CN1160020A

CN1160020A - Process for direct production of cupric sulfate from cupric oxide ore

Info

Publication number: CN1160020A
Application number: CN97100770A
Authority: CN
Inventors: 封瑞; 蔡萌生
Original assignee: Individual
Current assignee: Individual
Priority date: 1997-02-25
Filing date: 1997-02-25
Publication date: 1997-09-24

Abstract

A process for directly producing copper sulfate from copper oxide ore includes reaction of powdered copper oxide ore with sulfuric acid, separation of solution from slags, contact action of separated solution with copper and oxygen-enriched air, removing impurities, evaporating concentration, and cooling crystallization, and features easy operation control, short reaction time, no environmental pollution, low cost and high purity of product.

Description

Process for directly producing copper sulfate from copper oxide ore

The invention relates to a method for producing copper sulfate, in particular to a method for directly producing copper sulfate by taking copper oxide ore as a raw material.

Copper sulfate is an important chemical raw material for preparing other copper compounds and electrolytically refined copper, and is also an important chemical component for preparing pesticides such as insecticides and the like in fruit tree cultivation. Usually, copper sulfate can be prepared by the action of copper or copper oxide and sulfuric acid, or copper scrap recovered from waste products is used as a raw material to produce the copper sulfate, and the methods have the defects of long reaction time, large process difficulty, high production cost and the like. CN1095110A discloses a method for directly producing copper sulfate by using the action of copper oxide ore powder and sulfuric acid, which shortens the reaction time, makes full use of the waste copper oxide ore and greatly reduces the production cost, but adopts a chemical reaction inhibitor; the inhibition of the generation of harmful impurities such as non-copper sulfate and the like needs to carry out a plurality of tests and tests in the production process, and the reaction temperature and time are often difficult to control better, so that the inhibition effect is sometimes not ideal, and the product quality is influenced to a certain extent.

The invention aims to overcome the defects in the method provided by CN1095110A, and provides a novel process for producing copper sulfate by using copper oxide ore, which reduces or eliminates excessive complicated testing and testing procedures, ensures that the reaction temperature and time are not influenced so as to carry out continuous production, and can effectively remove non-copper sulfate impurities.

The copper oxide ore contains various impurities, such as iron, calcium, magnesium ions and the like, particularly, the iron content is high, sulfate can be produced when the copper oxide ore reacts with sulfuric acid, not only is excessive sulfuric acid consumed, but also the quality of copper sulfate is influenced as harmful impurities. Research experiments show that: after the copper oxide ore powder and the sulfuric acid react, the separated ferrous sulfate in the reaction solution can react under certain conditions as follows:

(I) the reaction can increasethe acidity in the solution, and in order to completely remove the ferrous sulfate, the free acid generated by the formula (I) can be neutralized by copper by the formula (II), so that the acidity is rapidly reduced,

(II) according to the calculation of the solubility product, only controlling the pH value of the solution to be 3-5, and generating Fe (OH) by the formula (I)₃Will precipitate out, thereby allowing the FeSO in the reaction solution to be₄By generating Fe (OH)₃The precipitate is removed. The effect of purifying the reaction solution is achieved, the PH value in the solution can be adjusted to be increased by the formula (II), and the generated copper sulfate can effectively utilize the added sulfuric acid. Based on the principle, the novel process for producing the copper sulfate by using the cupric oxide ore powder as the raw material comprises the steps of sequentially adding water, crushed ore powder and concentrated sulfuric acid in a solid-liquid ratio into a reaction kettle, reacting at 60-80 ℃ for 30-40 minutes, carrying out solid-liquid separation, purifying the separated reaction solution, removing impurities such as iron ions in the solution, evaporating and concentrating the purified solution until the specific gravity of the solution reaches 1.35-1.4, cooling, crystallizing, centrifugally dewatering, drying and the like to obtain the product(FIG. 1). The purification treatment refers to a purification treatment process in which the solution separated by a solid-liquid separation method reacts with oxygen-enriched air and copper at 70-80 ℃. The concrete process steps can be as shown in figure 2, the copper sulfate-containing solution after solid-liquid separation in the circulating liquid pool 5 is sent to a solution heater 7 by a pump 6 to be heated, then sent to a spray head 8 of a purification tower 4 to be sprayed on copper wires 9, the temperature in the tower is kept at 70-80 ℃, so that the copper sulfate solution flows from top to bottom and is just in countercurrent contact with oxygen-enriched air sent from the bottom of the tower in the purification tower to generate a reaction as shown in a reaction formula (I), and the generated sulfuric acid is in contact with the copper wires 9 to generate a reaction as shown in a reaction formula (II) in an oxygen-enriched air flow, so that the acidity is reduced; the neutralized sulfuric acid generates copper sulfate, and the copper sulfate and the original copper sulfate solution return to the circulation through the tower bottomThe liquid circulating pool 5 is used for repeatedly and circularly purifying until the pH value of the tower liquid reaches 3.5-5, and Fe (OH) in the solution₃And precipitating out in the circulating liquid pool 5, thereby removing ferrous ions in the solution. The purified copper sulfate solution is obtained and is filtered by a plate and frame filter press 10 to enter the evaporation process.

Tests show that malachite and orchite in carbonate ores in the copper deposit oxidation zone; the silicate minerals include sildendum and alexandrite; the chalcopyrite and the cuprite (which need to be treated slightly) in the copper oxide minerals can be used for producing the copper sulfate. In addition, the method is also suitable for copper oxide ores containing noble metals, and the noble metals such as gold and silver are separated by a gravity separation method before or after reaction and then the process flow is carried out.

The novel process for directly producing the copper sulfate by using the copper oxide ore as the raw material not only reserves the advantages of the method disclosed by CN1095110A, such as high reaction speed, waste recycling, no pollution to the environment, high product purity, low cost and the like; the purification treatment is carried out by adopting a purification tower device, the operation and control are simple and easy, and the whole production process can be effectively controlled by only measuring the PH value of the solution in the circulating liquid pool 5 and the specific gravity of the evaporated solution on time, thereby ensuring the quality of the product.

Example (b):

processing a high-quality product of the copper oxide ore after manual hand selection into fine powder of 180-200 meshes by a jaw crusher, a fine particle jaw crusher and a grinding mill in sequence, analyzing the copper content to 9%, and calculating the adding amount of sulfuric acid;

firstly 1.6m³To 1.8m³In a stainless steel reaction kettle; simultaneously introducing steam into a jacket of a reaction kettle to heat the water to 65 ℃, starting a stirrer, adding 460Kg of the fine mineral powder into the kettle, slowly adding 78Kg of concentrated sulfuric acid into the kettle in a trickle mode, controlling the acid adding speed, stirring for 35 minutes after the sulfuric acid is added until bubbles generated by the reaction do not overflow the reaction kettle, measuring the pH value to be 3-4, and stopping the reaction; solid-liquid separation is carried out by a spiral discharge sedimentation centrifuge (WL-350B produced by China Chongqing chemical machinery factory); sending the separated sulfate-containing liquid into a circulating liquid pool 5 as shown in figure 2, pumping clear liquid in the circulating pool 5 by a pump 6, sending the clear liquid to a solution heater 7 for heating, sending the clear liquid to a nozzle 8 for spraying on a copper wire 9, enabling the sulfate solution to flow from top to bottom, starting an oxygen-enriched air device, sending the oxygen-enriched membrane 1 into a tower bottom through an air blower 2 and a heater 3 to be in countercurrent contact with the flowing solution, sending the solution to the circulating liquid pool 5 through the bottom surface of a purification tower 4, and determining the pH value of the solution in the circulating liquid pool 5 to be 4 by using a pH test paper, namely finishing purification; then filtering the purified copper sulfate solution by a plate-and-frame filter press 10, and inputting the filtered copper sulfate solution into a stainless steel tube type vacuum evaporator for evaporation and concentration until the specific gravity of the solution reaches 1.35; and finally, removing the solution from the evaporation, cooling, crystallizing, centrifugally dewatering, drying, weighing and packaging to obtain 80.5kg of first-grade copper sulfate. 81kg of the copper sulfate solution separated by centrifugation with a specific gravity of 1.2 can be added into the solution separated in the next production and evaporated and concentrated.

And carrying out three-stage countercurrent washing on the separated slag, and returning the washing to the production line. Used as mother liquor for the next reaction. See the schematic process flow diagram of figure (1).

Description of the drawings:

FIG. 1 is a schematic process flow diagram for the direct production of copper sulfate from noble metal-free copper oxide ore;

FIG. 2 is a schematic view of a purification process:

1. oxygen-enriched membrane 2, air blower 3, hot air heat exchanger 4 and purification tower

5. A circulating liquid pool 6, a high-temperature acid-resistant pump 7, a solution heater 8 and a spray head

9. Red copper wire 10, plate and frame filter press

Claims

1. A method for directly producing copper sulfate by using copper oxide ore comprises sequentially adding water, fine mineral powder and concentrated sulfuric acid in a solid-liquid ratio into a reaction kettle; reacting for 30-40 minutes at 60-80 ℃; performing solid-liquid separation; the method is characterized in that the separated reaction solution is purified, and then is evaporated, concentrated, cooled and crystallized to obtain the product; the purification treatment is a purification process in which the reaction solution reacts with oxygen-enriched air and copper at 70-80 ℃.

2. The method for directly producing copper sulfate from copper oxide ore as claimed in claim 1, wherein the purification process comprises the steps of feeding the copper sulfate solution in the circulating liquid tank 5 into the solution heater 7 by the pump 6 as shown in the figure, heating, feeding the heated copper sulfate solution into the spray head 8 of the purification tower 4, spraying the heated copper sulfate solution onto the copper wire 9, maintaining the temperature in the tower at 70-80 ℃, enabling the copper sulfate solution to flow from top to bottom, making the copper sulfate solution contact with the oxygen-enriched air fed from the bottom of the tower in a countercurrent manner in the purification tower, returning the copper sulfate solution to the circulating liquid tank 5 through the bottom of the tower, and repeatedly and circularly purifying until the pH value of the solution reaches 3..