CN109626344B - Resource utilization method suitable for PCB deplating waste liquid - Google Patents
Resource utilization method suitable for PCB deplating waste liquid Download PDFInfo
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- CN109626344B CN109626344B CN201910046604.2A CN201910046604A CN109626344B CN 109626344 B CN109626344 B CN 109626344B CN 201910046604 A CN201910046604 A CN 201910046604A CN 109626344 B CN109626344 B CN 109626344B
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/42—Preparation from nitrates
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Abstract
The invention discloses a resource utilization method suitable for PCB deplating waste liquid, wherein the deplating waste liquid is copper nitrate waste liquid, and the resource utilization method comprises the following steps: pre-treating, namely filtering the copper nitrate waste liquid to remove impurities, adding a sulfuric acid solution into the filtered copper nitrate waste liquid, and adjusting the acid concentration of the system to obtain an inorganic phase for later use; extracting, namely putting the inorganic phase into an extraction device, adding an extracting agent TBP, controlling the extraction condition, and extracting with nitric acid to obtain an extract phase and a raffinate phase; back extraction, namely putting the extract phase into an extraction device, adding water, controlling back extraction conditions, and performing back extraction of nitric acid to obtain a nitric acid solution; and crystallizing, namely adding copper oxide or copper hydroxide solid into the raffinate phase, neutralizing redundant acid, adjusting the pH of a system to be 2-3, filtering, and crystallizing the filtrate to obtain copper sulfate crystals. The technical scheme of the invention realizes the recycling of copper and waste acid at normal temperature and normal pressure, reduces energy consumption, avoids resource waste, prevents environmental pollution and reduces production cost.
Description
Technical Field
The invention relates to the technical field of deplating waste liquid treatment, in particular to a resource utilization method suitable for PCB deplating waste liquid.
Background
Electroplating is an important production process in the Printed Circuit Board (PCB) industry and the electroplating industry. The deplating waste liquid is mainly copper nitrate waste liquid, aiming at the copper nitrate waste liquid, the existing production process mainly focuses on resource utilization of copper, only low-grade copper mud or copper products are obtained, such as an acid-base neutralization method and a replacement method, the resource utilization of nitric acid is not considered, resources are wasted, and the cost is increased. According to the solubility product difference, the copper ions are recycled by adopting the forms of copper oxalate and copper acetate, and the scrapped nitric acid is returned to a deplating system by reducing the form of the copper ions of the system. The electrolysis process pretreatment also adopts alkali to neutralize the acid of the system, and then uses an electrolysis device to recover copper. Because of the existence of nitric acid in the system, nitrogen oxides are generated in the electrolysis process, the requirement on corrosion resistance of equipment is high, and the cost of the electrolysis equipment is high. Research is also carried out on primary recovery of nitric acid in a copper nitrate system by means of diffusion dialysis or reduced pressure distillation, but research and development centers of gravity are all placed on tail end copper recovery, and the evaporation process also has the problems of overflow of nitrogen oxides and corrosion prevention requirements of equipment.
Disclosure of Invention
The invention mainly aims to provide a resource utilization method suitable for PCB deplating waste liquid, which aims to realize the recycling of copper and waste acid at normal temperature and pressure, reduce energy consumption, avoid resource waste, prevent environmental pollution and reduce production cost.
In order to achieve the purpose, the resource utilization method for the PCB deplating waste liquid provided by the invention is characterized in that the deplating waste liquid is copper nitrate waste liquid, and the resource utilization method comprises the following steps:
step S1: pre-treating, namely filtering the copper nitrate waste liquid to remove impurities, adding a sulfuric acid solution into the filtered copper nitrate waste liquid, and adjusting the acid concentration of the system to obtain an inorganic phase for later use;
step S2: extracting, namely putting the inorganic phase into an extraction device, adding an extracting agent TBP, controlling extraction conditions, and extracting nitric acid to obtain an extract phase and a raffinate phase;
step S3: back extraction, namely putting the extract phase into an extraction device, adding water, controlling back extraction conditions, and performing back extraction of nitric acid to obtain a nitric acid solution;
step S4: and crystallizing, namely adding copper oxide or copper hydroxide solid into the raffinate phase, neutralizing redundant acid, adjusting the pH of a system to be 2-3, filtering, and crystallizing the filtrate to obtain copper sulfate crystals.
Preferably, in step S1, the addition amount of the sulfuric acid solution is 1.5 to 2.5 times the mole number of copper ions in the copper nitrate waste liquid.
Preferably, in step S2, the extraction conditions are specifically: the extraction temperature is set to be 20-50 ℃; the extraction time is set to be 1-30 min; setting the extraction ratio to be 1-3; the extraction stage number is set to be 2-5 stages.
Preferably, the step S3 specifically includes dividing the extract phase into a plurality of equal portions, contacting the plurality of equal portions of extract phase with the same portion of water, respectively, performing the back extraction with nitric acid, and controlling the back extraction conditions to obtain the nitric acid solution.
Preferably, the stripping conditions are in particular: the extraction temperature is set to be 20-50 ℃; the extraction time is set to be 0.5-5 min; the extraction phase ratio was set to 1; the extraction stage number is set to be 3-10 stages.
Preferably, the extraction manners in step S2 and step S3 are both set as counter-current extraction.
Preferably, in step S4, the crystallizing treatment of the filtrate specifically includes: and (4) evaporating, concentrating, cooling and crystallizing the filtrate in sequence to obtain copper sulfate crystals.
Compared with the prior art, the invention has the beneficial effects that: the traditional process method is broken through, the deplating waste acid is recycled through the combined process route of extraction-back extraction-crystallization, and the copper and acid are recycled:
(1) the nitric acid product obtained by the invention is pure nitric acid solution, and the product can return to a deplating working section and can be sold to other customers for different occasions according to market demands;
(2) the invention crystallizes the copper sulfate product in the copper sulfate solution system after separating the nitric acid, has higher quality, is beneficial to the sale of the product, improves the added value of the product and increases the profit of enterprises;
(3) the invention recycles the nitric acid and the copper ions in the copper nitrate waste liquid to obtain the corresponding product, and the recycling utilization rate is high;
(4) the method does not need to use alkali for pre-neutralization treatment, thereby reducing the production cost of enterprises;
(5) the extracting agent can be repeatedly used, is disposable in investment and can be used for a long time, and the production cost of enterprises is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a flow chart of a resource utilization method of deplating waste liquid according to the invention;
FIG. 2 is a flow chart of the overall process for recycling deplating waste liquid according to the invention;
the implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
Referring to fig. 1 and 2, the resource utilization method for the deplating waste liquid of the PCB, which is provided by the embodiment, includes the following steps:
step S1: and (2) preprocessing, filtering the copper nitrate waste liquid to remove impurities, adding a sulfuric acid solution into the filtered copper nitrate waste liquid, and adjusting the acid concentration of the system to obtain an inorganic phase for later use. The inorganic phase comprises copper nitrate, copper sulfate, nitric acid and sulfuric acid.
It should be noted that the copper nitrate waste liquid system contains Cu2+、H+、NO3-Part of nitrate radicals are dissociated into the system by adding sulfuric acid, so that the recovery of nitric acid is facilitated. The purpose of this example is to recover nitric acid and copper sulfate, so a sulfuric acid solution is added for pretreatment, facilitating the subsequent preparation of copper sulfate. During extraction, the higher the extraction acidity and the higher the extraction rate, but the later stage needs to beIn order to neutralize the excessive acid by using the copper oxide or the copper hydroxide, if the acidity is too high, a large amount of copper oxide or copper hydroxide solid is needed, which causes energy waste, and therefore, the addition amount of the sulfuric acid solution is 1.5 to 2.5 times of the mole number of copper ions in the copper nitrate waste liquid in step S1, which is obtained through a large amount of experimental data.
Step S2: and (3) extracting, namely putting the inorganic phase into an extraction device, adding an extracting agent TBP, controlling the extraction condition, and extracting with nitric acid to obtain an extract phase and a raffinate phase. The extract phase comprises a nitric acid-TBP extract compound, TBP and nitric acid, and the raffinate phase mainly comprises a mixed solution of copper sulfate and sulfuric acid. Adding an extracting agent to extract nitric acid, wherein the concentration of the nitric acid in the system is lower and lower along with the progress of the extraction distribution ratio, the balance is necessarily carried out in the direction of low concentration according to reaction kinetics because the balance is broken, and the content of the nitric acid in the copper nitrate waste liquid system is slowly reduced along with the progress of the extraction reaction until the extraction is saturated.
Further, in order to improve the extraction efficiency, the extraction conditions are specifically as follows: the extraction temperature is set to be 20-50 ℃; the extraction time is set to be 1-30 min; the extraction phase ratio (namely the ratio of the extracting agent to the inorganic phase) is set to be 1-3; the extraction stage number is set to be 2-5 stages. It should be noted that, when extracting nitric acid, the requirements of the extractant are as follows: (ii) C5-10 ketone; ② cyclic or straight-chain polyether with molecular weight of 100-1000; polyalkylene glycol with molecular weight of 1000-3000; and fourthly, phosphorus-containing organic matters and the like. The commonly used nitric acid extracting agents are TBP, trioctylamine and N235, and in this embodiment, the extracted nitric acid is to be subjected to back extraction and recycling, so that the TBP is selected as the extracting agent, thereby improving the extraction efficiency, facilitating the extraction, and facilitating the subsequent back extraction and recycling of the nitric acid. Through multistage extraction, can realize the complete extraction to nitric acid, and adopt the mode of countercurrent extraction, be favorable to improving the concentration of nitric acid, be favorable to industrial production.
Step S3: and (3) back extraction, namely putting the extract phase into an extraction device, adding water, controlling back extraction conditions, and performing back extraction of nitric acid to obtain a nitric acid solution. It should be noted that the solubility of nitric acid in water is relatively high, and the nitric acid solution can be directly obtained by back extraction of nitric acid with water as an extractant, and the back extraction effect is good, the efficiency is high, and the cost is low.
Step S3 specifically includes dividing the extract phase equally into a plurality of equal portions, contacting the plurality of equal portions of extract phase with the same portion of water, respectively, performing a back extraction of nitric acid, and controlling back extraction conditions to obtain a nitric acid solution. The back extraction conditions are specifically as follows: the extraction temperature is set to be 20-50 ℃; the extraction time is set to be 0.5-5 min; the extraction phase ratio was set to 1; the extraction stage number is set to be 3-10 stages. It should be noted that, the extraction phase is divided into a plurality of equal portions for respective extraction, so as to further improve the concentration of the nitric acid solution, which is beneficial to industrial production, and a large amount of experimental data show that, in this embodiment, the extraction phase is divided into 5 portions, and compared with 1 portion, the five extraction phases are respectively subjected to back extraction operation, so as to obtain a nitric acid solution with a higher concentration, complete recycling of nitric acid is completed, and the extraction method still adopts a counter-current extraction method.
Step S4: and crystallizing, namely adding a copper oxide or copper hydroxide solution into the raffinate phase, neutralizing redundant acid, adjusting the pH of a system to be 2-3, filtering, and crystallizing the filtrate to obtain copper sulfate crystals. Further, the crystallization treatment of the filtrate specifically comprises: and (4) evaporating, concentrating, cooling and crystallizing the filtrate in sequence to obtain copper sulfate crystals. And the copper in the deplating waste liquid is recycled.
It should be noted that the invention carries out resource recycling on the nitric acid and the copper ions in the copper nitrate waste liquid, obtains the corresponding product, has high resource utilization rate, obtains the nitric acid product as a pure nitric acid solution, can return to the deplating working section, and can be sold to other customers for different occasions according to market demands. The extractant can be repeatedly used, one-time investment and long-term use are realized, and the production cost of enterprises is reduced.
The present invention will be described with reference to specific examples.
The first embodiment is as follows:
1. and (3) taking 1000ml of nitric acid waste liquid, analyzing the content of copper ions and acid, slowly dropwise adding concentrated sulfuric acid with the same mole as the copper ions, and cooling to analyze that the content of acid is 5.59 mol/L.
2. Taking 1000ml of the prepared solution, preparing 1000ml of TBP extractant, pouring two parts of solution from the upper opening of a separating funnel, and covering a cover; shaking the separating funnel to make the two phases fully contacted; after oscillation, the knob is unscrewed, and the gas in the separating funnel is discharged; and continuing to shake and deflate for several times, wherein the total shaking time is 5 min.
3. Standing the separating funnel on an iron ring until the liquid is separated into two clear phases; after the phase separation is completed, the lower layer liquid is discharged through the bottom opening, and the upper layer liquid is discharged from the upper opening.
4. And extracting the separated upper layer liquid for multiple times according to the steps 2-3 again, and repeating for 3 times to ensure that the organic phase can reach extraction balance.
5. The organic phase saturated by extraction was divided into 5 parts, and the organic phase was contacted with the same stripping agent (water) at a phase ratio of 1, to obtain a nitric acid solution having a concentration of 4.6mol/L and a nitric acid concentration of 9.2mol/L, i.e., 45.2% nitric acid, after concentration twice.
6. Extracting the lower inorganic phase in the step 3 for multiple times, adding a proper amount of copper oxide or copper hydroxide to adjust the pH value to 3, evaporating, concentrating, cooling and crystallizing to obtain a copper sulfate pentahydrate crystal, and analyzing the solid after air drying, wherein the content of the copper sulfate pentahydrate is 98.52%.
Example two:
1. and (3) taking 1000ml of nitric acid waste liquid, analyzing the content of copper ions and acid, slowly dropwise adding concentrated sulfuric acid with twice molar concentration of the copper ions, and cooling to analyze the content of the acid to be 6.6 mol/L.
2. 1000ml of the prepared solution is taken. Simultaneously preparing 1000ml of TBP extractant, pouring two solutions from the upper opening of a separating funnel, and covering a cover; shaking the separating funnel to make the two phases fully contacted; after oscillation, the knob is unscrewed, and the gas in the separating funnel is discharged; and continuing to shake and deflate for several times, wherein the total shaking time is 5 min.
3. Standing the separating funnel on an iron ring until the liquid is separated into two clear phases; after the phase separation is completed, the lower layer liquid is discharged through the bottom opening, and the upper layer liquid is discharged from the upper opening.
4. And extracting the separated upper layer liquid for multiple times according to the steps 2-3 again, and repeating for 3 times to ensure that the organic phase can reach extraction balance.
5. The organic phase saturated by extraction was divided into 5 parts, and the organic phase was contacted with the same stripping agent (water) in a phase ratio of 1, to obtain a nitric acid solution having a concentration of 4.5mol/L and a nitric acid concentration of 9mol/L, i.e., 44% nitric acid, after concentration twice.
6. Extracting the lower inorganic phase in the step 3 for multiple times, adding a proper amount of copper oxide or copper hydroxide to adjust the pH value to 3, evaporating, concentrating, cooling and crystallizing to obtain a copper sulfate pentahydrate crystal, and analyzing the solid after air drying, wherein the content of the copper sulfate pentahydrate is 98.6%.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (5)
1. A resource utilization method suitable for PCB deplating waste liquid is characterized by comprising the following steps:
step S1: pretreating, namely filtering the copper nitrate waste liquid to remove impurities, adding a sulfuric acid solution into the filtered copper nitrate waste liquid, adjusting the acid concentration of a system to enable part of nitrate radicals to be dissociated into the system, and conveniently recovering nitric acid to obtain an inorganic phase for later use;
step S2: extracting, namely putting the inorganic phase into an extraction device, adding an extracting agent TBP, controlling extraction conditions, and extracting nitric acid to obtain an extract phase and a raffinate phase; the extract phase comprises a nitric acid-TBP extract compound, TBP and nitric acid, and the raffinate phase comprises a mixed solution of copper sulfate and sulfuric acid;
step S3: back extraction, namely putting the extract phase into an extraction device, adding water, controlling back extraction conditions, and performing back extraction of nitric acid to obtain a nitric acid solution;
step S4: crystallizing, namely adding a copper oxide or copper hydroxide solid into the raffinate phase, neutralizing redundant acid, adjusting the pH of the system to 2-3, filtering, and crystallizing the filtrate to obtain a copper sulfate crystal;
in step S2, the extraction conditions are specifically:
the extraction temperature is set to be 20-50 ℃;
the extraction time is set to be 1-30 min;
setting the extraction ratio to be 1-3;
the extraction stage number is set to be 2-5;
step S3 specifically includes dividing the extract phase equally into a plurality of equal portions, contacting the plurality of equal portions of extract phase with the same portion of water, respectively, performing a back extraction of nitric acid, and controlling back extraction conditions to obtain a nitric acid solution.
2. The resource utilization method of the PCB deplating waste liquid as claimed in claim 1, wherein in step S1, the addition amount of the sulfuric acid solution is 1.5-2.5 times of the mole number of the copper ions in the copper nitrate waste liquid.
3. The resource utilization method suitable for the PCB deplating waste liquid according to claim 1, wherein the back extraction conditions are as follows:
the extraction temperature is set to be 20-50 ℃;
the extraction time is set to be 0.5-5 min;
the extraction phase ratio was set to 1;
the extraction stage number is set to be 3-10 stages.
4. A resource utilization method suitable for PCB deplating waste liquid according to claim 1, wherein the extraction modes in step S2 and step S3 are both set as counter-current extraction.
5. The resource utilization method of the PCB deplating waste liquid as claimed in claim 1, wherein the step S4, the crystallizing treatment of the filtrate specifically comprises the following steps: and (4) evaporating, concentrating, cooling and crystallizing the filtrate in sequence to obtain copper sulfate crystals.
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Address after: 518000 101, maozhouhe industrial complex, Langxia community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Xinghe environment Co.,Ltd. Address before: No.01-03, B2 / F, building 2, Shenzhen Bay science and technology ecological park, 1809 Shahe West Road, high tech community, Yuehai street, Nanshan District, Shenzhen, Guangdong 518000 Patentee before: SHENZHEN STARIVER ENVIRONMENT TECHNOLOGY Co.,Ltd. |