CN1676639A

CN1676639A - Method for producing white arsenic using high-surfur high-arsenic-tin ore tailing

Info

Publication number: CN1676639A
Application number: CNA200510020383XA
Authority: CN
Inventors: 王熙
Original assignee: Individual
Current assignee: Individual
Priority date: 2005-02-15
Filing date: 2005-02-15
Publication date: 2005-10-05

Abstract

This invention is a method using rich sulfur arsenic tin ore debris to produce white arsenic. The main method is to add water, xanthic acid and oils and fats colleting agents and mersolates adjusting agent to implement paste mixing and medical pre-treatment to widen the difference between the arsenic ore and sulfur ore; use floatation machine to floating select and separate to get sulfur refined products and rich arsenic tin debris: use reflecting furnace to oxidation melt the rich arsenic tin debris under 450-800deg.C and make the arsenic matters overflow in the form of arsenous oxide, and use sedimentation and cloth dust collection methods to get while arsenic products and use heavy, magnetic and floating concentration methods to recycle the left tin. This invention adopts the route of devulcanizing first, realize the separation of sulfur and arsenic and oxygenate to get white arsenic and at last choose the qualified tin refined products. The technique flow is short, the design is novel, the methods is proper, and realize the high effective recycle of arsenic, sulfur and tin, and the economic and technological indexes are idea. This invention has a great significance to the utilization of debris resources.

Description

Method for producing white arsenic by using high-sulfur high-arsenic tin ore old tailings

The invention belongs to the technical field of a method for recycling old tailing resources, and particularly relates to a method for producing white arsenic by using high-sulfur high-arsenic tin ore old tailings.

The tailings in the background art are wastes accumulated in the production of various metal or nonmetal ore dressing plants all year round, and are resources without utilization value under the current economic and technical conditions. In many tin ore production enterprises, tens of thousands of tons of tailings are continuously pumped to a tailing dam to be stocked every year, and after decades of accumulation, the stock of the tailing dam reaches millions or even thousands of tons. Due to the limitation of technical conditions, a large amount of valuable metal and non-metal elements are not recycled. The tin ore primary ores mined from mines are mostly multi-metal symbiotic sulphide ores, contain main metal tin and are accompanied by copper, sulfur, iron, arsenic and other minerals, and are not taken as recovery objects because of low content or low value and are stockpiled along with the waste tailings. With the gradual depletion of resources and the change of market prices of raw materials, elements which are not originally used become valuable and even very pretty and robbed. This forces people to look at the old waste tailings. The high-sulfur high-arsenic tin ore old tailings are the old tailings. The mineral of tin in the old tailings is mainly cassiterite, most of the cassiterite is recycled, and most of the residual part of the mineral contains less than 0.5 percent of tin. The sulfur mineralis mainly pyrite, and the arsenic is mainly arsenopyrite. Experts and scholars at home and abroad for the smelting method for comprehensively recovering tin, sulfur and arsenic perform many researches, such as: the separation and smelting combined process of producing tin-rich middling by the full gravity separation process without grinding, desulfurizing and desliming and grading and fuming to obtain tin concentrate; the tin is recovered by gravity separation and flotation, namely, the tailings are discarded by gravity separation, tin and sulfide minerals are enriched in gravity separation rough concentrate, and the tin concentrate is separated by removing sulfur and iron by a flotation method; the contents of arsenic, lead and zinc are reduced by grinding and magnetic separation concentration to obtain sulfur concentrate, and lead, zinc and tin enriched in the tailings of the concentrate are comprehensively recovered by adopting a magnetic-floating-heavy process and the like. Most of the processes only focus on the recovery of tin, so that the actual comprehensive recovery is very little, the equipment used follows the same equipment for treating raw ores, and the processes are not changed greatly. The attention is only paid to the technology and technology for recovering heavy tin, and because the content of tin is very low, the satisfactory economic effect cannot be obtained, and the technology and technology are rarely used in production practice.

The invention aims to provide a method for producing white arsenic by using high-sulfur high-arsenic tin ore old tailings, which has high sulfur and arsenic separation efficiency and short process flow and comprehensively recovers sulfur, arsenic and tin, so as to solve the defects of the prior art.

The invention provides a method for producing white arsenic by using high-sulfur high-arsenic tin ore old tailings, which is characterized bycomprising the following steps:

(1) adding water and adding xanthate, grease collecting agent and sodium alkyl sulfonate regulator to carry out size mixing and medicament pretreatment on old tailings, so as to enlarge the flotation property difference of arsenic minerals and sulfur minerals;

(2) carrying out flotation separation by using a flotation machine to obtain a sulfur concentrate product and tin-containing high-arsenic tailings;

(3) oxidizing and roasting the tin-containing high-arsenic tailings by using a reverberatory furnace to enable arsenic minerals to escape in the form of arsenic trioxide gas, collecting white arsenic products by using a settling and cloth bag dust collection mode, and retaining tin in the roasted sand.

The calcine is used for recovering tin by using a heavy, magnetic and floatation ore dressing method.

The pH value of the pretreated ore pulp is 6-8.

The temperature of the oxidizing roasting is 400-800 ℃.

The temperature of the oxidizing roasting is preferably controlled at 450-500 ℃.

The settling chamber for collecting arsenic trioxide gas is an eight-stage settling chamber, the settled tail gas is supplemented with cloth bags for collecting white arsenic, and then alkali is added into the cloth bags, and desulfurization treatment is carried out by using a leaching tower and a turbulent ball tower.

Effective separation of sulfur and arsenic is critical to achieve the objectives of the present invention. If the pyrite and other sulfur minerals can be effectively removed, the method is favorable for improving the arsenic grade and reducing the amount of materials entering the furnace in the next process (smelting), saves energy consumption and labor consumption, is favorable for reducing the content of pyrite in arsenic products, reducing the content of sulfur dioxide in flue gas, reducing the treatment cost of the flue gas, improving the purity of arsenic trioxide, reducing the content of arsenic in sulfur concentrate and improving the quality of the sulfur concentrate.

In the treatment process of the invention, the separation of sulfur and arsenic in the old tailings is the separation of pyrite and arsenopyrite. The main components of the pyrite in the tailings are pyrrhotite and pyrite. The surfaces of the pyrrhotite and the arsenopyrite are easily oxidized in a natural state, and the floatability difference of the pyrrhotite and the arsenopyrite is small after oxidation, so that the pyrrhotite and the arsenopyrite are difficult to separate by a flotation method. Experiments show that a certain electrochemical reaction can occur between the collecting agent adsorbed on the surface of the arsenic sulfide mineral and the surface of the mineral, the reaction speed between the arsenic sulfide mineral and the collecting agent can be accelerated by adding the sodium alkyl sulfonate, the collecting agent is selectively removed, the effect on the pyrite is not obvious, the hydrophobic difference between the two minerals is enlarged, and the separation of the two minerals is convenient to realize. This is an important inventive point of the present invention.

Arsenic main mineral arsenopyrite undergoes a strong oxidation reaction in an oxidation atmosphere at the temperature of 450-500 ℃, and arsenic is As₂O₃The form is volatilized and removed, and the chemical reaction process is as follows:

if the oxidizing atmosphere is too strong, As₂O₃Will be over-oxidized to As₂O₅And generating arsenate (e.g., FeAsO)₄Etc.) are fixed in the calcine, arsenate can cover the surface of the mineral to form a package, and the oxidation reaction is prevented from continuing. Sulfur will also be oxidized to sulfur dioxide at 700-. Therefore, it is very important to control the reaction atmosphere and the reaction temperature and avoid the generation of arsenate and sulfur dioxide.

For As generated by firing₂O₃The qualified white arsenic product can be obtained by adopting the existing eight-stage sedimentation of the sedimentation chamber and the supplementary collection of a cloth bag. The process of the invention has the advantages that the actual yield of arsenic in the tin ore old tailings can reach 90 percent, the content of arsenic in the sulfur concentrate is below 0.5 percent, the main grade reaches 34 percent, and the process completely meets the standard of sulfuric acid plant acid production. The calcine can obtain qualified tin concentrate products by a conventional beneficiation method, and the recovery rate of tin metal reaches 55%.

The invention adopts the process route of firstly desulfurizing, realizing the separation of sulfur and arsenic, then oxidizing, roasting and removing arsenic to obtain white arsenic and finally sorting to obtain qualified tin concentrate, has short process flow and novel conception, ensures that the method is appropriate, realizes the comprehensive recovery of various valuable elements of sulfur and tin while efficiently recovering arsenic, has ideal technical and economic indexes and has great significance for fully utilizing old tailing resources.

Description of the drawings the figure is a process flow diagram of the present invention.

According to the specific embodiment, the high-sulfur high-arsenic tin ore old tailings piled up in a certain tailing dam of the Yunnan old mining area contain tin, copper, iron, sulfur and arsenic respectively up to 0.526%, 0.37%, 49.2%, 31.5% and 11.2% by analyzing samples. The main metal minerals are cassiterite, bornite, pyrrhotite, pyrite and arsenopyrite. Copper is relatively dispersed and low in each mineral. Sulfur is mainly produced in pyrrhotite and pyrite in large quantities. The main mineral of arsenic is arsenopyrite. Tin is mainly present in cassiterite. The main gangue minerals are calcite, dolomite, feldspar, tremolite, actinolite, pyroxene, chlorite, silicate efflorescence, etc. The old tailings are treated by the method of the invention in a certain tin ore production enterprise from 1999 to 2000, 90 tons of the old tailings are treated every day, the total production time is 273 days, 24000 tons of the old tailings are treated together, about 110 tons of tin concentrate containing 43% of tin, 114 tons of enriched middlings containing 3.5% of tin, 13200 tons of sulfur concentrate containing less than 0.5% of arsenic and 3700 tons of arsenic trioxide (white arsenic) with the purity of more than 97% are produced. The recovery rates of the three elements of S, As and Sn reach more than 70%, 90% and 55% respectively.

The regulator for the sulfur-arsenic separation operation in this example is sodium alkylsulfonate, which has the chemical formula: R-SO₃Na and R are alkyl, the carbon atom number C is 7-20, and the main component is 12 alkyl sodium sulfonate. The collecting agent is xanthate and oil, such as ethidium and oleic acid. The pH value of the ore pulp is 6-8. The temperature of the oxidizing roasting is 400-800 ℃, the sulfur content is controlled between 450-500 ℃, and the rest conditions are as above.

Claims

1. A method for producing white arsenic by using high-sulfur high-arsenic tin ore old tailings is characterized by comprising the following steps:

(1) adding water and xanthate, grease collecting agent and sodium alkyl sulfonate regulator to carry out size mixing and medicament pretreatment on old tailings, so as to enlarge the flotation property difference between arsenic minerals and sulfur minerals;

(3) oxidizing and roasting the tin-containing high-arsenic tailings by using a reverberatory furnace to enable arsenic to escape in the form of arsenic trioxide gas, obtaining a white arsenic product by using a settling and cloth bag dust collection mode, and keeping tin in the roasted sand.

2. The method for producing white arsenic from the high-sulfur high-arsenic tin ore old tailings according to claim 1, wherein the calcine is used for recovering tin by a heavy, magnetic and flotation beneficiation method.

3. The method for producing white arsenic from the high-sulfur high-arsenic tin ore old tailings according to claim 1, wherein the pH value of the pretreated ore pulp is 6-8.

4. The method for producing white arsenic from the old tailings of the high-sulfur high-arsenic tin ore as claimed in claim 1, wherein the temperature of the oxidizing roasting is 400-800 ℃.

5. The method for producing white arsenic from the old tailings of the high-sulfur high-arsenic tin ore as claimed in claim 1 or 4, wherein the temperature of the oxidizing roasting is controlled at 450-500 ℃.

6. The method for producing white arsenic from the high-sulfur high-arsenic tin ore old tailings according to claim 1, wherein the settling chamber for collecting arsenic trioxide gas is an eight-stage settling chamber, the white arsenic is collected by supplementing the settled tail gas with a cloth bag, and then the cloth bag tail gas is subjected to desulfurization treatment by adding alkali with a leaching tower and a turbulent ball tower.

7. The method for producing white arsenic from high-sulfur high-arsenic old tin ore tailings according to claim 1, wherein the alkyl carbon atom number of the alkyl sodium sulfonate is 7-20, preferably 12.