CN1041405C

CN1041405C - Process for producing cuprous chloride by combined method

Info

Publication number: CN1041405C
Application number: CN94105209A
Authority: CN
Inventors: 彭济时; 范兴永
Original assignee: Xian University of Architecture and Technology
Current assignee: Xian University of Architecture and Technology
Priority date: 1994-05-17
Filing date: 1994-05-17
Publication date: 1998-12-30
Anticipated expiration: 2014-05-17
Also published as: CN1112090A

Abstract

The present invention provides a technology for preparing cuprous chloride with copper containing sulfate solution or copper containing chloride solution, which has a more advanced technology, wider adaptability of raw material and a more obvious economic benefit than the existing methods. Compared with the prior arts, the present invention ensures that the direct recovery rate of cuprous chloride preparation is increased by at least 20%; the overall recovery rate of copper reaches at least 98%; the product qualification rate approaches to 100%; the utilization rate of chlorine is increased by at least one time; the processing cost of products per ton is decreased by at least 20%, thereby having an obvious economic benefit.

Description

A kind of technology of producing cuprous chloride

The present invention relates to a kind of novel process of producing cuprous chloride.

The industrial production of cuprous chloride mainly contains two kinds of methods, i.e. elutriation method and direct-reduction process at present.Elutriation method mainly is to be raw material with the red copper, is chlorizating agent with salt, hydrochloric acid, and sodium chlorate is an oxygenant, red copper is dissolved as monovalence copper chloro-complex in high chlorine solution, thin up then, and elutriation goes out cuprous chloride.The main drawback of this technology is: (1) sodium chlorate consumption is big, price is expensive, and dangerous; (2) direct yield of cuprous chloride is low, is generally about 50%, reaches 60% in the time of preferably; (3) a large amount of iron content copper sponges of output; (4) adopt alcohol as antioxidant, cause fire easily; (5) products therefrom needs can obtain powdery grey cuprous chloride through ball milling after the vacuum-drying, and environment is very abominable, and the cuprous chloride loss is big; (6) contain in the liquid behind the iron powder replacement in 1～2g/l copper, the chlorion in the back liquid is not utilized effectively; (7) the cuprous chloride crystallization that obtains behind the elutriation is tiny, the easy oxidation of filtration difficulty; (8) cost height.

Direct-reduction process is that the oxide compound with cupric salt or copper is a raw material, is chlorizating agent with sodium-chlor, utilizes SO ₂For reductive agent is reduced into cuprous chloride with cupric.The main drawback of this technology is: (1) reductive agent SO ₂Consumption big because whole Cu in the solution ²⁺All to use SO ₂Reduce, also useful copper powder is made reductive agent, but the copper powder valency passes through, consumption is big; (2) direct yield of cuprous chloride is low is generally 50～60%; (3) the same elutriation method of other shortcomings.Because this method cost is higher, therefore, is used in the laboratory at present more.As: the people such as P.B.LINRSON of chemical industry system of australian university once utilized sulfurous gas to make reductive agent, carried out reclaiming from cupric vitriol or chloride solution the laboratory study of copper; The Fu Chong of China Zhongnan Polytechnic Univ says that professor and co-worker thereof also were engaged in similarly research work, but this method is directly applied to industrial production, does not appear in the newspapers so far both at home and abroad.

The present invention innovates to obtain on the basis of direct-reduction process and elutriation method, and it is a kind ofly can improve product direct yield and quality product, reduces cost the new process of the production cuprous chloride that adaptability is extensive.

Technical scheme of the present invention is achieved in that

With copper bearing vitriol or chloride solution, purple composition brass, cupric oxide is raw material, and sodium-chlor is chlorizating agent, with SO ₂Gas is reductive agent, concrete operations technological process following (can with reference to schema):

(1) dosing: copper sulfate or copper-bath are pressed 8: 1 chlorine copper mol ratio and sodium-chlor mixing dosing, require copper concentration to reach 30～50g/l;

(2) molten copper: adding dosing in purple composition brass, is oxygenant with the bivalent cupric ion in the dosing, and chlorion is a complexing agent, 60～90 ℃ of controlled temperature, and the time is 2～5 hours, produces monovalence copper chloro-complex solution;

(3) reduction: the high chlorine copper molar solution that produces in the molten copper process is mixed by 1: 1 bronze medal mol ratio with not chloride copper-bath, under 30～80 ℃ of conditions of temperature, add SO ₂Gas reduces, and makes the cupric in the mixed solution be converted into monovalence copper, produces to contain the cuprous reduction slurry of chlorination;

(4) elutriation: the slip that will reduce mixes with clear water and carries out elutriation, leaves standstill 1～2 hour, after solid-liquid separation, produces wet cuprous chloride; Filter cake obtains pure white finished product cuprous chloride through washing, dehydration, antioxidation treatment, drying;

(5) the elutriation filtrate after the solid-liquid separation, part is returned molten copper dosing, and remaining fluid is neutralized to pH=2～3 with lime carbonate, isolates behind the calcium sulfate and is neutralized to the heavy copper in pH=7～8 with liquid caustic soda or soda ash again, and heavy copper ashes returns molten copper dosing.

The present invention mainly has following character of innovation on technology:

1. the present invention makes oxygenant without the sodium chlorate of elutriation method, and using copper sulfate instead is oxygenant, and selects best chlorine copper mol ratio to carry out dosing, not only cheaply but also safety.

2. solution of the present invention carries out dosing by 8: 1 chlorine copper mol ratios, makes Cu in the terminal point solution of molten copper ⁺, Cu ²⁺, SO ₄ ^2-, Cl ^-Certain ratio is arranged, obtained behind the molten copper Cu maximum in the liquid ⁺Chloro-complex concentration.In reduction process, adding copper mol ratio is 1: 1 a copper-bath, and this is for reducing SO ₂SO in the liquid of reduction back is kept in the consumption of reductive agent ₄ ^2-Concentration reaches certain value, obtains high cuprous chloride direct yield and improve oxidation-resistance most important.

Direct-reduction process SO ₂The purpose of making reductive agent then is with CuSO purely ₄The Cu of solution ²⁺Be reduced to Cu ⁺, so that obtain the complex compound of cuprous chloride.Therefore the direct yield of this method is lower, and Anti-oxidization of Cuprous Chloride is poor, SO ₂Consumption is big.

3. another technical characterictic that is different from elutriation method and direct-reduction process among the present invention is that elutriation liquid partly recycles, sulfuric acid in the elutriation liquid has replaced the hydrochloric acid that strong and stimulating is arranged in the elutriation method, the comprehensive utilization ratio of raw material improved, saved the consumption of salt, copper, acid, reduced cost.

The present invention compared with prior art has following beneficial effect:

1. the present invention makes cuprous chloride production that a high direct yield be arranged, and compares with elutriation method, and direct yield can improve more than 20%;

2. constant product quality is good, meets " GB1619-79 ", qualification rate 100%, and also every index mostly is better than the GB requirement, and antioxidant property is good, and product is the loose cuprous chloride powder of white;

3. production efficiency height is compared with elutriation method and can be enhanced productivity more than the twice;

4. starting material and water, electricity, vapour consumption indicators are low, and the utilization ratio of chlorine is enhanced about more than once, and the copper unit consumption is basic near theoretical consumption, and the water unit consumption has only half of elutriation method;

5. throughput is changeable, and adaptability to raw material is strong;

6. production cost is lower, and the process cost of ton product are compared with elutriation method and can be reduced more than 20%, and economic and technical norms are better, have tangible economic benefit.

The present invention is further illustrated below in conjunction with schema.

Figure one is a principle flow chart of the present invention.

Embodiment:

The present invention produces the content of the relevant element in the solution of cuprous chloride and be advisable Cu:20～100g/l, H in following scope ₂SO ₄: 0～15g/l, Fe≤10g/l, Ni≤10g/l also can produce for iron content, solution that nickel is high and to meet the qualified product that national standard " GB1619-79 " requires, but cost slightly raises.

Get and contain Cu ²⁺The sulphuric acid soln 200ml of 40g/l is that 8: 1 chlorine copper mol ratio adds NaCl in proportion, after the heated and stirred dissolving, adds enough purple composition brasses, 80 ℃ of following constant temperature 3.5 hours, filtered while hot then, with this solution again with 200mlCu ²⁺The copper-bath of 80g/l mixes in the three-necked flask that adds 500ml, feeding sulfurous gas down at 60 ℃ reduced 1.5 hours, the cuprous chloride slurry of output adds water 500ml again and left standstill 1 hour, carry out solid-liquid separation, washing, antioxidation treatment, put into beaker and under 120 ℃, carry out drying, met the cuprous chloride 41.91g of " GB1619-79 " standard, wherein CuCl content 98.44%, CuCl ₂Content 0.84%, acid non-soluble substance 0.15%, iron level 0.0025, sulfate radical contain less than 0.3%, and solution partly returns dosing behind the elutriation, rest part CaCO ₃Be neutralized to pH=2～3, isolate calcium sulfate and add liquid caustic soda again and be neutralized to pH=7～8, reclaim the emission standard that waste water behind the copper reaches national trade effluent.

The present invention successfully is applied in China factory industrial production, and the production statistic data shows that this invention is rationally feasible, technical indicator advanced person, and economic benefit is obvious.Its direct yield is brought up to about 85% by original 60%, and copper recovery can reach more than 98%, product percent of pass 100%, and labour productivity doubles, and the process cost of ton cuprous chloride reduce by 20% than former elutriation method.

Claims

1. technology of producing cuprous chloride is raw material with copper bearing vitriol or chloride solution, purple composition brass, cupric oxide, and sodium-chlor is chlorizating agent, with SO ₂Gas is reductive agent, it is characterized in that the concrete operations step is as follows:

(1) dosing:, require copper concentration to reach 30～50g/l copper sulfate or copper-bath chlorine copper mol ratio and sodium-chlor mixing dosing by 8: 1;

(2) molten copper: in 60～90 ℃ of temperature ranges, this dosing and purple composition brass are reacted, keep the certain acidity of solution, can form qualified high chlorine copper solutions through reaction in 2～5 hours;

(3) reduction: after solution and copper-bath behind the molten copper pressed 1: 1 bronze medal mixed in molar ratio, in mixing solutions, add SO ₂Reductive agent reduces in 30～80 ℃ of scopes;

(4) elutriation: the slip that will reduce mixes with clear water, leaves standstill 1～2 hour, after solid-liquid separation, produces wet cuprous chloride;

(5) filter cake obtains pure white finished product cuprous chloride through washing, dehydration, antioxidation treatment, drying;

(6) the elutriation filtrate after the solid-liquid separation, part is returned molten copper dosing, and all the other filtrates to pH=2～3, again with liquid caustic soda or soda ash are neutralized to pH=7～8 heavy copper after isolating calcium sulfate with lime carbonate neutralizing acids, and heavy copper ashes returns molten copper dosing.