and copper ion concentration, to ORP come The copper ion concentration of estimation reactor outlet judges reactiveness.It can determine that by the membership function of ORP and dORP and react at this time Copper ion concentration and variation tendency in device.
Step 2.1:ORP and dORP are described using trapezoidal membership function, common version is:
Wherein i=1,2 indicate ORP and dORP, j=1,2 respectively, and 3 indicate the mistake low state (L) of ORP, stable state respectively (S) high state (H) and the negative state (N) of dORP, nought state (Z) and positive status (P) are crossed and
Step 2.2:Copper removal procedure exit copper ion concentration requires between 0.2g/L and 0.4g/L, and copper ion fluctuation exists Stablize the most between 0.25g/L to 0.35g/L, the dynamic model built according to the first step is converted to ORP and is:
The ORP upper limits are set according to actual industrial process as 100mV, lower limit 0mV.According to copper removal process control period Δ T= 10min andIf variation is stable state to ORP between 40mV and 70mV in 10min, and in 47.5mV Stablize the most to being fluctuated between 62.5mV.
Then ORP and dORP membership function parameters are:
Third walks:Create the fuzzy rule base of copper removal process production status assessment
The fuzzy set obtained according to second step assesses the rule of copper removal process to create, since ORP represents reaction Current state, dORP represent the value of ORP in the situation being likely to occur in the future.Therefore fuzzy rule need to take into account the two simultaneously It is interior, the specific steps are:
Step A:Create fuzzy rule matrix table:
Wherein, reactiveness uses copper ion concentration too low (VL) respectively, low (L), relatively low (ML), normal (S), higher (MH), high (H), excessively high (VH) are indicated.
Step B:Defuzzification is carried out to sampled point with gravity model appoach, obtains assessed value g.
Embodiment one:
Superiority for certain Qian Xin factories wet method refining Zinc hydrometallurgy process copper removal process to illustrate the invention.
The first step establishes the copper removal process reaction dynamic model based on oxidation-reduction potential ORP.
Desired outlet copper ion concentration range is converted into ORP by second step according to the dynamic model of foundation, blurring ORP and ORP rate of changes (dORP), and membership function is built, function distribution is as shown in Figure 1 and Figure 2.
Third walks, and the mould of the copper removal process production status assessment based on ORP and dORP is created according to the fuzzy set of acquisition Paste rule, regular matrix table are shown as follows:
Production status assesses fuzzy reasoning table
Then gravity model appoach is used, to sampled point defuzzification, to obtain life in 48 hours on MATLAB platforms by fuzzy rule The assessed value of operating mode is produced, shown in following production status assessed value table, wherein h represents hour, and g represents assessed value.
Production status assessed value
Using copper removal process production status appraisal procedure, production status in 48 hours is assessed, actual acquisition is used in combination Copper ion concentration compare, as shown in Figure 3.From the figure 3, it may be seen that can effectively be assessed using the blur estimation method proposed Copper removal process production status, and predict the trend of copper ion concentration in reactor, there is directive significance to the addition of zinc powder, to reach To the target of steady production.

Claims (2)

1. a kind of zinc hydrometallurgy copper removal process production status appraisal procedure, which is characterized in that comprise the steps of:
Step 1:Mutual indepedent principle, material balance principle and Arrhenius establishing equations based on chemical reaction are gone back with oxidation The related copper removal process reaction dynamic models of former current potential ORP:
Wherein, t is current time;C0It is reactor inlet copper ion concentration;CtIt is t moment copper ion concentration;eorpIt is that oxidation is gone back Former current potential value;p1, p2, q1, q2, A1, A2It is parameter to be identified, the C based on industry spot acquisition0, Ct, eorpValue identification obtains;
Step 2:According to the dynamic model of step 1 foundation that copper ion concentration as defined in industrial production is excessively high, stable, mistake low state Be converted to corresponding oxidation reduction potential value eorp, it is then based on fuzzy control theory structure ORP and ORP change rates dORP not With the membership function under state;
Step 3:The assessment copper removal process fuzzy rule based on ORP and dORP is created according to the membership function that step 2 obtains, then is adopted The assessed value g of production status is obtained to the online defuzzification of sampled point with gravity model appoach;
The membership function built in the step 2 under ORP and ORP change rate dORP different conditions is as follows:
Step 2.1:ORP and dORP are described using trapezoidal membership function, the common version of trapezoidal membership function is:
Wherein,It represents x and is subordinate to angle value under jth kind state;
When i=1, x represents the value of ORP, and j=1,2,3 indicate mistake the low state L, stable state S of ORP and cross high state H respectively;
When i=2, x represents the value of dORP, and j=1,2,3 indicate the negative state N, nought state Z and positive status P of dORP respectively;
A, b, c, d are parameter to be calculated;
Step 2.2:The copper removal procedure exit copper ion concentration in stable state is turned according to the dynamic analog pattern that step 1 is built It is changed to ORP:
Step 2.3:The stabilization shape that ORP and dORP trapezoidal membership functions expression formula and step 2.2 in conjunction with obtained by step 2.1 obtain The corresponding ORP of copper removal procedure exit copper ion concentration of state obtains ORP to be calculated in step 2.1 and joins with dORP membership functions Number is as follows:
2. according to the method described in claim 1, it is characterized in that, the assessment copper removal process based on ORP and dORP is fuzzy The following matrix table of rule:
Fuzzy rule matrix table
Wherein, reactiveness uses copper ion concentration too low VL, low L, relatively low ML, normal S, higher MH, high H and excessively high VH respectively To indicate.
CN201610044941.4A 2016-01-22 2016-01-22 A kind of zinc hydrometallurgy copper removal process production status appraisal procedure Active CN105740605B (en)

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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Bei Sun et.al.A gradient optimization scheme for solution purification process.《Control Engineering Practice》.2015,第44卷 *
Evaluation strategy for the control of the copper removal process based on oxidation–reduction potential;Bin Zhang et.al;《Chemical Engineering Journal》;20150906;第284卷;第2.2节、第2.3节、第3节倒数第1段、图2、表2、表3 *
基于特征加权FSVM的锌液净化除铜工况评估;谢永芳 等;《信息与控制》;20141231;第43卷(第3期);全文 *

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