CN218951035U

CN218951035U - Continuous production system of basic cupric carbonate based on ammonia circulation system

Info

Publication number: CN218951035U
Application number: CN202221908574.5U
Authority: CN
Inventors: 李晓清
Original assignee: Individual
Current assignee: Individual
Priority date: 2022-07-22
Filing date: 2022-07-22
Publication date: 2023-05-02
Anticipated expiration: 2032-07-22

Abstract

The utility model relates to a continuous production system of basic copper carbonate based on an ammonia circulation system, which relates to the field of chemical industry, and comprises a stripping deamination tower, wherein a pretreatment module is connected to the left inlet of the stripping deamination tower, and a post-treatment module is connected to the outlet of the lower end of the stripping deamination tower, so that reactants and products can be treated respectively; the stripping and decomplexing reaction is carried out in a stripping tower, and the process has the characteristics of continuous and stable production, low energy consumption and small waste water and waste gas amount, so that the process has important economic and social benefits, and can also be used for producing basic nickel carbonate by using nickel plates, nickel beans or nickel-containing waste as raw materials; the electrolytic zinc and nickel-containing waste can be used as raw materials to produce nickel carbonate; silver carbonate can be produced by using electrolytic silver and silver-containing waste as raw materials.

Description

Continuous production system of basic cupric carbonate based on ammonia circulation system

Technical Field

The utility model relates to the field of chemical engineering, in particular to a continuous production system of basic copper carbonate based on an ammonia circulation system.

Background

Basic copper carbonate, also known as patina and patina, has the chemical formula Cu ₂ (OH) ₂ CO ₃ Copper reacts with oxygen, carbon dioxide, water vapor, and other substances in the air to produce a substance. Heating in air decomposes the copper oxide, water and carbon dioxideThe method is dissolved in acid and generates corresponding copper salt, the existing production process can generate a large amount of waste gas and waste water, and reactants can not be recycled.

Disclosure of Invention

The utility model aims to provide a continuous production system of basic copper carbonate based on an ammonia circulation system, which solves the problems in the prior art.

The utility model solves the technical problems by adopting the following technical scheme:

a continuous production system of basic cupric carbonate based on an ammonia circulation system,

preferably, the copper raw material is pulverized to be in a powder state

Wherein the copper raw material comprises electrolytic copper, copper plate, copper oxide or copper-containing waste, the particle size of the copper powder is 50-1000 meshes, and the powder preparation equipment can adopt an atomization device or a ball milling device or a combination of the atomization device and the ball milling device;

preferably, the copper powder in the first step is subjected to ammonia leaching complexation reaction

The reaction raw materials are copper powder and ammonia water and ammonium bicarbonate mixed solution, oxygen or hydrogen peroxide is introduced into the mixed solution, the mass content of ammonia is kept at 5-20%, the mass content of ammonium bicarbonate is kept at 2-20%, the ammonia leaching complexing reaction time is controlled at 0.5-20 hours, the reaction temperature is controlled at 40-90 ℃, the pressure is controlled at 0-1.0MPa, and the complexing reaction formula is:

2Cu+6NH3+2NH4HCO3+O2——>2Cu(NH3)4CO3+2H2O

the ammonia leaching complex reaction process is a continuous reaction process, and the reactor is one or a combination of a plurality of continuous multi-kettle series reactors, horizontal multi-stage stirring kettles, pipeline reactors, oscillating flow pipe reactors, supergravity continuous reactors and impinging stream continuous reactors;

preferably, filtering the leaching solution obtained after the reaction in the step two to obtain filtrate

The filtering is to filter impurities such as iron, tin, aluminum hydroxide and unleached copper in the solution after the reaction, and the filter cake is washed and then subjected to post-treatment to obtain filtrate, wherein the main components of the filtrate are water, ammonia, ammonium bicarbonate and copper-containing complex;

preferably, adding a proper amount of liquid alkali into the filtrate to form tower bottom liquid, thereby preheating;

preferably, the tower bottom liquid enters a stripping deamination tower to react, so as to obtain a product basic cupric carbonate and a mixed liquid of recyclable ammonium bicarbonate and ammonia;

the tower bottom liquid enters a stripping deamination tower from the middle upper part, steam is added into the tower bottom of the stripping deamination tower, the copper ammonia complex is subjected to decomplexing reaction under the condition of high temperature, basic copper carbonate solid, ammonia and ammonium bicarbonate are generated, and the ammonium bicarbonate is subjected to decomposition reaction under the condition of high temperature, wherein the specific reaction formula is as follows:

2Cu(NH3)4CO3+2H2O——>Cu CO3·Cu(OH)2+(NH4)2CO3+6NH3↑NH4HCO3——>2NH3↑+CO2↑+H2O

ammonia and carbon dioxide steam in the stripping deamination tower go to the tower top, water and basic cupric carbonate go to the tower bottom, the ammonia content is less than 2g/L, ammonia and carbon dioxide steam are stripped to the tower top, the ammonia and carbon dioxide steam are condensed by a condenser, the ammonia reacts with the carbon dioxide in the condensation process to produce ammonium bicarbonate, and the condensate is a mixed solution of ammonium bicarbonate and ammonia due to excessive ammonia, wherein the ammonia content is 15-20%, and the ammonium bicarbonate is about 10%;

the stripping deamination tower is a main device of the system, has the advantage of high tower plate efficiency, can also accommodate high-content solid suspended matters to pass through without blocking faults, and ensures the reliability of continuous and stable operation of the device;

the condenser is a shell-and-tube heat exchanger;

preferably, preparing a mixed leaching solution of ammonia water and ammonium bicarbonate, and supplementing the ammonia water in the fifth step

Because of the stripping deamination process, a small amount of ammonia loss is generated, a small amount of 20% ammonia water is periodically supplemented, ammonia balance of the solution is ensured, carbon dioxide and water are introduced into an ammonia immersion liquid preparation device, the ammonia content of the prepared ammonia immersion liquid is 10-15%, and the ammonium bicarbonate content is 8-15%;

the ammonia immersion liquid preparing device adopts an intermittent production mode, and can adopt a stirring kettle or a stirring tank for carrying out a compounding reaction;

preferably, the tower bottom liquid after extraction and deamination is treated

The preheated leaching solution is cooled to be within 60 ℃ by using a preheater, then is filtered, and after a filter cake is washed by water, the filter cake can be dried to prepare basic copper carbonate for sale, or can be directly used for preparing active copper oxide or can be used for preparing copper powder by reduction in other workshops;

the preheater is one or a combination of a plurality of plate heat exchangers, tube heat exchangers and spiral heat exchangers;

preferably, the filtrate is treated

The filtrate contains a small amount of ammonia, ammonium bicarbonate or sodium carbonate, and can be concentrated by reverse osmosis of a membrane, and the concentrated water returns to the production before stripping deamination to recover ammonia, and the produced water can be used as production water.

The utility model has the advantages and positive effects that:

1. according to the utility model, electrolytic copper or copper-containing waste is prepared into metal copper powder, and then ammonia leaching complex reaction is carried out, so that the reaction interface of gas, liquid and solid is increased, the leaching reaction rate is accelerated, and the continuous reaction is ensured.

2. The ammonia distillation process adopts the stripping tower to carry out deamination and decomplexing reaction, the reaction can be continuously carried out due to the characteristic of the stripping deamination tower, and only ammonia, carbon dioxide and part of water are stripped, so that the efficiency is improved and the energy consumption is reduced compared with the ammonia distillation process of the traditional reaction kettle; by adopting the method of condensing and recycling ammonia water, most ammonia is condensed, only a small amount of non-condensable gas is entrained and absorbed by dilute sulfuric acid or dilute hydrochloric acid, and the waste gas amount is greatly reduced compared with the traditional process.

3. The utility model can be used for producing basic nickel carbonate, and can produce basic nickel carbonate by using nickel plates, nickel beans or nickel-containing waste as raw materials.

4. The utility model has the characteristics of continuous and stable production, low energy consumption and small waste water and gas amount, and has important economic and social benefits.

Drawings

The utility model will be further described with reference to the drawings and examples.

FIG. 1 is a schematic diagram of the overall structure of a basic copper carbonate continuous production system based on an ammonia recycle system according to the present utility model;

the index marks in the drawings are as follows: 11. ball milling equipment; 12. a mixing kettle; 13. a slurry pump; 14. a reactor; 15. a leaching liquid pump; 16. a first filter; 17. a preheater; 20. stripping deamination tower; 30. a condenser; 32. an ammonia water pump; 33. preparing a kettle; 34. an ammonia leaching pump; 40. a tower bottom pump; 41. a second filter; 42. a wastewater treatment device; 43. a treatment pump.

Detailed Description

The utility model will now be described in further detail with reference to the accompanying drawings. The drawings are simplified schematic representations which merely illustrate the basic structure of the utility model and therefore show only the structures which are relevant to the utility model.

The utility model will be described in detail with reference to fig. 1, wherein for convenience of description, the following orientations are defined as follows: the vertical, horizontal, vertical, front-to-back directions described below are the same as the vertical, horizontal, vertical, and horizontal directions of the view of fig. 1. Fig. 1 is a front view of the device of the present utility model, and the direction of fig. 1 is the same as the vertical, horizontal, vertical, front-to-back, horizontal, and horizontal directions of the device of the present utility model.

Embodiments of the utility model are described in further detail below with reference to the attached drawing figures:

referring to fig. 1, an embodiment of the present utility model is provided: the utility model provides a continuous production system based on ammonia circulation system's basic cupric carbonate, includes strip deamination tower 20, strip deamination tower 20 left side access connection is equipped with pretreatment module, strip deamination tower 20 lower extreme exit linkage is equipped with the aftertreatment module to can handle reactant and product respectively, strip deamination tower 20 right side upper end is connected and is equipped with circulation module, just circulation module with communicate between the pretreatment module, thereby can be under circulation module's effect, intermediate product is prepared, and then get back to in the pretreatment module again, and then accomplish cyclic utilization.

In addition, in one embodiment, the pretreatment module comprises a ball milling device 11, a mixing kettle 12, a slurry pump 13, and the ball milling device 11, the mixing kettle 12 and the slurry pump 13 are sequentially communicated, so that the placed copper raw materials can be crushed under the action of the ball milling device 11, wherein the copper raw materials comprise electrolytic copper, copper plates, copper oxide or copper-containing waste, the particle size of the copper powder is 50-1000 meshes, and then the copper raw materials enter the mixing kettle 12, are mixed by adding clear water, and are transported under the action of the slurry pump 13.

In addition, in one embodiment, the pretreatment module further includes a reactor 14 and a leaching solution pump 15, one end of the reactor 14 is communicated with the slurry pump 13, and the other end is communicated with the leaching solution pump 15, so that reactants transported by the slurry pump 13 can be reacted in the reactor 14, oxygen or hydrogen peroxide is introduced into the reactants, during the reaction, the mass content of ammonia is kept at 5-20%, the mass content of ammonium bicarbonate is 2-20%, the ammonia leaching complexing reaction time is 0.5-20 hours, the reaction temperature is controlled between 20-90 ℃ of a tower kettle pump, the pressure is 0-1.0MPa, and the complexing reaction formula is:

2Cu+6NH3+2NH4HCO3+O2——>2Cu(NH3)4CO3+2H2O

the ammonia leaching complex reaction process is a continuous reaction process, and the reactor is one or a combination of a plurality of continuous multi-kettle series reactors, horizontal multi-stage stirring kettles, pipeline reactors, oscillating flow pipe reactors, supergravity continuous reactors and impinging stream continuous reactors.

In addition, in one embodiment, the pretreatment module further includes a first filter 16 and a preheater 17, one end of the first filter 16 is communicated with the leaching liquid pump 15, the other end is communicated with the preheater 17, and the other end of the preheater 17 is communicated with the stripping deamination tower 20, so that the reacted solution can be filtered under the action of the first filter 16, iron, tin, aluminum hydroxide and unleached copper can be filtered, the filter cake is washed and then is post-treated to obtain a filtrate, the main components of the filtrate are water, ammonia, ammonium bicarbonate and copper-containing complex, and a proper amount of caustic soda solution can be added into the preheater 17 to form a tower kettle solution, so that the preheating is performed.

In addition, in one embodiment, the tower bottom liquid is led into the stripping deamination tower 20 to react, so as to obtain a product basic cupric carbonate and a mixed solution of ammonium bicarbonate and ammonia, the tower bottom liquid is led into the stripping deamination tower from the middle upper part, steam is added into the tower bottom of the stripping deamination tower, the copper ammonia complex is subjected to decomplexing reaction under the condition of high temperature, basic cupric carbonate solid, ammonia and ammonium bicarbonate are generated, and the ammonium bicarbonate is subjected to decomposition reaction under the condition of high temperature, wherein the specific reaction formula is as follows:

in the stripping deamination tower 20, ammonia and carbon dioxide steam go to the top of the tower, water and basic copper carbonate go to the bottom of the tower, the ammonia content is less than 2g/L, and the ammonia and carbon dioxide steam are stripped to the top of the tower.

In addition, in one embodiment, the circulation module comprises a condenser 30 and an ammonia water pump 32, one end of the condenser 30 is communicated with the stripping deamination tower 20, the other end of the condenser is communicated with the ammonia water pump 32, so that condensation can be performed under the action of the condenser 30, ammonia reacts with carbon dioxide in the condensation process to produce ammonium bicarbonate, and due to the excessive ammonia, the condensate is a mixed solution of ammonium bicarbonate and ammonia, wherein the ammonia content is 10-20%, and the ammonium bicarbonate is about 5-15%.

In addition, in one embodiment, the circulation module further includes a preparation kettle 33 and an ammonia immersion pump 34, one end of the preparation kettle 33 is communicated with the ammonia water pump 32, the other end of the preparation kettle 33 is communicated with the ammonia immersion pump 34, and the other end of the ammonia immersion pump 34 is communicated with the reactor 14, so that the solution can be prepared in the ammonia immersion pump 34, and a small amount of ammonia loss is generated in the process of stripping deamination, so that a small amount of 20% ammonia water is periodically replenished, the ammonia balance of the solution is ensured, carbon dioxide and water are introduced into an ammonia immersion device, the ammonia content of the prepared ammonia immersion liquid is 5-20%, the ammonium bicarbonate content is 2-15%, the ammonia immersion device adopts an intermittent production mode, a mixing kettle or a mixing tank can be adopted for carrying out a compounding reaction, and the solution is returned into the reactor 14 after the preparation is completed, and then the solution is recycled as a reactant.

In addition, in one embodiment, the post-treatment module includes a tower kettle pump 40, a second filter 41, a waste water treater 42 and a treatment pump 43, the tower kettle pump 40 is communicated with the stripping deamination tower 20, the other end is communicated with the preheater 17, the preheater 17 is communicated with the second filter 41, the second filter 41 is communicated with the waste water treater 42, the waste water treater 42 is communicated with the treatment pump 43, so that the preheated leaching solution is cooled to be within 60 ℃ by the preheater 17, the preheated leaching solution is filtered under the action of the second filter 41, the filtered solution is treated under the action of the waste water treater 42, the filtered solution contains a small amount of ammonia, ammonium bicarbonate or sodium carbonate, the ammonia can be recovered before stripping deamination by using a membrane reverse osmosis concentration, and the produced water can be used as production water.

Additionally, in one embodiment, the copper feedstock can be replaced with a nickel feedstock to produce basic nickel carbonate, the copper feedstock can be replaced with a zinc feedstock to produce zinc carbonate, and the copper feedstock can be replaced with a silver feedstock to produce silver carbonate.

In specific implementation, firstly, the copper raw material is placed in the ball milling equipment 11, crushed into powder, enters the mixing kettle 12, is mixed by adding water, enters the reactor 14 to carry out ammonia leaching complexation reaction, is filtered in the first filter 16, is preheated in the preheater 17 to enter the stripping deamination tower 20, and produces two parts of products, one part is required basic copper carbonate, the other part is a mixed solution of ammonium bicarbonate and ammonia, the two parts are prepared in the preparation kettle 33, the reactants required by the ammonia leaching complexation reaction in the reactor 14 are reformed, the circulation is completed, and the other part of products are treated.

It should be emphasized that the examples described herein are illustrative rather than limiting, and therefore the utility model is not limited to the examples described in the detailed description, but rather falls within the scope of the utility model as defined by other embodiments derived from the technical solutions of the utility model by those skilled in the art.

Claims

1. A continuous production system for basic copper carbonate based on an ammonia recycle system comprising a stripping deamination column (20), characterized in that: the left side inlet connection of the stripping deamination tower (20) is provided with a pretreatment module, the outlet connection of the lower end of the stripping deamination tower (20) is provided with a post-treatment module, the upper end connection of the right side of the stripping deamination tower (20) is provided with a circulation module, and the circulation module is communicated with the pretreatment module.

2. A continuous production system for basic copper carbonate based on an ammonia recycle system according to claim 1, wherein: the pretreatment module comprises ball milling equipment (11), a mixing kettle (12) and a slurry pump (13), wherein the ball milling equipment (11), the mixing kettle (12) and the slurry pump (13) are sequentially communicated, the ball milling equipment (11) pulverizes the placed copper raw material, and the particle size of the copper powder is 50-1000 meshes.

3. A continuous production system for basic copper carbonate based on an ammonia recycle system according to claim 2, wherein: the pretreatment module further comprises a reactor (14) and a leaching liquid pump (15), wherein one end of the reactor (14) is communicated with the slurry pump (13), and the other end of the reactor is communicated with the leaching liquid pump (15).

4. A continuous production system for basic copper carbonate based on an ammonia recycle system according to claim 3, wherein: the pretreatment module further comprises a first filter (16) and a preheater (17), one end of the first filter (16) is communicated with the leaching liquid pump (15), the other end of the first filter is communicated with the preheater (17), and the other end of the preheater (17) is communicated with the stripping deamination tower (20).

5. A continuous production system for basic copper carbonate based on an ammonia recycle system according to claim 3, wherein: the circulation module comprises a condenser (30) and an ammonia water pump (32), wherein one end of the condenser (30) is communicated with the stripping deamination tower (20), and the other end of the condenser is communicated with the ammonia water pump (32).

6. The continuous production system of basic copper carbonate based on an ammonia recycle system according to claim 5, wherein: the circulation module further comprises a preparation kettle (33) and an ammonia leaching pump (34), one end of the preparation kettle (33) is communicated with the ammonia leaching pump (32), the other end of the preparation kettle (33) is communicated with the ammonia leaching pump (34), and the other end of the ammonia leaching pump (34) is communicated with the reactor (14).

7. The continuous production system of basic copper carbonate based on an ammonia recycle system according to claim 4, wherein: the post-treatment module comprises a tower kettle pump (40), a second filter (41), a wastewater treatment device (42) and a treatment pump (43), wherein the tower kettle pump (40) is communicated with the stripping deamination tower (20), the other end of the tower kettle pump is communicated with the preheater (17), the preheater (17) is communicated with the second filter (41), the second filter (41) is communicated with the wastewater treatment device (42), and the wastewater treatment device (42) is communicated with the treatment pump (43).