CN113862493B - Method for co-processing and utilizing arsenic-containing materials in nonferrous smelting - Google Patents
Method for co-processing and utilizing arsenic-containing materials in nonferrous smelting Download PDFInfo
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- CN113862493B CN113862493B CN202111139255.2A CN202111139255A CN113862493B CN 113862493 B CN113862493 B CN 113862493B CN 202111139255 A CN202111139255 A CN 202111139255A CN 113862493 B CN113862493 B CN 113862493B
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Abstract
The invention provides a method for the synergistic treatment and utilization of nonferrous smelting arsenic-containing materials, wherein arsenic sulfide in arsenic sulfide slag in a low-temperature inner cylinder generates solid metal sulfide and gaseous arsenic trioxide. The smelting smoke dust in the high-temperature inner cylinder or the solid arsenic trioxide in the oxidized metal mineral powder is heated to be in a gaseous state. The low-temperature inner cylinder and the high-temperature inner cylinder are infinitely close to an oxygen-free atmosphere, and carbon powder is input into the high-temperature inner cylinder. The method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material has the advantages that multiple materials are subjected to synergistic treatment, arsenic is removed, sulfur is fixed, valuable metals in reactants are upgraded in a vulcanization mode, and the sulfur in the reactants is reserved, so that the subsequent pyrometallurgy is facilitated; compared with traditional furnace types such as a fluidized bed, a blast furnace, a reverberatory furnace and the like, the flue gas quantity is very little, the sulfur loss is small, and the secondary pollution is low; the method has strong adaptability, can adjust corresponding process parameters and material addition proportions according to different non-ferrous metal smelting products, has good effects, simple process flow and can realize industrial large-scale treatment.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a method for the synergistic treatment and utilization of a nonferrous smelting arsenic-containing material.
Background
In industrial production, the arsenic sulfide slag is stacked together for centralized treatment after being generated. As is the main component of the arsenic sulfide slag2S3The common treatment methods are classified into a pyrogenic method and a wet method. Fire methodMainly adopts a roasting method, and the wet method mainly comprises an alkaline leaching method, a ferric sulfate leaching method, a copper sulfate replacement method and the like. Fire method: low arsenic recovery rate, easy environmental pollution and poor product quality. Alkaline leaching method: the sodium hydroxide consumption is large, and the operation cost is high; and (3) a ferric sulfate leaching method: the process is complex, the material return is more in the process, the impurity content of the product is higher, and the investment is large; copper sulfate replacement method: the arsenic recovery rate is only about 55%.
The smelting smoke dust is generated by products of the dust collection and condensation of volatile elements carried away with smoke gas in the smelting process of non-ferrous metals such As gold, copper, tin, lead, zinc and the like, and the main compounds of the smelting smoke dust comprise CuO, PbO, ZnO and As2O3、Fe2O3And K2O, and the like. The composition difference of smelting smoke dust and phase slag is large, and a uniform treatment method is not available.
Therefore, it is necessary to provide a method for the co-processing and utilization of the arsenic-containing materials in nonferrous smelting to solve the above technical problems.
Disclosure of Invention
The invention provides a method for the synergistic treatment and utilization of a non-ferrous smelting arsenic-containing material, which aims to solve the technical problems that in the prior art, the common treatment of a sulfur-containing arsenic-containing material and an arsenic-containing metal oxide aims at dearsenization, the main process is a pyrogenic process, the loss of sulfur cannot be avoided, the dearsenization effect is poor, the environment pollution is serious, great potential safety hazards exist in industrial production, and secondary resource utilization of treated tailings is not facilitated.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a method for the synergistic treatment and utilization of nonferrous smelting arsenic-containing materials, which is used for performing arsenic removal and sulfur fixation treatment on arsenic sulfide slag containing arsenic sulfide and performing arsenic removal treatment on smelting smoke dust or oxidized metal mineral powder, and is characterized by comprising the following steps of:
step A, inputting the arsenic sulfide slag and the smelting smoke dust or the oxidized metal mineral powder into a raw material mixer for mixing, and outputting a pyrolysis raw material, wherein the smelting smoke dust is generated by taking volatile elements along with flue gas in the non-ferrous metal smelting process and collecting dust and condensing the volatile elements, and the oxidized metal mineral powder is a raw ore mining material or an intermediate product in an ore dressing process;
step B, conveying the pyrolysis raw material output by the step A to a low-temperature pyrolysis furnace;
step C, continuously inputting inert gas for forming an oxygen-free atmosphere into the low-temperature pyrolysis furnace in the step B;
d, heating and pyrolyzing the low-temperature pyrolysis furnace in the step B according to a first set temperature, and preserving heat according to a first set time length to enable sulfur in the arsenic sulfide to form a solid metal sulfide and arsenic in the arsenic sulfide to form gaseous arsenic trioxide, and respectively outputting a pyrolysis material containing the metal sulfide and a low-temperature pyrolysis gas containing the arsenic trioxide;
e, inputting carbon powder for decomposing arsenate and the pyrolysis material output in the step D into a high-temperature pyrolysis furnace;
step F, continuously inputting inert gas for forming an oxygen-free atmosphere into the high-temperature pyrolysis furnace in the step E; and the number of the first and second groups,
and G, carrying out heating pyrolysis on the high-temperature pyrolysis furnace in the step E according to a second set temperature, and carrying out heat preservation according to a second set time length to change the solid arsenic trioxide in the smelting smoke dust or the oxidized metal mineral powder into a gaseous state, decompose arsenate, and output pyrolysis tailings containing metal sulfide and high-temperature pyrolysis gas containing arsenic trioxide.
In the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material, in the step D, the first set temperature is set to be 200-400 ℃, and the first set time is set to be 60-180 min.
In the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material, in the step G, the second set temperature is set to be 500-700 ℃, and the second set time is set to be 60-180 min.
In the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material, the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material also comprises a step H before the step A, wherein the arsenic sulfide slag is input into a crusher, crushed into particles with the particle size of 1mm-30mm and output.
In the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material, the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material further comprises the following steps: and step I, inputting the low-temperature pyrolysis gas output in the step D and the high-temperature pyrolysis gas output in the step G into a high-temperature gas-solid separation tower, keeping the arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas in a gas state, filtering dust in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas to form a filtered pyrolysis gas, inputting the filtered pyrolysis gas into a condensation arsenic collecting device, condensing the condensed pyrolysis gas to collect arsenic, and outputting refined white arsenic.
In the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material, the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material further comprises a step J, the low-temperature pyrolysis gas output in the step D and the high-temperature pyrolysis gas output in the step G are input into a high-temperature gas-solid separation tower, so that arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas is kept in a gaseous state, the low-temperature pyrolysis gas and dust in the high-temperature pyrolysis gas are filtered to form a filtered pyrolysis gas, and the filtered pyrolysis gas is input into a reduction tower to be subjected to carbon reduction, so that metal arsenic is output.
In the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material, the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material further comprises a step K of inputting the low-temperature pyrolysis gas output in the step D and the high-temperature pyrolysis gas output in the step G into a high-temperature gas-solid separation tower, so that arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas is kept in a gaseous state, dust in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas is filtered out, then a part of the filtered low-temperature pyrolysis gas and the filtered high-temperature pyrolysis gas are input into a condensation arsenic-collecting device, and are condensed to collect arsenic, refined white arsenic is output, and the other part of the filtered low-temperature pyrolysis gas and the filtered high-temperature pyrolysis gas are input into a reduction tower, and are subjected to carbon reduction, and metal arsenic is output.
In the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material, the pyrolysis raw material in the low-temperature pyrolysis furnace is heated and pyrolyzed through external smoke in the step D, the pyrolysis material in the high-temperature pyrolysis furnace is heated and pyrolyzed through the external smoke in the step G, the low-temperature pyrolysis gas and the high-temperature pyrolysis gas in the high-temperature gas-solid separation tower are subjected to high-temperature filtration through the external smoke in the step K, and the external smoke used in the step D is set as the mixed gas of the external smoke used in the step G and the external smoke used in the step K.
Compared with the prior art, the invention has the beneficial effects that: according to the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material, nitrogen is continuously input into the low-temperature inner cylinder, so that the low-temperature inner cylinder is infinitely close to an oxygen-free atmosphere, the generation of sulfur dioxide by the reaction of arsenic sulfide in arsenic sulfide slag and oxygen is favorably inhibited, the environment is prevented from being polluted, and the treatment cost is increased. Arsenic sulfide in the arsenic sulfide slag reacts with the smelting smoke dust or the oxidized metal in the oxidized metal mineral powder to generate solid metal sulfide and gaseous arsenic trioxide. And nitrogen is continuously input into the high-temperature inner cylinder, so that the high-temperature inner cylinder is infinitely close to an oxygen-free atmosphere, and arsenic trioxide can be effectively prevented from reacting with oxidized metal and oxygen to generate arsenate. Carbon powder is input into the high-temperature inner cylinder, possible arsenate can be decomposed, and complete arsenic removal is effectively guaranteed. The method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material has the advantages that multiple materials are subjected to synergistic treatment, arsenic is removed, sulfur is fixed, valuable metals in reactants are upgraded in a vulcanization mode, and the sulfur in the reactants is reserved, so that the subsequent pyrometallurgy is facilitated; compared with traditional furnace types such as a fluidized bed, a blast furnace, a reverberatory furnace and the like, the flue gas quantity is very little, the sulfur loss is small, and the secondary pollution is low; the method has strong adaptability, can adjust corresponding process parameters and material addition proportions according to different non-ferrous metal smelting products, has good effects, has simple process flow, and can be used for industrial large-scale treatment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments are briefly introduced below, and the drawings in the following description are only corresponding to some embodiments of the present invention.
FIG. 1 is a block diagram of the structure of the equipment for the co-processing and utilization of the nonferrous smelting arsenic-containing materials of the present invention.
FIG. 2 is a partial flow chart of the method for the co-processing and utilization of the nonferrous smelting arsenic-containing materials of the invention.
FIG. 3 is another partial flow chart of the method for the co-processing and utilization of the nonferrous smelting arsenic-containing materials of the invention.
Wherein the content of the first and second substances,
the labels of FIG. 1 are as follows:
11. a low-temperature sulfur-fixing device, a high-temperature sulfur-fixing device,
111. a crusher, 112, a raw material mixer, 113, a raw material feeding mechanism, 114, a low-temperature pyrolysis furnace, 115 and a nitrogen maker,
12. a high-temperature pyrolysis device is arranged on the device,
121. a pyrolysis material feeding mechanism 122, a high-temperature pyrolysis furnace 123, a pyrolysis material discharging mechanism 124 and an additive feeding mechanism,
13. the arsenic collecting device is arranged on the upper portion of the device,
131. a high-temperature gas-solid separation tower 132, a condensation arsenic-collecting device 133 and a reduction tower,
14. a heat supply device is arranged on the base plate,
141. a flue gas main pipe 142 and a combustion mechanism.
15. An exhaust gas purification system.
In the drawings, elements having similar structures are denoted by the same reference numerals.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the present invention, directional terms such as "up", "down", "front", "back", "left", "right", "inner", "outer", "side", "top" and "bottom" are used only with reference to the orientation of the drawings, and the directional terms are used for illustration and understanding of the present invention, and are not intended to limit the present invention.
The terms "first," "second," and the like in the terms of the invention are used for descriptive purposes only and not for purposes of indication or implication relative importance, nor as a limitation on the order of precedence.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The common treatment of the sulfur-containing and arsenic-containing materials and the arsenic-containing metal oxides in the prior art aims at dearsenization, and the main process is a pyrogenic process, so that the loss of sulfur cannot be avoided, the dearsenization effect is poor, and the environment is seriously polluted. The method has great potential safety hazard during industrial production, and is not beneficial to secondary resource utilization of the treated tailings.
The following is a preferred embodiment of the equipment for co-processing and utilizing the nonferrous smelting arsenic-containing material and the method for co-processing and utilizing the nonferrous smelting arsenic-containing material, which can solve the technical problems.
Referring to fig. 1, the present invention provides a co-processing and utilizing apparatus for non-ferrous smelting arsenic-containing material to perform arsenic-removing and sulfur-fixing operation, wherein the co-processing and utilizing apparatus for non-ferrous smelting arsenic-containing material comprises a low temperature sulfur-fixing device 11, a high temperature pyrolysis device 12, an arsenic-collecting device 13, a heat supply device 14 and a tail gas purification system 15.
The low-temperature sulfur fixation device 11 comprises a crusher 111, a raw material mixer 112, a raw material feeding mechanism 113, a low-temperature pyrolysis furnace 114 and a nitrogen gas making machine 115.
The crusher 111 is used for crushing the arsenic sulfide slag into particles with the particle size of 1mm-30 mm. The raw material mixer 112 is connected with the crusher 111 and is used for mixing the arsenic sulfide slag with smelting smoke dust or oxidized metal mineral powder. The raw material feeding mechanism 113 is connected to the raw material mixer 112, and is configured to receive and convey the pyrolysis raw material output by the raw material mixer 112.
The low-temperature pyrolysis furnace 114 includes a low-temperature inner cylinder, a low-temperature jacket, and a low-temperature agitation mechanism. The low-temperature inner cylinder is used for accommodating pyrolysis raw materials output by the raw material feeding mechanism 113, and is provided with a low-temperature pyrolysis feeding hole, a low-temperature pyrolysis discharging hole and a low-temperature pyrolysis gas outlet. The low-temperature pyrolysis feed inlet is connected with the raw material feeding mechanism 113 and used for receiving pyrolysis raw materials output by the raw material feeding mechanism 113, the low-temperature pyrolysis discharge outlet is used for outputting pyrolysis materials containing metal sulfides, and the low-temperature pyrolysis gas outlet is used for outputting low-temperature pyrolysis gas containing arsenic trioxide. The low-temperature jacket is wrapped outside the low-temperature inner cylinder and used for heating and pyrolyzing pyrolysis raw materials in the low-temperature inner cylinder through inputting external flue gas. The low-temperature stirring mechanism is arranged in the low-temperature inner cylinder and used for stirring pyrolysis raw materials in the low-temperature inner cylinder.
The nitrogen making machine 115 is connected with the raw material feeding mechanism 113 and the low-temperature inner cylinder, and is used for inputting nitrogen into the raw material feeding mechanism 113 and the low-temperature inner cylinder to form an oxygen-free atmosphere.
The pyrolysis device 12 includes a pyrolysis material feeding mechanism 121, a pyrolysis furnace 122, an additive feeding mechanism 124, and a pyrolysis material discharging mechanism 123.
The inside of pyrolysis material feed mechanism 121 is provided with helical structure, and pyrolysis material feed mechanism 121 is connected with the low temperature pyrolysis discharge gate for carry the pyrolysis material of low temperature pyrolysis discharge gate output. The pyrolysis material feeding mechanism 121 is also connected to the nitrogen maker 115 for feeding nitrogen gas into the pyrolysis material feeding mechanism 121 to form an oxygen-free atmosphere.
The high-temperature pyrolysis furnace 122 includes a high-temperature inner cylinder, a high-temperature jacket, and a high-temperature agitation mechanism. The high-temperature inner cylinder is used for accommodating pyrolysis materials output by the pyrolysis material feeding mechanism 121, and is connected with the nitrogen making machine 115 and used for inputting nitrogen into the high-temperature inner cylinder to form an oxygen-free atmosphere. The high-temperature inner cylinder comprises a high-temperature pyrolysis feed inlet, a high-temperature pyrolysis discharge port and a high-temperature pyrolysis gas outlet, the high-temperature pyrolysis feed inlet is connected with the pyrolysis material feeding mechanism 121 and used for inputting pyrolysis materials output by the pyrolysis material feeding mechanism 121, the high-temperature pyrolysis discharge port is used for outputting pyrolysis tailings containing metal sulfides, and the high-temperature pyrolysis gas outlet is used for outputting high-temperature pyrolysis gas containing arsenic trioxide. The high-temperature jacket is wrapped outside the high-temperature inner cylinder and used for heating and pyrolyzing pyrolysis raw materials in the high-temperature inner cylinder through inputting external flue gas. The high-temperature stirring mechanism is arranged in the high-temperature inner barrel and is used for stirring pyrolysis materials in the high-temperature inner barrel.
And the additive feeding mechanism 124 is internally provided with a spiral structure, and the additive feeding mechanism 124 is connected with the high-temperature inner cylinder and is used for inputting carbon powder into the high-temperature inner cylinder so as to decompose arsenate in the high-temperature inner cylinder. The additive feed mechanism 124 is also connected to the nitrogen maker 115 for feeding nitrogen into the additive feed mechanism 124 to create an oxygen-free atmosphere.
The inside of pyrolysis material discharge mechanism 123 is provided with helical structure, and pyrolysis material discharge mechanism 123 is connected with the high temperature pyrolysis discharge gate for the pyrolysis tailings that output contains the metal sulphide.
Wherein, the arsenic collecting device 13 comprises a high-temperature gas-solid separation tower 131, a condensation arsenic collecting device 132 and a reduction tower 133.
The high-temperature gas-solid separation tower 131 is used for filtering the low-temperature pyrolysis gas output from the low-temperature pyrolysis gas outlet and the high-temperature pyrolysis gas output from the high-temperature pyrolysis gas outlet to obtain filtered pyrolysis gas. The high-temperature gas-solid separation tower 131 comprises a separation tower inner furnace and a separation tower jacket, the separation tower inner furnace comprises a separation tower gas inlet and a separation tower gas outlet, the separation tower gas inlet is connected with a low-temperature pyrolysis gas outlet and a high-temperature pyrolysis gas outlet, the separation tower gas inlet is used for inputting low-temperature pyrolysis gas and high-temperature pyrolysis gas, and the separation tower gas outlet is used for outputting filtered pyrolysis gas. The separation tower inner furnace is divided into an upper filtering cavity and a lower ash discharging cavity, the ash discharging cavity is conical, and an ash discharging opening is formed in the bottom of the ash discharging cavity. The separation tower inner furnace also comprises a supporting plate, a plurality of filtering membrane pipes and a back flushing pipe, wherein the supporting plate is fixed in the filtering cavity along the radial direction of the filtering cavity. The support plate divides the filtering cavity into two parts, the part far away from the ash discharging cavity is an upper cavity, the part close to the ash discharging cavity is a lower cavity, and the capacity of the upper cavity is smaller than that of the lower cavity. The gas inlet and the gas outlet of the separation tower are respectively positioned at two opposite sides of the lower cavity, and the gas outlet of the separation tower is higher than the gas inlet of the separation tower. The plurality of filtering membrane tubes are fixed in the filtering cavity along the axial direction of the filtering cavity, and the filtering membrane tubes are fixed on the supporting plate in a penetrating way. One end of the blowback pipe is located outside the high-temperature gas-solid separation tower 131, the other end is located the cavity, the one end that the blowback pipe is located the cavity is provided with a plurality of blowbacks, a plurality of blowbacks correspond the intercommunication with many filtration membrane pipes respectively, the blowback pipe is used for making the intraductal dust of filtration membrane to discharge from the ash discharge mouth. The separating tower jacket is wrapped on the periphery of the separating tower inner furnace, the separating tower jacket is used for inputting high-temperature flue gas to heat low-temperature pyrolysis gas and high-temperature pyrolysis gas in the separating tower inner furnace, and an outlet of the separating tower jacket and an outlet of the high-temperature jacket are both connected with an inlet of the low-temperature inner cylinder.
The condensation arsenic collecting device 132 is connected with a gas outlet of the separation tower and is used for condensing the filtered pyrolysis gas to collect arsenic to obtain refined white arsenic.
The reduction tower 133 is connected with the gas outlet of the separation tower and is used for carrying out carbon reduction on the filtered pyrolysis gas to obtain metal arsenic.
Wherein, tail gas clean system 15 sets up to the caustic wash tower, and tail gas clean system 15 and condensation receive arsenic device 132 and reduction tower 133 all to be connected for carry out innocent treatment with condensation receipts arsenic device 132 and the pyrolysis tail gas that reduction tower 133 discharged through sodium hydroxide solution.
Wherein, the heating device 14 comprises a flue gas main pipe 141 and a combustion mechanism 142. The flue gas main pipe 141 is used for conveying high-temperature flue gas, and an outlet of the flue gas main pipe 141 is connected with an inlet of the high-temperature jacket and an inlet of the separation tower jacket. The combustion mechanism 142 is used for generating high-temperature flue gas, and the combustion mechanism 142 is connected with the inlet of the flue gas main pipe 141.
The nonferrous smelting arsenic-containing material co-processing and utilizing equipment can mix and co-process various arsenic-containing materials, reduces the environmental pollution and simultaneously realizes the secondary utilization of resources.
Referring to fig. 2 and fig. 3, the invention further provides a method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing materials, which is used for performing arsenic removal and sulfur fixation treatment on arsenic sulfide slag containing arsenic sulfide, wherein the solid content of the arsenic sulfide slag contains 25-50% of As and 20-40% of S according to the mass percentage, and is used for performing arsenic removal treatment on smelting smoke dust or oxidized metal mineral powder. Wherein, the smelting smoke dust is the smoke dust generated by the product of the non-ferrous metal smelting process in which volatile elements are taken away with the smoke gas and are subjected to dust collection and condensation, and the solid components in the smelting smoke dust contain, by mass, 2-30% of CuO, 2-30% of PbO, 2-30% of ZnO and 2-30% of As2O310 to 30%. The oxidized metal ore powder is a raw ore mining material or an intermediate product in an ore dressing process link, and the solid components of the oxidized lead ore powder comprise 30-50% of PbO and 30-50% of As in percentage by mass2O31-15 percent of CuO, 15-30 percent of As and the solid components of the copper oxide ore powder according to mass percent2O3Is 1-15%. The method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material uses the synergistic treatment and utilization equipment of the nonferrous smelting arsenic-containing material to carry out arsenic removal and sulfur fixation operation. The method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material comprises the following steps.
Step A, inputting the arsenic sulfide slag into a crusher 111, crushing the arsenic sulfide slag into particles with the particle size of 1mm-30mm, and outputting the particles.
And step B, inputting the arsenic sulfide slag output in the step A and smelting smoke dust or oxidized metal mineral powder into a raw material mixer 112 for mixing, and outputting pyrolysis raw materials.
And step C, conveying the pyrolysis raw material output in the step B to a preheated low-temperature inner cylinder through a raw material feeding mechanism 113, and continuously feeding nitrogen for forming an oxygen-free atmosphere into the raw material feeding mechanism 113 through a nitrogen manufacturing machine 115.
Step D, nitrogen gas for forming an oxygen-free atmosphere is continuously supplied into the low temperature inner tube in step C through the nitrogen gas producing machine 115.
And E, stirring the pyrolysis raw materials in the low-temperature inner cylinder in the step C through a low-temperature stirring mechanism, heating and pyrolyzing the pyrolysis raw materials through external smoke in a low-temperature jacket according to a first set temperature, and preserving heat for a first set time, wherein the first set temperature is 200-400 ℃, and the first set time is 60-180 min, so that sulfur in arsenic sulfide forms solid metal sulfide, arsenic in arsenic sulfide forms gaseous arsenic trioxide, and a pyrolysis material containing the metal sulfide and a low-temperature pyrolysis gas containing the arsenic trioxide are respectively output.
And step F, inputting carbon powder for decomposing arsenate into the preheated high-temperature inner barrel through the additive feeding mechanism 124, inputting the pyrolysis material output in the step E into the high-temperature inner barrel through the pyrolysis material feeding mechanism 121, and continuously inputting nitrogen for forming an oxygen-free atmosphere into the additive feeding mechanism 124 and the pyrolysis material feeding mechanism 121 through the nitrogen manufacturing machine 115.
Step G, nitrogen gas for forming an oxygen-free atmosphere is continuously supplied into the high-temperature inner tube in step F by the nitrogen gas making machine 115.
And step H, stirring the pyrolysis material in the high-temperature inner cylinder in the step F through a high-temperature stirring mechanism, carrying out heating pyrolysis on the pyrolysis material through external smoke in a high-temperature jacket according to a second set temperature, and carrying out heat preservation according to a second set time length, wherein the second set temperature is set to be 500-700 ℃, and the second set time length is set to be 60-180 min, so that solid arsenic trioxide in smelting smoke dust or oxidized metal ore powder is changed into a gaseous state, arsenate which may be generated or arsenate which may exist in the pyrolysis material is decomposed, and pyrolysis tailings containing metal sulfide and high-temperature pyrolysis gas containing arsenic trioxide are output through a pyrolysis material discharging mechanism 123.
And step I, inputting the low-temperature pyrolysis gas output in the step E and the high-temperature pyrolysis gas output in the step H into a separation tower inner furnace, performing high-temperature filtration on the low-temperature pyrolysis gas and the high-temperature pyrolysis gas through external flue gas in a separation tower jacket to keep arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas in a gaseous state, filtering dust in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas to form filtered pyrolysis gas, inputting the filtered pyrolysis gas into a condensation arsenic collecting device 132, performing condensation and arsenic collection on the filtered pyrolysis gas, and respectively outputting refined white arsenic and pyrolysis tail gas, and/or inputting part of the filtered pyrolysis gas into a reduction tower 133, performing carbon reduction on the filtered pyrolysis gas, and respectively outputting metal arsenic and pyrolysis tail gas.
And step J, mixing the external flue gas output by the high-temperature jacket in the step H with the external flue gas output by the jacket of the separation tower in the step I, and inputting the mixture into the low-temperature jacket in the step E.
And K, performing harmless treatment on the pyrolysis tail gas output in the step I through a tail gas purification system 15, and discharging the pyrolysis tail gas up to the standard.
In the method in the step A, the arsenic sulfide slag is input into the crusher 111 and crushed into particles with the particle size of 1mm-30mm, so that the arsenic sulfide slag and the smelting smoke dust or the oxidized metal mineral powder in the subsequent step can be fully reacted, and the pyrolysis quality and efficiency are improved.
In the method in the step B, the arsenic sulfide slag output in the step A and the smelting smoke dust or the oxidized metal mineral powder are input into the raw material mixer 112 to be mixed, so that the subsequent steps can be favorably performed to fully pyrolyze the arsenic sulfide slag, and the pyrolysis quality and efficiency are improved.
In the methods in the step C, the step D and the step E, nitrogen is continuously input into the raw material feeding mechanism 113 and the low-temperature inner cylinder, so that the low-temperature inner cylinder is infinitely close to an oxygen-free atmosphere, the reaction of arsenic sulfide in arsenic sulfide slag and oxygen is favorably inhibited to generate sulfur dioxide, the sulfur can be fixed, the environment pollution can be prevented, and the treatment cost is increased.
In the method of step E, arsenic sulfide in the arsenic sulfide slag reacts with the smelting smoke dust or the oxidized metal in the oxidized metal mineral powder to generate solid metal sulfide and gaseous arsenic trioxide. The reaction chemical formula is 3CuO + As2S3＝As2O3(g)+3CuS，3PbO+As2S3＝As2O3(g) The +3PbS can not only retain the sulfur in the arsenic sulfide in the form of solid metal sulfide, but also form the arsenic in the arsenic sulfide into gaseous arsenic trioxide, thereby leading the arsenic sulfide slag to remove arsenic and fix sulfur. To be explainedThe chemical reaction formula of arsenic sulfide and partially oxidized metal is only listed above, and the reactions of arsenic sulfide and other oxidized metal have the same effect, and are not listed here.
In the method of the step E, the first set temperature is set to be 200-400 ℃, so that the pyrolysis quality and efficiency can be improved, and the energy can be saved. Experimental data prove that when the first set temperature is lower than 200 ℃, the reaction between the arsenic sulfide in the arsenic sulfide slag and the oxidized metal in the smelting smoke dust or the oxidized metal mineral powder is insufficient. When the first set temperature is higher than 400 ℃, the energy consumption is larger.
In the method of the step E, when the first set temperature is set to be 200-300 ℃, the first set time is set to be 120-180 min, and the method can effectively save energy. When the first set temperature is set to be 300-400 ℃, and the first set time is set to be 60-120 min, the method can effectively save pyrolysis time.
In the pyrolysis process of the step E and the step H, arsenic trioxide and oxidized metal may react to form arsenate, and the chemical reaction formula is As2O3+3CuO+O2(g)＝Cu3(AsO4)2，As2O3+3PbO+O2(g)＝Pb3(AsO4)2，1.667As2O3(g)+3CuO＝Cu3(AsO4)2+1.333As，1.667As2O3(g)+3PbO＝Pb3(AsO4)2+1.333 As. In the method of the above step F, step G and step H, nitrogen is continuously input into the additive feeding mechanism 124, the pyrolysis material feeding mechanism 121 and the high-temperature inner cylinder, so that the high-temperature inner cylinder is infinitely close to an oxygen-free atmosphere, and the oxygen-free atmosphere can effectively prevent arsenic trioxide from reacting with the oxidized metal and oxygen to generate arsenate compared with an aerobic atmosphere. Meanwhile, arsenate possibly exists in the pyrolysis raw material, and the carbon powder is input into the high-temperature inner barrel, so that the arsenate can be decomposed, and the complete arsenic removal is effectively ensured. The chemical reaction formula is 2Cu3(AsO4)2+8C＝As4(g)+6Cu+8CO2(g)，2Pb3(AsO4)2+8C＝As4(g)+6Pb+8CO2(g) In that respect It should be noted that, the above mentioned only illustrates the chemical reaction formula of arsenic trioxide and partially oxidized metal, and also only illustrates the chemical reaction formula of partial arsenate and carbon, and the chemical reactions of arsenic trioxide and other oxidized metal, and other arsenate and carbon have the same effect, and are not listed here.
In the method in the step H, experiments prove that if the second set temperature is lower than 500 ℃, sublimation of solid arsenic trioxide in the smelting smoke or oxidized metal ore powder into a gaseous state is not facilitated, and if the second set temperature exceeds 750 ℃, the arsenic trioxide reacts with carbon to generate arsenic, and at the moment, the arsenic is mixed with pyrolysis tailings, so that the difficulty in recovering the arsenic is increased, and the arsenic collection efficiency is reduced. And in the step H, the second set temperature is set to be 500-700 ℃, so that the pyrolysis quality and efficiency can be improved, arsenic cannot be generated, the arsenic can be intensively conveyed and treated in the form of gaseous arsenic trioxide, the arsenic collection efficiency is improved, and the arsenic collection difficulty is reduced.
In the method of the step H, the second set temperature is set to be 500-600 ℃, the second set time is set to be 120-180 min, and the method can effectively save energy. The second set temperature is set to be 600-700 ℃, the second set time is set to be 60-120 min, and the method can effectively save pyrolysis time.
In the pyrolysis process of the step E and the step H, the stirring is carried out through the low-temperature stirring mechanism and the high-temperature stirring mechanism, so that the pyrolysis is more sufficient, and the pyrolysis effect and the pyrolysis quality are improved.
In the method of the step I, the refined white arsenic can be obtained through condensation, the metal arsenic can be obtained through carbon reduction, and waste gas is effectively utilized. Wherein the chemical reaction formula for carbon reduction is 2As2O3+3C＝4As+3CO2. Before condensation and carbon reduction, a high-temperature filtering method is adopted, so that the arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas is kept in a gaseous state, and dust in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas is filtered to form filtered pyrolysis gas. Not only can effectively improve the precision of the subsequent white arsenic and metal arsenic, but alsoCan prevent gaseous arsenic trioxide from condensing to form glass arsenic to block the pipeline.
In the method of the step J, the external flue gas output by the separation tower jacket and the high-temperature jacket is input into the low-temperature jacket as a heat source, so that the repeated utilization of heat energy is realized.
When copper oxide is contained in the smelting dust or oxidized metal ore powder, a small amount of copper sulfide is decomposed into cuprous sulfide and elemental sulfur under the high temperature condition in step H, and thus a small amount of sulfur is lost in a gaseous state. In the step B, the smelting smoke dust or the oxidized metal mineral powder is set to be the metal mineral powder only containing lead oxide, so that in the step H, the loss caused by the generation of elemental sulfur can be avoided, and the recovery rate of sulfur is further improved.
The following are examples of the equipment for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material and the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material.
Example 1
A method for the synergistic treatment and utilization of nonferrous smelting arsenic-containing materials is provided, wherein arsenic sulfide slag and smelting smoke dust come from a certain smelting company in Yunnan, wherein the arsenic sulfide slag contains 25% of S and 38% of As by mass percent.
Putting the raw materials into a preheated low-temperature pyrolysis furnace 114 through a closed raw material feeding mechanism, heating to 400 ℃, preserving heat for 90min, simultaneously introducing nitrogen into the low-temperature pyrolysis furnace 114, leaving sulfur in the materials in the form of metal sulfides, and introducing arsenic into a high-temperature gas-solid separation tower 131 in the form of gaseous arsenic trioxide;
directly feeding the sulfur-fixed material into a preheated externally heated high-temperature pyrolysis furnace 122, heating to 600 ℃, preserving heat for 90min, heating the original solid arsenic trioxide in the material, feeding the heated solid arsenic trioxide into a high-temperature gas-solid separation tower 131 in a gaseous state, introducing nitrogen and adding carbon powder into the high-temperature pyrolysis furnace 122, so that the generation of arsenate is reduced, and the escape of the gaseous arsenic trioxide is increased;
directly stacking the obtained pyrolysis tailings;
the clean arsenic-containing gas from the high-temperature gas-solid separation tower 131 enters a condensation arsenic-collecting device 132 to prepare refined white arsenic;
and (3) introducing pyrolysis tail gas discharged by the condensation arsenic-collecting device 132 into a sodium hydroxide solution, and performing harmless treatment on the obtained waste liquid to achieve the standard and discharge.
Example 2
A method for the synergistic treatment and utilization of nonferrous smelting arsenic-containing materials is provided, wherein arsenic sulfide slag and smelting smoke dust come from a certain smelting company in Yunnan, wherein the arsenic sulfide slag contains 20% of S and 33% of As by mass percent.
Putting the raw materials into a preheated low-temperature pyrolysis furnace 114 through a closed raw material feeding mechanism, heating to 300 ℃, preserving heat for 60min, simultaneously introducing nitrogen into the low-temperature pyrolysis furnace 114, leaving sulfur in the materials in the form of metal sulfides in the materials, and introducing arsenic in the form of gaseous arsenic trioxide into a high-temperature gas-solid separation tower 131;
directly feeding the material after sulfur fixation into a preheated external heating type high-temperature pyrolysis furnace 122, heating to 700 ℃, preserving heat for 60min, heating the original solid arsenic trioxide in the material, then feeding the heated solid arsenic trioxide into a high-temperature gas-solid separation tower 131 in a gaseous state, introducing nitrogen and adding carbon powder into the furnace, which is favorable for reducing the generation of arsenate, and simultaneously increasing the escape of the gaseous arsenic trioxide;
directly stacking the obtained thermal decomposition material;
the clean arsenic-containing gas from the high-temperature gas-solid separation tower 131 enters a reduction tower 133 to prepare metal arsenic;
and introducing pyrolysis tail gas discharged from the reduction tower 133 into a sodium hydroxide solution, and performing harmless treatment on the obtained waste liquid to achieve the standard and discharge.
The method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material has the advantages that multiple materials are subjected to synergistic treatment, arsenic is removed, sulfur is fixed, valuable metals in reactants are upgraded in a vulcanization mode, and the sulfur in the reactants is reserved, so that the subsequent pyrometallurgy is facilitated; compared with traditional furnace types such as a fluidized bed, a blast furnace, a reverberatory furnace and the like, the flue gas quantity is very little, the sulfur loss is small, and the secondary pollution is low; the method has strong adaptability, can adjust corresponding process parameters and material addition proportions according to different non-ferrous metal smelting products, has good effects, has simple process flow, and can be used for industrial large-scale treatment.
In summary, although the present invention has been described with reference to the preferred embodiments, the above-described preferred embodiments are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore, the scope of the present invention shall be determined by the appended claims.
Claims (10)
1. A method for synergistic treatment and utilization of arsenic-containing materials in nonferrous smelting is used for arsenic-removing and sulfur-fixing treatment of arsenic sulfide slag containing arsenic sulfide, wherein the solid content of the arsenic sulfide slag contains 25-50% of As and 20-40% of S by mass percent, and the arsenic-removing treatment is used for dearsenifying smelting smoke dust or oxidized metal mineral powder, wherein the smelting smoke dust is generated by products obtained by carrying volatile elements along with smoke gas in the nonferrous smelting process and condensing the volatile elements through dust collection, the solid content of the smelting smoke dust contains 2-30% of CuO, 2-30% of PbO, 2-30% of ZnO and 2-30% of As by mass percent2O310-30%, wherein the oxidized metal mineral powder is a raw ore mining material or an intermediate product in an ore dressing process, the oxidized metal mineral powder is lead oxide mineral powder or copper oxide mineral powder, and the solid components of the lead oxide mineral powder comprise 30-50% of PbO and 30-50% of As by mass2O31-15 percent of CuO, 15-30 percent of As and the solid components of the copper oxide ore powder according to mass percent2O31-15%, and is characterized in that nonferrous smelting arsenic-containing material cooperative treatment and utilization equipment is used for arsenic removal and sulfur fixation operation, wherein the nonferrous smelting arsenic-containing material cooperative treatment and utilization equipment comprises a low-temperature sulfur fixation device, a high-temperature pyrolysis device, an arsenic collection device, a heat supply device and a tail gas purification system;
wherein, the low temperature solid sulphur device includes:
the crusher is used for crushing the arsenic sulfide slag into particles with the particle size of 1mm-30 mm;
the raw material mixer is connected with the crusher and is used for mixing the arsenic sulfide slag with the smelting smoke dust or the oxidized metal mineral powder;
the raw material feeding mechanism is connected with the raw material mixing machine and is used for receiving and conveying the pyrolysis raw materials output by the raw material mixing machine;
the low-temperature pyrolysis furnace comprises a low-temperature inner cylinder, a low-temperature jacket and a low-temperature stirring mechanism, wherein the low-temperature inner cylinder is used for accommodating pyrolysis raw materials output by the raw material feeding mechanism, the low-temperature inner cylinder is provided with a low-temperature pyrolysis feed inlet, a low-temperature pyrolysis discharge outlet and a low-temperature pyrolysis gas outlet, the low-temperature pyrolysis feed inlet is connected with the raw material feeding mechanism and is used for receiving the pyrolysis raw materials output by the raw material feeding mechanism, the low-temperature pyrolysis discharge outlet is used for outputting pyrolysis materials containing metal sulfides, and the low-temperature pyrolysis gas outlet is used for outputting low-temperature pyrolysis gas containing arsenic trioxide; the low-temperature jacket is wrapped outside the low-temperature inner cylinder and used for heating and pyrolyzing pyrolysis raw materials in the low-temperature inner cylinder through inputting external flue gas; the low-temperature stirring mechanism is arranged in the low-temperature inner cylinder and is used for stirring pyrolysis raw materials in the low-temperature inner cylinder; and the number of the first and second groups,
the nitrogen making machine is connected with the raw material feeding mechanism and the low-temperature inner cylinder and is used for inputting nitrogen into the raw material feeding mechanism and the low-temperature inner cylinder to form an oxygen-free atmosphere;
wherein, the high-temperature pyrolysis device includes:
the pyrolysis material feeding mechanism is internally provided with a spiral structure, is connected with the low-temperature pyrolysis discharge port and is used for conveying pyrolysis materials output by the low-temperature pyrolysis discharge port; the pyrolysis material feeding mechanism is also connected with the nitrogen making machine and used for inputting nitrogen into the pyrolysis material feeding mechanism to form an oxygen-free atmosphere;
the high-temperature pyrolysis furnace comprises a high-temperature inner cylinder, a high-temperature jacket and a high-temperature stirring mechanism; the high-temperature inner cylinder is used for containing pyrolysis materials output by the pyrolysis material feeding mechanism, the high-temperature inner cylinder is connected with the nitrogen making machine and used for inputting nitrogen into the high-temperature inner cylinder to form an oxygen-free atmosphere, the high-temperature inner cylinder comprises a high-temperature pyrolysis feed port, a high-temperature pyrolysis discharge port and a high-temperature pyrolysis gas outlet, the high-temperature pyrolysis feed port is connected with the pyrolysis material feeding mechanism and used for inputting the pyrolysis materials output by the pyrolysis material feeding mechanism, the high-temperature pyrolysis discharge port is used for outputting pyrolysis tailings containing metal sulfides, and the high-temperature pyrolysis gas outlet is used for outputting high-temperature pyrolysis gas containing arsenic trioxide; the high-temperature jacket is wrapped outside the high-temperature inner cylinder and used for heating and pyrolyzing pyrolysis raw materials in the high-temperature inner cylinder through inputting external flue gas; the high-temperature stirring mechanism is arranged in the high-temperature inner barrel and is used for stirring pyrolysis materials in the high-temperature inner barrel;
the additive feeding mechanism is internally provided with a spiral structure and is connected with the high-temperature inner cylinder and used for inputting carbon powder into the high-temperature inner cylinder so as to decompose arsenate in the high-temperature inner cylinder; the additive feeding mechanism is also connected with the nitrogen making machine and used for inputting nitrogen into the additive feeding mechanism to form an oxygen-free atmosphere; and the number of the first and second groups,
the interior of the pyrolysis material discharging mechanism is provided with a spiral structure, and the pyrolysis material discharging mechanism is connected with the high-temperature pyrolysis discharging port and used for outputting pyrolysis tailings containing metal sulfides;
wherein, receive arsenic device includes:
the high-temperature gas-solid separation tower is used for filtering the low-temperature pyrolysis gas output by the low-temperature pyrolysis gas outlet and the high-temperature pyrolysis gas output by the high-temperature pyrolysis gas outlet to obtain filtered pyrolysis gas; the high-temperature gas-solid separation tower comprises a separation tower inner furnace and a separation tower jacket, the separation tower inner furnace comprises a separation tower gas inlet and a separation tower gas outlet, the separation tower gas inlet is connected with the low-temperature pyrolysis gas outlet and the high-temperature pyrolysis gas outlet, the separation tower gas inlet is used for inputting low-temperature pyrolysis gas and high-temperature pyrolysis gas, and the separation tower gas outlet is used for outputting filtered pyrolysis gas; the separation tower inner furnace is divided into an upper filtering cavity and a lower ash discharging cavity, the ash discharging cavity is conical, and an ash discharging port is formed in the bottom of the ash discharging cavity; the separation tower inner furnace further comprises a support plate, a plurality of filter membrane pipes and a back flushing pipe, wherein the support plate is radially fixed in the filter cavity body along the radial direction of the filter cavity body, the support plate divides the filter cavity body into two parts, the part far away from the ash discharge cavity body is an upper cavity body, the part close to the ash discharge cavity body is a lower cavity body, the capacity of the upper cavity body is smaller than that of the lower cavity body, the gas inlet and the gas outlet of the separation tower are respectively positioned at two opposite sides of the lower cavity body, the gas outlet of the separation tower is higher than the gas inlet of the separation tower, the filter membrane pipes are axially fixed in the filter cavity body along the axial direction of the filter cavity body, the filter membrane pipes are fixedly penetrated on the support plate, one end of the back flushing pipe is positioned outside the high-temperature gas-solid separation tower, and the other end of the back flushing pipe is positioned in the upper cavity body, the back flushing pipe is provided with a plurality of back flushing ports at one end of the upper cavity, the back flushing ports are respectively and correspondingly communicated with the filtering membrane pipes, and the back flushing pipe is used for discharging dust in the filtering membrane pipes from the dust discharging port; the separation tower jacket is wrapped on the periphery of the separation tower inner furnace, the separation tower jacket is used for inputting high-temperature flue gas and heating low-temperature pyrolysis gas and high-temperature pyrolysis gas in the separation tower inner furnace, and an outlet of the separation tower jacket and an outlet of the high-temperature jacket are both connected with an inlet of the low-temperature inner cylinder;
the condensation arsenic-collecting device is connected with the gas outlet of the separation tower and is used for condensing the filtered pyrolysis gas to collect arsenic to obtain refined white arsenic; and the number of the first and second groups,
the reduction tower is connected with the gas outlet of the separation tower and is used for carrying out carbon reduction on the filtered pyrolysis gas to obtain metal arsenic;
the tail gas purification system is arranged as an alkaline washing tower, is connected with the condensation arsenic-collecting device and the reduction tower and is used for carrying out harmless treatment on pyrolysis tail gas discharged by the condensation arsenic-collecting device and the reduction tower through a sodium hydroxide solution;
wherein, the heating device includes:
the outlet of the flue gas main pipe is connected with the inlet of the high-temperature jacket and the inlet of the separation tower jacket; and the number of the first and second groups,
the combustion mechanism is used for generating high-temperature flue gas and is connected with the inlet of the flue gas main pipe;
the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material comprises the following steps:
step A, inputting the arsenic sulfide slag into the crusher, crushing the arsenic sulfide slag into particles with the particle size of 1mm-30mm, and outputting the particles;
b, inputting the arsenic sulfide slag output in the step A and the smelting smoke dust or the oxidized metal mineral powder into the raw material mixer for mixing, and outputting a pyrolysis raw material;
step C, conveying the pyrolysis raw material output in the step B into the low-temperature inner cylinder through the raw material feeding mechanism, and continuously inputting nitrogen for forming an oxygen-free atmosphere into the raw material feeding mechanism through the nitrogen making machine;
step D, continuously inputting nitrogen for forming an oxygen-free atmosphere into the low-temperature inner cylinder in the step C through the nitrogen manufacturing machine;
step E, stirring the pyrolysis raw material in the low-temperature inner cylinder in the step C through the low-temperature stirring mechanism, performing heating pyrolysis on the pyrolysis raw material through external flue gas in the low-temperature jacket according to a first set temperature, and performing heat preservation according to a first set time length, wherein the first set temperature is set to be 200-400 ℃, and the first set time length is set to be 60-180 min, so that sulfur in arsenic sulfide forms solid metal sulfide, arsenic in arsenic sulfide forms gaseous arsenic trioxide, and pyrolysis materials containing the metal sulfide and low-temperature pyrolysis gas containing the arsenic trioxide are respectively output;
step F, inputting carbon powder for decomposing arsenate into the high-temperature inner cylinder through the additive feeding mechanism, inputting the pyrolysis material output in the step E into the high-temperature inner cylinder through the pyrolysis material feeding mechanism, and continuously inputting nitrogen for forming an oxygen-free atmosphere into the additive feeding mechanism and the pyrolysis material feeding mechanism through the nitrogen manufacturing machine;
step G, continuously inputting nitrogen for forming an oxygen-free atmosphere into the high-temperature inner cylinder in the step F through the nitrogen manufacturing machine;
step H, stirring the pyrolysis material in the high-temperature inner cylinder in the step F through the high-temperature stirring mechanism, performing heating pyrolysis according to a second set temperature through external smoke in the high-temperature jacket, and performing heat preservation according to a second set time length, wherein the second set temperature is set to be 500-700 ℃, the second set time length is set to be 60-180 min, so that solid arsenic trioxide in the smelting smoke dust or the oxidized metal mineral powder is changed into a gaseous state, arsenate is decomposed, and pyrolysis tailings containing metal sulfide and high-temperature pyrolysis gas containing arsenic trioxide are output through the pyrolysis material discharging mechanism;
step I, inputting the low-temperature pyrolysis gas output in the step E and the high-temperature pyrolysis gas output in the step H into the separation tower inner furnace, performing high-temperature filtration on the low-temperature pyrolysis gas and the high-temperature pyrolysis gas through external flue gas in a separation tower jacket to enable arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas to be kept in a gaseous state, filtering dust in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas to form filtered pyrolysis gas, inputting the filtered pyrolysis gas into a condensation arsenic-collecting device, performing condensation on the filtered pyrolysis gas to collect arsenic, and respectively outputting refined white arsenic and pyrolysis tail gas, and/or inputting part of the filtered pyrolysis gas into a reduction tower, performing carbon reduction on the filtered pyrolysis gas, and respectively outputting metal arsenic and pyrolysis tail gas;
step J, mixing the external flue gas output by the high-temperature jacket in the step H with the external flue gas output by the separation tower jacket in the step I, and inputting the mixture into the low-temperature jacket in the step E; and the number of the first and second groups,
and K, performing harmless treatment on the pyrolysis tail gas output by the step I through the tail gas purification system, and discharging the pyrolysis tail gas after reaching the standard.
2. A method for the synergistic treatment and utilization of arsenic-containing materials in nonferrous smelting is used for performing arsenic removal and sulfur fixation treatment on arsenic sulfide slag containing arsenic sulfide and performing arsenic removal treatment on smelting smoke dust or oxidized metal mineral powder, wherein the smelting smoke dust is generated by products obtained by taking volatile elements along with smoke gas in the nonferrous smelting process and performing dust collection and condensation on the volatile elements, and the oxidized metal mineral powder is an intermediate product in a raw ore mining material or a mineral processing process link, and is characterized by comprising the following steps of:
step A, inputting the arsenic sulfide slag and the smelting smoke dust or the oxidized metal mineral powder into a raw material mixer for mixing, and outputting a pyrolysis raw material;
step B, conveying the pyrolysis raw material output by the step A to a low-temperature pyrolysis furnace;
step C, continuously inputting inert gas for forming an oxygen-free atmosphere into the low-temperature pyrolysis furnace in the step B;
d, heating and pyrolyzing the low-temperature pyrolysis furnace in the step B according to a first set temperature, and preserving heat according to a first set time length to enable sulfur in the arsenic sulfide to form a solid metal sulfide and arsenic in the arsenic sulfide to form gaseous arsenic trioxide, and respectively outputting a pyrolysis material containing the metal sulfide and a low-temperature pyrolysis gas containing the arsenic trioxide;
e, inputting carbon powder for decomposing arsenate and the pyrolysis material output in the step D into a high-temperature pyrolysis furnace;
step F, continuously inputting inert gas for forming an oxygen-free atmosphere into the high-temperature pyrolysis furnace in the step E; and the number of the first and second groups,
and G, carrying out heating pyrolysis on the high-temperature pyrolysis furnace in the step E according to a second set temperature, and carrying out heat preservation according to a second set time length to change the solid arsenic trioxide in the smelting smoke dust or the oxidized metal mineral powder into a gaseous state, decompose arsenate, and output pyrolysis tailings containing metal sulfide and high-temperature pyrolysis gas containing arsenic trioxide.
3. The method for co-processing and utilizing the nonferrous smelting arsenic-containing material according to claim 2, wherein in the step D, the first set temperature is set to 200-400 ℃, and the first set time period is set to 60-180 min.
4. The method for co-processing and utilizing the nonferrous smelting arsenic-containing material according to claim 2, wherein in the step G, the second set temperature is set to 500-700 ℃, and the second set time period is set to 60-180 min.
5. The method for co-processing and utilizing nonferrous smelting arsenic-containing material according to claim 2, wherein the method for co-processing and utilizing nonferrous smelting arsenic-containing material further comprises a step H of inputting the arsenic sulfide slag into a crusher, crushing the arsenic sulfide slag into particles with the particle size of 1mm-30mm and outputting the particles before the step A.
6. The method of nonferrous smelting arsenic-containing material for co-processing and utilization according to claim 2, wherein the method of co-processing and utilization of nonferrous smelting arsenic-containing material further comprises: and step I, inputting the low-temperature pyrolysis gas output in the step D and the high-temperature pyrolysis gas output in the step G into a high-temperature gas-solid separation tower, keeping the arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas in a gas state, filtering dust in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas to form a filtered pyrolysis gas, inputting the filtered pyrolysis gas into a condensation arsenic collecting device, condensing the condensed pyrolysis gas to collect arsenic, and outputting refined white arsenic.
7. The method for the synergistic processing and utilization of the nonferrous smelting arsenic-containing material according to claim 2, wherein the method for the synergistic processing and utilization of the nonferrous smelting arsenic-containing material further comprises a step J of inputting the low-temperature pyrolysis gas output in the step D and the high-temperature pyrolysis gas output in the step G into a high-temperature gas-solid separation tower, keeping arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas in a gaseous state, filtering out dust in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas to form a filtered pyrolysis gas, and inputting the filtered pyrolysis gas into a reduction tower, performing carbon reduction on the filtered pyrolysis gas, and outputting metallic arsenic.
8. The method for the co-processing and utilizing of the nonferrous smelting arsenic-containing material according to claim 2, characterized in that the method for the synergistic treatment and utilization of the nonferrous smelting arsenic-containing material also comprises a step K of inputting the low-temperature pyrolysis gas output by the step D and the high-temperature pyrolysis gas output by the step G into a high-temperature gas-solid separation tower, so that the arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas keeps in a gaseous state, filtering out the low-temperature pyrolysis gas and the dust in the high-temperature pyrolysis gas, inputting a part of the filtered low-temperature pyrolysis gas and the filtered high-temperature pyrolysis gas into a condensation arsenic-collecting device, condensing the arsenic to collect arsenic, outputting refined white arsenic, inputting the other part of the filtered low-temperature pyrolysis gas and the filtered high-temperature pyrolysis gas into a reduction tower, performing carbon reduction on the gases, and outputting metal arsenic.
9. The method for the synergistic processing and utilization of the nonferrous smelting arsenic-containing material according to claim 8, wherein the step D is implemented by performing thermal pyrolysis on the pyrolysis raw material in the low-temperature pyrolysis furnace through external flue gas, the step G is implemented by performing thermal pyrolysis on the pyrolysis material in the high-temperature pyrolysis furnace through external flue gas, the step K is implemented by performing high-temperature filtration on the low-temperature pyrolysis gas and the high-temperature pyrolysis gas in the high-temperature gas-solid separation tower through external flue gas, and the external flue gas used in the step D is implemented as a mixed gas of the external flue gas used in the step G and the external flue gas used in the step K.
10. A method for synergistic treatment and utilization of arsenic-containing materials in nonferrous smelting is used for arsenic-removing and sulfur-fixing treatment of arsenic sulfide slag containing arsenic sulfide, wherein the solid content of the arsenic sulfide slag contains 25-50% of As and 20-40% of S by mass percent, and the arsenic-removing treatment is used for dearsenifying smelting smoke dust or oxidized metal mineral powder, wherein the smelting smoke dust is generated by products obtained by carrying volatile elements along with smoke gas in the nonferrous smelting process and condensing the volatile elements through dust collection, the solid content of the smelting smoke dust contains 2-30% of CuO, 2-30% of PbO, 2-30% of ZnO and 2-30% of As by mass percent2O310E30 percent of the oxidized metal mineral powder, 30 to 50 percent of the solid components of the oxidized metal mineral powder and 30 to 50 percent of PbO and As in percentage by mass2O31-15 percent of CuO, 15-30 percent of As and the solid components of copper oxide ore powder in percentage by mass2O31-15%, characterized by comprising:
step A, inputting the arsenic sulfide slag into a crusher, crushing the arsenic sulfide slag into particles with the particle size of 1mm-30mm, and outputting the particles;
b, inputting the arsenic sulfide slag output in the step A and the smelting smoke dust or the oxidized metal mineral powder into a raw material mixer for mixing, and outputting a pyrolysis raw material;
step C, conveying the pyrolysis raw material output by the step B to a preheated low-temperature pyrolysis furnace;
d, continuously inputting inert gas for forming an oxygen-free atmosphere into the low-temperature pyrolysis furnace in the step C;
step E, stirring the pyrolysis raw materials in the low-temperature pyrolysis furnace in the step C, heating and pyrolyzing the pyrolysis raw materials through external flue gas at a first set temperature, and keeping the temperature for a first set time, wherein the first set temperature is set to be 200-400 ℃, the first set time is set to be 60-180 min, so that sulfur in arsenic sulfide forms solid metal sulfide, arsenic in arsenic sulfide forms gaseous arsenic trioxide, and pyrolysis materials containing the metal sulfide and low-temperature pyrolysis gas containing the arsenic trioxide are respectively output;
f, inputting carbon powder for decomposing arsenate and the pyrolysis material output in the step E into a preheated high-temperature pyrolysis furnace;
step G, continuously inputting inert gas for forming an oxygen-free atmosphere into the high-temperature pyrolysis furnace in the step F;
step H, stirring the pyrolysis material of the high-temperature pyrolysis furnace in the step F, performing heating pyrolysis according to a second set temperature through external smoke, and performing heat preservation according to a second set time length, wherein the second set temperature is set to be 500-700 ℃, and the second set time length is set to be 60-180 min, so that solid arsenic trioxide in the smelting smoke dust or the oxidized metal ore powder is changed into a gaseous state, arsenate is decomposed, and pyrolysis tailings containing metal sulfide and high-temperature pyrolysis gas containing arsenic trioxide are output;
step I, inputting the low-temperature pyrolysis gas output in the step E and the high-temperature pyrolysis gas output in the step H into a high-temperature gas-solid separation tower, heating and filtering the low-temperature pyrolysis gas and the high-temperature pyrolysis gas at high temperature through external flue gas to enable arsenic trioxide in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas to be kept in a gaseous state, filtering dust in the low-temperature pyrolysis gas and the high-temperature pyrolysis gas to form filtered pyrolysis gas, inputting the filtered pyrolysis gas into a condensation arsenic-collecting device, condensing the filtered pyrolysis gas to collect arsenic, and respectively outputting refined white arsenic and pyrolysis tail gas, and/or inputting part of the filtered pyrolysis gas into a reduction tower, performing carbon reduction on the filtered pyrolysis gas, and respectively outputting metal arsenic and pyrolysis tail gas;
step J, setting the external smoke used in the step E as a mixed gas of the external smoke used in the step I and the external smoke used in the step I; and the number of the first and second groups,
and K, performing harmless treatment on the pyrolysis tail gas output by the step I through a tail gas purification system, and discharging the pyrolysis tail gas up to the standard.
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Effective date of registration: 20220926 Address after: 661007 LAOCHANG Town, Gejiu City, Honghe Hani and Yi Autonomous Prefecture, Yunnan Province Patentee after: HONGHE ARSENIC CO.,LTD. Patentee after: Shenzhen Zhongyuan Environmental Technology Co.,Ltd. Address before: 661007 LAOCHANG Town, Gejiu City, Honghe Hani and Yi Autonomous Prefecture, Yunnan Province Patentee before: HONGHE ARSENIC CO.,LTD. Patentee before: GUANGDONG TIANYUAN ENVIRONMENTAL TECHNOLOGY Co.,Ltd. |