阅读说明：本技术 一种含铜蚀刻废液回收装置和含铜蚀刻废液回收方法 (Copper-containing etching waste liquid recovery device and copper-containing etching waste liquid recovery method ) 是由 陈福泰 解迪 郝福锦 褚永前 于 2021-11-04 设计创作，主要内容包括：本申请具体公开了一种含铜蚀刻废液回收装置和含铜蚀刻废液回收方法,含铜蚀刻废液回收装置包括蒸发结晶机构,粉末回收机构,喷淋回收机构；所述蒸发结晶机构包括壳体,壳体内设置有支撑柱,支撑柱上转动连接有加热板,加热板上方设置有结晶喷淋头,壳体内还设置有真空泵,所述粉末回收机构包括刮刀；所述喷淋回收机构包括喷淋回收仓,喷淋回收仓内设置有回收喷淋头。含铜蚀刻废液回收方法包括以下步骤,S1原液检测；S2使用硫酸和氢氧化铜调节废液中铜离子浓度与硫酸根离子浓度相等；S3使用含铜蚀刻废液回收装置处理废液。本申请的处理方法具有简化含铜废液处理步骤的优点。(The application particularly discloses a copper-containing etching waste liquid recovery device and a copper-containing etching waste liquid recovery method, wherein the copper-containing etching waste liquid recovery device comprises an evaporation crystallization mechanism, a powder recovery mechanism and a spraying recovery mechanism; the evaporative crystallization mechanism comprises a shell, a support column is arranged in the shell, a heating plate is rotatably connected to the support column, a crystallization spray header is arranged above the heating plate, a vacuum pump is further arranged in the shell, and the powder recovery mechanism comprises a scraper; the spraying recovery mechanism comprises a spraying recovery bin, and a recovery spray head is arranged in the spraying recovery bin. The method for recovering the copper-containing etching waste liquid comprises the following steps of S1 stock solution detection; s2 adjusting the concentration of copper ions in the waste liquid to be equal to that of sulfate ions by using sulfuric acid and copper hydroxide; s3 waste liquid is treated by a copper-containing etching waste liquid recovery device. The treatment method has the advantage of simplifying the treatment steps of the copper-containing waste liquid.)

1. The copper-containing etching waste liquid recovery device is characterized by comprising an evaporative crystallization mechanism (1), a powder recovery mechanism (2) and a spraying recovery mechanism (3);

the evaporative crystallization mechanism (1) comprises a shell (11), a support column (12) is vertically arranged in the shell (11), a heating plate (13) is rotatably connected onto the support column (12), a crystallization spray header (15) used for spraying waste liquid onto the surface of the heating plate (13) is arranged above the heating plate (13), a driving assembly (14) used for driving the heating plate (13) to rotate around the support column (12) is further arranged on the support column (12), and a vacuum pump used for providing negative pressure into the device is arranged in the shell (11);

the powder recovery mechanism (2) comprises a scraping component (4) arranged above the heating plate (13), and the scraping component (4) comprises a scraper (43);

the spraying recovery mechanism (3) comprises a spraying recovery bin (31), the lower end of the spraying recovery bin (31) is communicated with an air guide pipe (32), the other end of the air guide pipe (32) is communicated with the inside of the shell (11) above the shell (11), and a recovery spraying head (34) is arranged in the spraying recovery bin (31).

2. The apparatus for recovering waste etching solution containing copper according to claim 1, wherein: an included angle formed by the direction from one end of the scraper (43) close to the axis of the heating plate (13) to one end of the scraper (43) far away from the axis of the heating plate (13) and the rotating direction of the projection position of one end of the scraper (43) far away from the axis of the heating plate (13) on the heating plate (13) forms an acute angle.

3. The apparatus according to claim 1 or 2, wherein the apparatus further comprises: the scraper (43) is at least three and parallel to each other, the distance between the scraper (43) and the upper surface of the heating plate (13) is gradually reduced along with the rotation direction of the heating plate (13) in the plurality of scrapers (43), and the scraper (43) located at the most downstream of the rotation direction of the heating plate (13) is attached to the upper surface of the heating plate (13).

4. The apparatus for recovering waste etching solution containing copper according to claim 3, wherein: the scrapers (43) are simultaneously provided with connecting rods (51), and the connecting rods (51) are respectively in rotating connection with the scrapers (43);

the connecting rod (51) is rotatably connected with an adjusting block (52), a lead screw (53) penetrates through the adjusting block (52), the lead screw (53) is rotatably connected with the adjusting block (52), and one end, far away from the heating plate (13), of the lead screw (53) penetrates into the top plate (41) and is in threaded connection with the top plate (41);

the scraping component (4) further comprises a top plate (41), and the top plate (41) is fixedly connected with a scraper (43) which is closest to the heating plate (13).

5. The apparatus for recovering waste etching solution containing copper according to claim 4, wherein: the powder recovery mechanism (2) further comprises a support frame (21), wherein the support frame (21) is provided with two sliding rails (23), the top plate (41) is arranged between the two sliding rails (23) and connected with the sliding rails (23) in a sliding mode, the length direction of the guide rails is parallel to the length direction of the scraper (43), and the sliding rails (23) are provided with driving cylinders (24) used for driving the top plate (41) to slide.

6. The apparatus for recovering waste etching solution containing copper according to claim 5, wherein: the support frame (21) is also provided with a discharging plate (25) used for cleaning the surface of the scraper (43), and when the scraper (43) slides towards the outer side of the heating plate (13) on the slide rail (23), the discharging plate (25) is attached to the surface of the scraper (43).

7. The apparatus for recovering waste etching solution containing copper according to claim 1, wherein: a circulating pump (35) is further arranged in the spraying recovery bin (31), the water inlet end of the circulating pump (35) is communicated with the lower end of the spraying recovery bin (31), and the water outlet end of the circulating pump (35) is communicated with the recovery spray header (34).

8. The method for recovering the copper-containing etching waste liquid is characterized by comprising the following steps: the method comprises the following steps:

s1, detecting stock solution, namely detecting the concentration of each ion in the stock solution to be treated, wherein the sum of the concentration of copper ions and the concentration of hydrogen ions in the stock solution is not less than 90% of the sum of the concentrations of all cations in the stock solution;

s2 adjusting the concentration of copper ions in the waste liquid to be equal to that of sulfate ions by using sulfuric acid and copper hydroxide;

s3 copper-containing etching waste liquid recovery device according to any one of claims 1 to 7 is used for processing the solution obtained in S2 to obtain copper sulfate crystals in the powder recovery mechanism (2) and dilute hydrochloric acid in the spray recovery mechanism (3).

9. The method according to claim 8, wherein a degree of vacuum in the copper-containing etching waste liquid recovery apparatus is from-85 to-95 kPa.

10. The method for recovering waste etching solution containing copper according to claim 8, wherein the temperature of the heating plate (13) of the apparatus for recovering waste etching solution containing copper is 35-50 ℃.

Technical Field

The application relates to the field of waste liquid recovery and treatment, in particular to a copper-containing etching waste liquid recovery device and a copper-containing etching waste liquid recovery method.

Background

The acidic copper sulfate waste liquid is copper sulfate consumption liquid in an electroplating bath discharged by a semiconductor wafer in a copper plating process, the main components of the acidic copper sulfate waste liquid are copper sulfate and sulfuric acid, wherein the content of copper ions is dozens of grams to hundreds of grams per liter, the weight ratio of the sulfuric acid is about 15%, in addition, a small amount of organic and inorganic additives are contained, the acidic copper sulfate waste liquid belongs to HW 22-class hazardous wastes, and if the acidic copper sulfate waste liquid is not effectively treated, the environmental pollution and the resource waste can be caused.

At present, the resource technology of the acidic copper sulfate waste liquid mainly comprises an extraction-electrodeposition recovery technology, an eddy current electrolysis technology, an ion exchange method, an iron powder replacement copper recovery technology and a copper sulfate production technology by neutralizing an acid etching solution and an alkaline etching solution.

However, the prior art is complex in process, low in efficiency of treating the acidic copper sulfate waste liquid, incapable of realizing the requirement of mass production, low in purity of the obtained final product copper sulfate, serious in secondary pollutants and high in treatment cost.

Disclosure of Invention

In order to simplify the recovery treatment process of the copper-containing etching waste liquid, the application provides a copper-containing etching waste liquid recovery device and a copper-containing etching waste liquid recovery method.

In a first aspect, the present application provides a copper-containing etching waste liquid recovery device, which adopts the following technical scheme:

a copper-containing etching waste liquid recovery device comprises an evaporative crystallization mechanism, a powder recovery mechanism and a spraying recovery mechanism;

the evaporative crystallization mechanism comprises a shell, wherein a support column is vertically arranged in the shell, a heating plate is rotatably connected onto the support column, a crystallization spray header for spraying waste liquid on the surface of the heating plate is arranged above the heating plate, a driving assembly for driving the heating plate to rotate around the support column is further arranged on the support column, and a vacuum pump for providing negative pressure into the device is arranged in the shell;

the powder recovery mechanism comprises a scraping component arranged above the heating plate, and the scraping component comprises a scraper;

the spraying recovery mechanism comprises a spraying recovery bin, the lower end of the spraying recovery bin is communicated with an air guide pipe, the other end of the air guide pipe is communicated with the inside of the shell above the shell, and a recovery spray head is arranged in the spraying recovery bin.

Through adopting above-mentioned technical scheme, the waste liquid of treating is sprayed on the hot plate by the crystallization shower head, moisture and hydrogen chloride in the waste liquid volatilize fast, copper sulfate in the waste liquid is at the quick crystallization of hot plate surface, when the hot plate rotated to scraper department, the crystal that the scraper obtained with the crystallization of hot plate surface is scraped down to accomplish the recovery of copper sulfate in the waste liquid, volatile hydrogen chloride enters into and sprays recovery mechanism in, and is absorbed by the water or alkali lye of retrieving the shower head spraying, obtains corresponding salt or hydrochloric acid.

The treatment mode is simple to operate and fast, copper sulfate and hydrogen chloride in the waste liquid can be continuously separated, the obtained copper sulfate pentahydrate crystal and hydrochloric acid can be reused as raw materials in the production of the etching liquid, and can also be sold as commodities, so that the environment is protected, and the economic effect of the waste liquid is improved.

Preferably, an included angle formed by the direction from one end of the scraper close to the axis of the heating plate to one end of the scraper far away from the axis of the heating plate and the rotating direction of the projection of one end of the scraper far away from the axis of the heating plate on the heating plate forms an acute angle.

By adopting the technical scheme, when the scraper scrapes the crystal on the surface of the heating plate, the crystal rotating around the axis of the heating plate generates a component force far away from the axis of the heating plate after contacting the scraper, so that the crystal is promoted to move to the outer side of the heating plate and fall into the aggregate bin; thereby reducing the accumulation of the crystal on the scraper and the situation that the crystal moves to the middle part of the heating plate; the convenience of crystal processing is improved.

Preferably, the scraper is parallel to each other and is provided with three at least, and among a plurality of scrapers, the distance from the scraper to the upper surface of the heating plate is gradually reduced along with the rotating direction of the heating plate, and the scraper located at the most downstream of the rotating direction of the heating plate is attached to the upper surface of the heating plate.

Through adopting above-mentioned technical scheme, at least three scraper sets up along direction of height gradient, when the crystallization rotates along with the heating plate at the copper sulfate crystal on heating plate surface, the crystal in proper order with the scraper contact of co-altitude not to the different thickness layers of crystal are scraped by different scrapers in proper order, thereby have made things convenient for the scraper to scrape the crystal from the heating plate surface completely and have left, improve the stability of scraping material subassembly work.

Preferably, the plurality of scrapers are simultaneously provided with connecting rods which are respectively in rotating connection with the plurality of scrapers;

the connecting rod is rotatably connected with an adjusting block, a lead screw penetrates through the adjusting block and is rotatably connected with the adjusting block, and one end of the lead screw, which is far away from the heating plate, penetrates through the top plate and is in threaded connection with the top plate;

the scraping component also comprises a top plate, and the top plate is fixedly connected with the scraper closest to the heating plate.

Through adopting above-mentioned technical scheme, the setting of connecting rod and lead screw has made things convenient for the staff to adjust the difference in height between two adjacent scrapers according to the concentration of the copper sulfate of waste liquid to be convenient for strike off the crystal of different thickness, thereby improved the stability of scraping material subassembly work.

Preferably, the powder recovery mechanism further comprises a support frame, slide rails are arranged on the support frame, the slide rails are provided with two slide rails, the top plate is arranged between the two slide rails and connected with the slide rails in a sliding manner, the length direction of the guide rails is parallel to the length direction of the scraper, and a driving cylinder used for driving the top plate to slide is arranged on the slide rails.

Through adopting above-mentioned technical scheme, when driving actuating cylinder work, when the piston rod that drives actuating cylinder withdraws, the scraper slides to the outside of hot plate to the scraper breaks away from the hot plate upper surface, because the scraper is injectd with the hot plate position during the installation, when the scraper slides to the hot plate outside, the scraper can drive the powder on the hot plate and move to the hot plate outside, and then the copper sulfate crystal of crystallization falls into in the collection hopper on the hot plate, thereby accomplishes and receives the material operation.

The setting that the scraper subassembly slided can clean the crystal of piling up on the hot plate on the one hand, makes it fall into the collecting hopper, and on the other hand, the scraper breaks away from the hot plate upper surface to the temperature on scraper surface reduces, has reduced because the scraper is high temperature for a long time, and then leads to blue vitriod to be heated and loses water, influences purity.

Preferably, the support frame is further provided with a discharging plate for cleaning the surface of the scraper, and when the scraper slides to the outer side of the heating plate on the slide rail, the discharging plate is attached to the surface of the scraper.

Preferably, a circulating pump is further arranged in the spraying recovery bin, the water inlet end of the circulating pump is communicated with the lower end of the spraying recovery bin, and the water outlet end of the circulating pump is communicated with the recovery spraying head.

Through adopting above-mentioned technical scheme, the setting of circulating pump for the water that sprays in the recovery storehouse can cyclic utilization, when spraying the water pH that retrieves in the storehouse and be less than 3, then can change and spray the absorption water that retrieves in the storehouse.

In a second aspect, the present application provides a method for recovering copper-containing etching waste liquid, which adopts the following technical scheme:

the method for recovering the copper-containing etching waste liquid comprises the following steps:

s1, detecting stock solution, namely detecting the concentration of each ion in the stock solution to be treated, wherein the sum of the concentration of copper ions and the concentration of hydrogen ions in the stock solution is not less than 90% of the sum of the concentrations of all cations in the stock solution;

s2 adjusting the concentration of copper ions in the waste liquid to be equal to that of sulfate ions by using sulfuric acid and copper hydroxide;

s3 the solution obtained in S2 is processed by the copper-containing etching waste liquid recovery device to obtain copper sulfate crystals in the powder recovery mechanism and dilute hydrochloric acid in the spray recovery mechanism.

Through adopting above-mentioned technical scheme, the copper sulfate waste liquid is through detecting the back, selects to add concentrated sulfuric acid or copper hydroxide, transfers copper ion concentration and sulfate radical ion concentration in the waste liquid to equal, then uses copper-containing etching waste liquid recovery unit to retrieve copper sulfate and hydrogen chloride, and the waste liquid sprays on the hot plate, and after the hot plate heating, waste water, the hydrogen chloride evaporation in the waste liquid get into and spray the recovery storehouse and retrieve once more, and blue vitriod is through powder recovery mechanism, retrieves. The treatment method improves the treatment efficiency of the waste liquid, and can obtain copper sulfate pentahydrate crystals with higher purity. The purity of the obtained blue copperas crystal meets the requirements of the high-class products in the industrial blue copperas HG/T5215-2017.

Preferably, the vacuum degree in the copper-containing etching waste liquid recovery device is-85 to-95 kPa.

By adopting the technical scheme, the boiling point of the waste liquid can be reduced by adjusting the vacuum degree, so that the waste liquid is quickly evaporated to dryness at a lower temperature, and the condition that the product purity is influenced by the decomposition and dehydration of the blue vitriol at a high temperature is reduced.

Preferably, the copper-containing etching waste liquid recovery device has a heating plate temperature of 35-50 ℃.

By adopting the technical scheme, the waste liquid treatment rate can be effectively improved by adjusting the temperature of the heating plate, but when the temperature of the heating plate is too high, particularly after the temperature of the heating plate is higher than 50 ℃, blue copperas is easy to dehydrate and decompose, thereby influencing the purity of the blue copperas.

In summary, the present application has the following beneficial effects:

1. the device of this application can separate copper sulfate and chloride ion in the copper-containing etching waste liquid fast, and copper sulfate is at hot plate surface crystallization layer to retrieve by powder recovery mechanism, chloride ion turns into hydrogen chloride, volatilizees and gets into and spray the recovery storehouse, is sprayed the reabsorption, and copper sulfate pentahydrate and hydrochloric acid that obtain after the processing can be reused in production again, thereby has practiced thrift the raw materials and has reduced manufacturing cost, and green has reduced the pollution to the environment.

2. To the quantity of scraper in this application device, arrange the further injeciton of position to and the scraper slides on the hot plate, can make crystal on the hot plate more smooth scrape from the hot plate on the one hand, on the other hand, the controlled temperature that can also be accurate reduces the scraper temperature and rises, thereby leads to blue vitriod dehydration to decompose, has improved the purity of blue vitriod product.

3. The method has the characteristics of high waste liquid treatment speed, simple process and continuous treatment, and the obtained blue vitriol has high purity and meets the requirement of high-class products of industrial bluestone HG/T5215-2017.

Drawings

FIG. 1 is a schematic diagram showing the overall structure of a copper-containing etching waste liquid recovery apparatus according to the present application;

FIG. 2 is a schematic structural diagram embodying a drive assembly;

FIG. 3 is a schematic view showing the overall structure of the powder recovery mechanism;

FIG. 4 is a schematic view of the overall structure embodying the adjustment assembly;

FIG. 5 is a schematic view of the relationship of the position of the scraper blade and the heating plate;

fig. 6 is an enlarged view of detail a in fig. 3.

In the figure, 1, an evaporative crystallization mechanism; 11. a housing; 12. a support pillar; 13. heating plates; 14. a drive assembly; 141. a toothed ring; 142. a drive gear; 143. a drive motor; 15. a crystallization spray header; 2. a powder recovery mechanism; 21. a support frame; 22. a collection hopper; 23. a slide rail; 231. a chute; 24. a driving cylinder; 25. a stripper plate; 3. a spray recovery mechanism; 31. spraying a recovery bin; 32. an air guide pipe; 33. a weather edge; 34. recovering the spray header; 35. a circulation pump; 4. a scraping component; 41. a top plate; 411. a sliding strip; 42. an accommodation hole; 43. a scraper; 44. a support block; 5. an adjustment assembly; 51. a connecting rod; 52. an adjusting block; 53. and a lead screw.

Detailed Description

The present application will be described in further detail with reference to the following drawings and examples.

A copper-containing etching waste liquid recovery device is shown in figure 1 and comprises an evaporative crystallization mechanism 1, a powder recovery mechanism 2 and a spraying recovery mechanism 3.

As shown in FIG. 1, the evaporative crystallization apparatus 1 includes a housing 11, and a support column 12 is disposed in the housing 11. The coaxial cover is equipped with a hot plate 13 on the support column 12, and hot plate 13 is whole for discoid, and hot plate 13 rotates with support column 12 to be connected. The heating plate 13 is provided with a driving assembly 14 for driving the heating plate 13 to rotate. The heating plate 13 is also provided with a crystal spray header 15 above for spraying the waste liquid to be treated to the upper surface of the heating plate 13, when the waste liquid is sprayed on the surface of the heating plate 13, the water and hydrogen chloride gas in the waste liquid volatilize, so that the copper sulfate crystal in the waste liquid is separated out and stays on the surface of the heating plate 13, along with the rotation of the heating plate 13 driven by the driving component 14, the crystal is taken to the powder recovery device, and the powder recovery device scrapes the crystal on the surface of the heating plate 13 and recovers the crystal. And the water vapor and the hydrogen chloride enter a spraying recovery device for further treatment. The housing 11 is also provided with a vacuum pump to maintain the interior of the housing 11 in a negative pressure state, thereby promoting the volatilization of water and hydrogen chloride in the waste liquid.

As shown in fig. 2, the driving assembly 14 includes a gear ring 141 coaxially fixed to the lower surface of the heating plate 13, and a driving gear 142 disposed at an inner circumference of the gear ring 141 and engaged with the gear ring 141. A driving motor 143 is further disposed below the heating plate 13, and an output shaft of the driving motor 143 is disposed vertically upward and coaxially and fixedly connected with the driving gear 142. When the driving motor 143 is operated, the driving motor 143 rotates the driving gear 142, and the heating plate 13 is rotated by the engagement of the driving gear 142 with the gear ring 141. In other embodiments of the present application, the transmission structure of the toothed ring 141 and the driving gear 142 may be replaced by a transmission structure of a belt and a pulley, a transmission structure of a chain and a sprocket, and the like.

The heating mode of the heating plate 13 can adopt the forms of electric heating, water vapor heating and the like.

The crystallization spray header 15 may be provided in plurality along the radial direction of the heating plate 13, and the spray area of the crystallization spray header 15 on the heating plate 13 is annular along with the rotation of the heating plate 13.

The vertical setting of support column 12 in this application, the vertical setting of the axis of the hot plate 13 that corresponds to make 15 spun waste liquids of crystallization shower head can be stable remain on hot plate 13 surfaces, and by the evaporation gradually. If the support column 12 is horizontally arranged, when the axis of the corresponding heating plate 13 is horizontally arranged, the following two conditions can be generated:

if the heating plate 13 is at a low temperature, the waste liquid sprayed on the heating plate 13 will drip under the heating plate 13 due to gravity, which on the one hand results in waste, and on the other hand, the disposal of the dripping waste liquid increases the disposal cost. And if the temperature of the heating plate 13 is high, and the waste liquid flows on the surface of the heating plate 13 under the action of gravity, crystals generated by the waste liquid are unevenly distributed on the surface of the heating plate 13, and the stable operation of the powder recovery device is influenced.

If the temperature of the heating plate 13 is high, after the waste liquid is sprayed on the surface of the heating plate 13, the waste liquid is quickly evaporated, copper sulfate crystals are on the surface of the heating plate 13, on one hand, the energy consumption for maintaining the high temperature of the heating plate 13 is high, on the other hand, the temperature of the heating plate 13 is high, so that the copper sulfate pentahydrate crystals crystallized on the surface of the heating plate 13 are easily subjected to side reaction, the crystal water of the copper sulfate pentahydrate crystals is lost, and the purity of the collected copper sulfate pentahydrate crystals is influenced.

So synthesize above factor, with the vertical setting of support column 12, the vertical setting of 13 axes of hot plate, hot plate 13 upper surface level sets up, helps making copper-containing waste liquid under lower temperature, evenly at the crystallization of 13 surfaces of hot plate, is convenient for retrieve the crystal, can also reduce the emergence of side reaction simultaneously, improves purity.

As shown in fig. 3 and 4, the powder recovery mechanism 2 includes a support frame 21, a collection hopper 22 is provided on the support frame 21, the collection hopper 22 is located below the heating plate 13, and the collection hopper 22 partially extends beyond the outer edge of the heating plate 13. The top level of support frame 21 is provided with two slide rails 23, and two slide rails 23 parallel arrangement each other are provided with between two slide rails 23 and scrape material subassembly 4.

As shown in fig. 4, the scraping assembly 4 includes a top plate 41, a plurality of receiving holes 42 are formed in the top plate 41, in this embodiment, 3 receiving holes 42 are provided, a scraping blade 43 is inserted into the receiving hole 42, and 3 corresponding scraping blades 43 are provided. The 3 scrapers 43 are arranged in parallel with each other and the distance from the lower edge of the scraper 43 to the heating plate 13 is gradually reduced along with the rotation direction of the heating plate 13, and the lower surface of the scraper 43 located at the most downstream in the rotation direction of the heating plate 13 abuts against the upper surface of the heating plate 13. When the crystal on the upper surface of the heating plate 13 approaches the scraper assembly 4 with the rotation of the heating plate 13, the crystal first contacts the scraper 43 farthest from the upper surface of the heating plate 13, and then the upper layer of the crystal is scraped by the scraper 43; as the heating plate 13 continues to rotate, the crystal comes into contact with the middle scraper 43, and the middle layer of the crystal is scraped off by the scraper 43; similarly, as the crystal continues to rotate into contact with the scraper 43 against the upper surface of the plate 13, all of the crystal is scraped away from the plate 13 by the scraper 43. The multiple sets of blades 43 and the limited distance of the blades 43 from the heating plate 13 facilitate the blades 43 scraping the crystal off the heating plate 13. The multiunit scraper 43 strikes off the different thickness layers of crystal respectively to the efficiency that the crystal struck off has been improved, on the other hand multiunit scraper 43's setting has still reduced the impact force when single scraper 43 contacts with the crystal, has improved scraper 43 job stabilization nature.

As shown in fig. 5, the length direction of the scraper 43 can be arranged along the radial direction of the heating plate 13, but it is more preferable to implement the angle α between the direction a from the end of the scraper 43 close to the axis of the heating plate 13 to the end of the scraper 43 far from the axis of the heating plate 13 and the rotation direction b of the heating plate 13 at the projection of the end of the scraper 43 far from the axis of the heating plate 13 on the heating plate 13. That is, when a radius on the heating plate 13 rotates around the axis of the heating plate 13, the end of the scraper 43 facing the axis of the heating plate 13 contacts with the radius, and then the contact point between the radius and the scraper 43 in the length direction gradually moves to the end of the scraper 43 away from the axis of the heating plate 13 along with the rotation of the radius.

Further, the included angle α is 30 to 75 °.

The advantage of this arrangement of the scraper 43 is that: when the scraper 43 scrapes off the crystal on the surface of the heating plate 13, the crystal rotating around the axis of the heating plate 13 generates a component force away from the axis of the heating plate 13 after contacting the scraper 43, so that the crystal is promoted to move to the outer side of the heating plate 13 and fall into the collecting hopper 22; thereby reducing the accumulation of crystals on the scraper 43 or the movement of crystals toward the middle of the heating plate 13; the convenience of crystal processing is improved.

In other embodiments of the present application, the scraper 43 may be configured in an arc shape, and the arc convex surface is disposed toward the rotation direction of the heating plate 13.

As shown in fig. 5, the scraping assembly 4 further includes an adjusting assembly 5 for adjusting the distance between the scraper 43 and the heating plate 13, the adjusting assembly 5 includes a connecting rod 51 simultaneously disposed on the side walls of the 3 scrapers 43, the connecting rod 51 is simultaneously rotatably connected with the 3 scrapers 43, and the axes of rotation of the connecting rod 51 and the scrapers 43 are disposed in parallel with the length direction of the scrapers 43. The link 51 is also rotatably connected with a regulating block 52, and the rotating directions of the regulating block 52 and the link 51 are parallel to the rotating directions of the link 51 and the scraper 43. The adjusting block 52 is provided with a lead screw 53, the axis of the lead screw 53 is perpendicular to the heating plate 13, and the lead screw 53 passes through the adjusting block 52 and is rotatably connected with the adjusting block 52. One end of the screw 53, which is far away from the heating plate 13, is penetrated on the top plate 41 and the screw 53 is in threaded fit with the top plate 41. The scraper 43 closest to the heating plate 13 is fixed to the top plate 41, and the scraper 43 suspended above the heating plate 13 is connected to the top plate 41 so as to slide in the height direction.

Further, in the adjusting assembly 5, two connecting rods 51 are provided, two connecting rods 51 are distributed along the height direction, two adjusting blocks 52 are provided corresponding to the adjusting blocks 52, the two adjusting blocks 52 are respectively rotatably connected with the two connecting rods 51, and the screw 53 simultaneously penetrates through the two adjusting blocks 52 and is rotatably connected with the adjusting blocks 52. Similarly, two adjusting assemblies 5 may be provided, and the two adjusting assemblies 5 are respectively located at two ends of the length direction of the scraper 43.

When the worker rotates the screw 53, the screw 53 controls the adjusting block 52 to adjust the height direction, so as to control the connecting rod 51 to rotate, and the connecting rod 51 drives the scraper 43 which is adjusted to have a gap with the heating plate 13 to lift in the height direction, thereby adjusting the distance between the scraper 43 and the heating plate 13.

When copper-containing waste liquid is treated, because the copper sulfate concentration in the waste liquid of different batches is different, so to the waste liquid of different batches, the copper sulfate crystal that unit volume waste liquid can be crystallized and obtain can produce the difference, and then the staff can adjust the distance between scraper 43 and the hot plate 13 through revolving wrong lead screw 53 to carry out the adaptation to the crystal of different thickness, improved the convenience of operation and the stability of scraping.

As shown in fig. 3 and 6, the lower surface of the top plate 41 is further fixedly connected with a plurality of supporting blocks 44, the supporting blocks 44 are disposed at two sides of the scraper 43 and abut against the scraper 43, the arrangement of the supporting blocks 44 can improve the stability of the installation of the scraper 43 in the top plate 41, and when the scraper 43 contacts with the crystal, the supporting blocks 44 provide stable support for the scraper 43, thereby improving the stability of the operation of the scraper 43.

As shown in fig. 3 and 6, two sides of the top plate 41 are respectively provided with a sliding bar 411, and one surface of the corresponding slide rail 23 facing the top plate 41 is provided with a sliding slot 231 matched with the sliding bar 411. The sliding slot 231 is disposed in parallel with the length direction of the scraper 43, so that the top plate 41 can slide on the sliding rail 23 along the length direction of the scraper 43, and the scraper 43 is controlled to slide to the outer side of the heating plate 13. The supporting frame 21 is further provided with a driving cylinder 24 for driving the top plate 41 to slide, the body of the driving cylinder 24 is fixedly connected with the supporting frame 21, and the piston rod of the driving cylinder 24 is fixedly connected with the top plate 41.

When driving actuating cylinder 24 during operation, drive actuating cylinder 24 piston rod and withdraw to control roof 41 and slide to the hot plate 13 outside, and then scraper 43 breaks away from hot plate 13 upper surface, because the existence of contained angle alpha, when scraper 43 slides to the hot plate 13 outside, scraper 43 will pile up the crystal powder on scraper 43 surface and scrape into below collecting hopper 22, thereby reduce and adhere to the crystal powder on scraper 43 surface, improved the long-time stability of working of powder recovery mechanism 2. The sliding of the scraping component 4 along the length direction of the scraping blade 43 can also reduce the abrasion of the scraping blade 43 to the heating plate 13 during sliding, thereby protecting the heating plate 13.

As shown in fig. 3, the support frame 21 is provided with the stripper plates 25, the stripper plates 25 correspond to the scrapers 43 one by one, and the stripper plate 25 is located at one side of the scrapers 43 for crystal deposition. When the scraper 43 slides to the outside of the heating plate 13 under the action of the driving cylinder 24, the stripper plate 25 and the scraper 43 contact with each other, so that the stripper plate 25 scrapes the side wall of the scraper 43 with the attached crystal powder into the collection hopper 22, thereby facilitating the continuous work of the scraper 43. Further, the upper end of the discharging plate 25 is inclined toward the heating plate 13, so that when the discharging plate 25 contacts with the scraper 43, the crystal powder can smoothly fall into the collecting hopper 22, and the situation that the crystal powder is accumulated on the discharging plate 25 is reduced. The stripper plate 25 faces the surface of the scraper 43 and is also perpendicular to the heating plate 13, when the stripper plate 25 scrapes the crystal on the surface of the scraper 43, the scraper 43 can be ground, so that the working surface of the scraper 43 is kept perpendicular to the heating plate 13, and the scraping efficiency of the scraper 43 on the crystal is improved.

When using above-mentioned copper-containing waste liquid recovery unit to handle the copper sulfate waste liquid, need the inside vacuum of adjusting device, then adjust the temperature of hot plate 13, adjust the rotational speed of hot plate 13 and the play liquid rate of crystallization shower head 15, make the waste liquid spray on hot plate 13 surface, when rotatory to scraping material subassembly 4 department through hot plate 13, liquid in the waste liquid volatilizees completely just, thereby be convenient for scraper 43 to collect the crystal of crystallization, the temperature of hot plate 13 also can not be too high simultaneously, if hot plate 13 high temperature, the crystal is premature to appear, the waste liquid volatilizees too early, lead to the crystal temperature that the crystallization came out to rise fast easily, and then cause blue vitriol to lose crystal water, thereby influence the product purity.

On the other hand, if the scraper 43 is placed on the heating plate 13 for a long time and the scraper 43 scrapes the crystal, heat is generated, which causes the surface temperature of the scraper 43 to increase, and the crystal powder accumulated on the side wall of the scraper 43 is easily decomposed to lose water.

And the scraper assembly 4 can make the surface of the heating plate 13 of the scraper 43 separate under the action of the driving cylinder 24, and the surface temperature of the scraper 43 can be reduced while the scraper assembly cooperates with the stripper plate 25 to scrape off crystals on the surface of the scraper 43, thereby facilitating continuous production. When the scraper 43 is away from the heating plate 13, the crystallization shower head 15 stops spraying the waste liquid to the heating plate 13, and when the scraper 43 is returned above the heating plate 13, the crystallization shower head 15 is operated again.

As shown in fig. 1, the spraying recovery mechanism 3 includes a spraying recovery bin 31, the spraying recovery bin 31 is located above the housing 11, an air duct 32 is communicated above the housing 11, an upper end of the air duct 32 penetrates into the spraying recovery bin 31, an upper end of the air duct 32 is higher than a bottom wall of the spraying recovery bin 31, and a wind-rain edge 33 is further disposed at a top end of the air duct 32. The top wall of the spraying recovery bin 31 is also provided with a recovery spray header 34, the recovery spray header 34 is connected with a circulating pump 35, and the water inlet end of the circulating pump 35 is communicated with the bottom wall of the spraying recovery bin 31 through a pipeline.

When the waste liquid containing copper sulfate is sprayed on the heating plate 13, hydrogen chloride and water in the waste liquid are heated and evaporated, and enter the spraying recovery bin 31 through the air guide pipe 32, and hydrogen chloride gas is absorbed by water sprayed out of the recovery spray header 34 in the spraying recovery bin 31 and falls into the bottom wall of the spraying recovery bin 31. The arrangement of the circulating pump 35 enables water in the spray recovery bin 31 to circularly absorb hydrogen chloride, and when the pH value of the water is less than 3, the original water can be discharged, and the water which is replaced by new water is sprayed again to absorb the hydrogen chloride. A discharge port is arranged above the spraying recovery bin 31, and redundant steam can be discharged through the discharge port.

The waste liquid is subjected to an evaporation crystallization structure, so that the separation of copper sulfate and hydrogen chloride is realized, the copper sulfate and the hydrogen chloride are respectively collected by the powder recovery mechanism 2 and the spraying recovery mechanism 3, and the collected copper sulfate and the collected hydrogen chloride can be reused as raw materials, so that the production cost is reduced, the environment is protected, and the economic benefit is improved.

The method for recovering the copper-containing etching waste liquid comprises the following steps:

s1, detecting stock solution, namely detecting the concentration of each ion in the stock solution to be treated, wherein the sum of the concentration of copper ions and the concentration of hydrogen ions in the stock solution is not less than 90% of the sum of the concentrations of all cations in the stock solution;

s2 adjusting the concentration of copper ions in the waste liquid to be equal to that of sulfate ions by using concentrated sulfuric acid and copper hydroxide;

s3, the solution obtained in the step S2 is led into a copper-containing etching waste liquid recovery device, the solution is sprayed out from a crystallization spray head, copper sulfate crystals are obtained in a powder recovery mechanism, and dilute hydrochloric acid is obtained in a spray recovery mechanism.

When a copper-containing etching waste liquid recovery device is used,

the vacuum degree in the device is-85 to-95 kPa, the temperature of the heating plate is 35 to 50 ℃, and the rotating speed of the heating plate is 1 to 3 r/min.

Staff can be through adjusting crystallization shower head play liquid speed, when making the waste liquid rotate scraper assembly department, the moisture in the waste liquid volatilizees completely.

Examples

The same stock solutions were used in all the following examples and comparative examples, and the concentrations of the respective ions in the stock solutions are shown in Table 1

TABLE 1 stock solution ingredients and contents

Composition (I)

SO4 2-

H2O2

F-

Cl-

Cu2+

Fe

As

Content (wt.)

63.7 g/L

102mg/L

22.31mg/L

1765mg/L

35.6g/L

Not detected out

Not detected out

Composition (I)

Pb

Cr

Ni

Cd

Hg

Ammonia nitrogen

pH

Content (wt.)

Not detected out

Not detected out

Not detected out

Not detected out

Not detected out

31.8 mg/L

1.13

Example 1

S1, the detection result of the stock solution is shown in the table 1.

And S2, adjusting the concentration of copper ions in the waste liquid to be equal to that of sulfate ions by using concentrated sulfuric acid and copper hydroxide.

Detected, c (SO)₄ ^2-)=0.6635mol/L ,c(Cu²⁺) =0.5563 mol/L. Therefore, 10.452g of copper hydroxide solid was added per liter of waste liquid.

S3, the solution obtained in the step S2 is led into a copper-containing etching waste liquid recovery device, the solution is sprayed out from a crystal spray header, copper sulfate crystals are obtained in a powder recovery mechanism, and dilute hydrochloric acid is obtained in a spray recovery mechanism.

The vacuum degree in the device is-90 kPa, the temperature of the heating plate is 45 ℃, and the rotating speed of the heating plate is 2 r/min.

Example 2

The difference from example 1 was that the degree of vacuum in the apparatus was-85 kPa.

Example 3

The difference from example 1 was that the degree of vacuum in the apparatus was-95 kPa.

Example 4

The difference from example 1 is that the temperature of the heating plate in the apparatus was 35 ℃.

Example 5

The difference from example 1 is that the temperature of the heating plate in the apparatus was 40 ℃.

Example 6

The difference from example 1 is that the temperature of the heating plate in the apparatus was 50 ℃.

Example 7

The difference from example 1 was that the vacuum in the apparatus was-95 kPa and the temperature of the hot plate was 35 ℃.

Example 8

The difference from example 1 was that the degree of vacuum in the apparatus was-95 kPa, and the temperature of the hot plate was 40 ℃.

Comparative example

Comparative example 1

The difference from example 1 is that the pressure in the comparative example apparatus was normal atmospheric pressure and the temperature of the heating plate was 120 ℃.

Comparative example 2

The difference from example 1 is that the comparative example has a heating plate temperature of 55 ℃.

Comparative example 3

The difference from example 1 was that the vacuum degree in the comparative example apparatus was-80 kPa.

Performance test

The total weight of the crystal products obtained by using the methods of examples 1 to 8 and comparative examples 1 to 3, respectively, and the amount of the substance of copper ions were measured for 10L of the stock solution, and the recovery rate of copper ions and the purity of copper sulfate pentahydrate were calculated based on the measured data.

The recovery rate of copper ions is calculated according to the formula (I)

ω ₁ =n ₁ /n ₂ （Ⅰ）；

Whereinn ₁ Is Cu in crystal product obtained after 10L stock solution treatment²⁺The amount of the substance(s) of (a),

n ₂ is Cu in 10L stock solution²⁺The amount of substance(s) of (c).

Purity: according to formula (II)

ω ₂ = （Ⅱ）

M ₁ Is CuSO₄·5H₂Relative molecular mass of O;

mis the total mass of the product;

n ₃ can be obtained by solving equation set (III);

（Ⅲ）

n ₁ is Cu in crystal product obtained after 10L stock solution treatment²⁺The amount of substance(s) of (c);

n ₃ is CuSO in the crystal product obtained after 10L of stock solution treatment₄·5H₂The amount of species of O;

n ₄ is CuSO in the crystal product obtained after 10L of stock solution treatment₄·3H₂The amount of species of O;

mis the total weight of the crystalline product。

The results are shown in table 2:

TABLE 2

Through detection, the blue copperas prepared in the examples 1 to 7 meet the standard of superior products in the industrial blue copperas HG/T5215-2017.

It can be seen from the combination of examples 1-8 that the increase in vacuum can effectively reduce the boiling point of the waste liquid, so that the waste liquid can be quickly evaporated to dryness at a lower temperature by the heating plate, thereby reducing the energy loss when the waste liquid is evaporated to dryness.

The reduction of the temperature of the heating plate can also inhibit the loss of water of the copper sulfate pentahydrate, thereby improving the purity of the copper sulfate pentahydrate in the obtained product, but if the temperature of the heating plate is too low, the reduction of the purity of the copper sulfate pentahydrate in the product can also be caused, probably because under the condition of lower temperature, hydrogen chloride is incompletely volatilized, thereby reducing the purity of the copper sulfate pentahydrate in the product. Therefore, the selection of the proper vacuum degree and the proper heating temperature of the heating plate is particularly important for improving the purity of the blue vitriol.

The inventor researches and discovers that when the vacuum degree in the device is selected to be-85 to-95 kPa and the temperature of a heating plate is 35 to 50 ℃, the purity of the blue copperas can be higher than 99 percent. Especially when the vacuum degree is selected to be-90 kpa and the temperature is selected to be 45 ℃, the purity of the blue vitriol is 99.6 percent; when the vacuum degree is selected to be-95 kpa and the temperature is selected to be 35 ℃, the purity of the copper sulfate hydrate is 99.4 percent; when the vacuum degree is selected to be-95 kpa and the temperature is selected to be 40 ℃, the purity of the copper sulfate hydrate is 99.6 percent.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.