CN110607451B

CN110607451B - Waste contact body, slurry and slag treatment system and process generated in organic silicon production process

Info

Publication number: CN110607451B
Application number: CN201911038697.0A
Authority: CN
Inventors: 张凡; 辜锋; 陈向贵; 邓传宏; 李学智; 余云柏; 沙发文; 魏清成
Original assignee: Yunnan Keli Environmental Protection Co ltd
Current assignee: Yunnan Keli Environmental Protection Co ltd
Priority date: 2019-10-29
Filing date: 2019-10-29
Publication date: 2021-11-05
Anticipated expiration: 2039-10-29
Also published as: CN110607451A

Abstract

The invention belongs to the technical field of waste treatment, and in particular relates to a waste contact body and a slurry and slag treatment system and process generated in the production process of organic silicon; including a mechanical activation device, a reactor, a washing reactor, a replacement reactor, a rotary kiln, a hydrolysis reaction The feed end of the mechanical activation device is connected to the material and the outlet of waste hydrochloric acid, the discharge end is connected to the reactor, the reactor is connected to the washing reactor and the replacement reactor respectively, the washing reactor is connected to the rotary kiln, The reactor is connected with the hydrolysis reactor, and the end of the hydrolysis reactor is connected with a crystallization evaporation device; the technology is mature, the process is short, the efficiency is high, it is conducive to large-scale treatment, no three wastes are discharged, and secondary pollution to the environment is avoided, so as to realize the waste contact body. And green treatment of pulp residue.

Description

System and process for treating waste contact bodies and slurry residues generated in organic silicon production process

Technical Field

The invention belongs to the technical field of waste treatment, and particularly relates to a system and a process for treating waste contacts and slurry residues generated in an organic silicon production process.

Background

In the production process of the organic silicon, silicon and chloromethane are used as production raw materials, and a ternary copper catalyst (main catalyst) and zinc (auxiliary agent) are commonly used for promoting the synthesis of organic silicon monomers such as dimethyldichlorosilane, methyltrichlorosilane, trimethylchlorosilane, methyldichlorosilane and the like. During the synthesis process, slurry and waste contacts are generated.

The main components of the waste contact body are silicon, copper, carbon, zinc and the like, and the weight contents of the silicon, the copper, the carbon, the zinc and the like in the waste contact body are respectively 65% -80%, 3% -20%, 1% -10% and 0.05% -2.0%. The waste contact bodies have fine particles and high activity of copper powder, so that oxidation reaction is easy to occur when the waste contact bodies meet air, organic substances and carbon in the waste contact bodies are burnt to emit pungent white smoke, and the waste contact bodies are difficult to store; the slurry residue is a liquid-solid mixture with fluidity obtained by a wet dust removal process in the process of synthesizing methyl chlorosilane by a direct method, is hydrolyzed into black solid powder, contains about 1 to 3 percent of copper, has serious environmental pollution and has the serious problem of three wastes.

The prior waste contact body treatment methods comprise three methods: the air oxidation method, the oxidant oxidation method and the acidification method all have the problems of low silicon recovery rate, serious water pollution, difficult realization of industrialization and the like. The slurry and the slag have no systematic research, and are mostly treated by burning and then burying at present.

Disclosure of Invention

The invention aims to provide a system and a process for treating waste contacts and slurry residues generated in the production process of organic silicon.

In order to solve the technical problems, the invention adopts the following technical scheme:

the waste contact body and slurry residue treatment system produced in the production process of organic silicon comprises a mechanical activation device, a reactor, a washing reactor, a displacement reactor, a rotary kiln, a hydrolysis reactor and a crystallization evaporation device, wherein the feeding end of the mechanical activation device is connected with a material outlet and a waste hydrochloric acid outlet, the discharging end of the mechanical activation device is connected with the reactor, the reactor is respectively connected with the washing reactor and the displacement reactor, the washing reactor is connected with the rotary kiln, the displacement reactor is connected with the hydrolysis reactor, and the tail end of the hydrolysis reactor is connected with the crystallization evaporation device.

Furthermore, a circulating pipeline is arranged on a pipeline for connecting the washing reactor and the rotary kiln, and the tail end of the circulating pipeline is connected between the mechanical activation device and the reactor.

The waste contact body and slurry slag treatment process produced in the production process of organic silicon comprises the following steps:

1) feeding and filtering: the method comprises the following steps of (1) reasonably mixing waste contact bodies and slurry residues to obtain silicon powder containing about 6-10% of copper, pumping the silicon powder into a reactor after passing through a mechanical activation device, adding 10-20% of waste hydrochloric acid in the organic silicon production process, blowing air to control the oxidation atmosphere in the process under the condition of stirring, slowly adding an additive A and an additive B, leaching for 2-4 hours, and filtering;

2) and (3) leachate treatment: adding 1-3 times of reduced iron powder of copper into the leachate to replace the copper, filtering to obtain a sponge copper product, adding a neutralizing agent into the replaced leachate to recover valuable elements such as iron, zinc and the like, and piling up or taking out iron ore concentrate obtained by filtering;

3) leaching silicon powder treatment: the leached silicon powder is subjected to secondary washing and filtering by waste hydrochloric acid, and then is washed by adding clean water to meet the general solid waste requirements of HJ/T300-2007 and HJ/T299-2007, and can be sold as a building material;

4) waste hydrochloric acid treatment: the used waste hydrochloric acid mainly contains sodium chloride after copper extraction and neutralization, enters an organic silicon project wastewater treatment system for treatment or concentration and crystallization to produce sodium chloride, and can also electrolyze and recover sodium and chlorine elements in the waste hydrochloric acid;

5) hydrogen chloride flue gas treatment: generating a small amount of hydrogen chloride flue gas, absorbing the hydrogen chloride flue gas by clear water through an absorption tower, reaching the environmental protection emission standard, emptying, and returning the absorption liquid to the flow.

Further, in step 1), the amount of air blown into the oxidizing atmosphere is: 10-100L/H.

Further, in the step 1), the additive A is a dispersing agent, and the addition amount of the additive A is 50kg per ton of the material; the additive B is a surfactant, and the addition amount of the additive B is 10kg per ton of the material.

Further, in step 2), the neutralizing agent is sodium carbonate or caustic soda.

Compared with the prior art, the invention has at least one of the following beneficial effects:

the waste contact body or slurry slag is mainly silicon powder containing various heavy metal and other impurities, according to the characteristics of copper, zinc, silicon and other elements and compounds thereof in the silicon powder, waste hydrochloric acid generated in the production process of organic silicon is utilized, under the combined action of various additives, oxidants and surfactants, metal ions such as copper, zinc and the like are leached, replaced or neutralized and recovered, and the obtained silicon powder is washed and treated to meet the requirements of common solid waste or industrial silicon powder. The process has flexible technological conditions, can be used for resource utilization of the silicon powder with high metal content and harmless treatment of the silicon powder with low metal content by effectively improving the leachability of metals such as copper, zinc and the like and the filterability of the silicon powder, and has the recovery rate of both copper and silicon of more than 90 percent.

Drawings

FIG. 1 is a flow chart of the system architecture of the present invention.

1-mechanical activation device, 2-reactor, 3-washing reactor, 4-replacement reactor, 5-rotary kiln, 6-hydrolysis reactor and 7-crystallization evaporation device.

Detailed Description

As shown in fig. 1, in order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1

The waste contact body and slurry slag treatment system produced in the production process of organic silicon comprises a mechanical activation device 1, a reactor 2, a washing reactor 3, a displacement reactor 4, a rotary kiln 5, a hydrolysis reactor 6 and a crystallization evaporation device 7, wherein the feeding end of the mechanical activation device 1 is connected with a material and a waste hydrochloric acid outlet, the discharging end is connected with the reactor 2, the reactor 2 is respectively connected with the washing reactor 3 and the displacement reactor 4, the washing reactor 3 is connected with the rotary kiln 5, the displacement reactor 4 is connected with the hydrolysis reactor 6, the tail end of the hydrolysis reactor 6 is connected with the crystallization evaporation device 7, the problem of low recovery of copper and silicon is solved through batching and mechanical activation, and the recovery rate of copper and silicon can reach more than 90%.

Example 2

In addition to example 1, a circulation line is provided in a line connecting the washing reactor 3 and the rotary kiln 5, and the end of the circulation line is connected between the mechanical activation device 1 and the reactor 2, so that the generated solution can be returned to the reaction again, thereby increasing the recovery efficiency.

Example 3

1) feeding and filtering: obtaining copper-containing silicon powder about 6% of copper by reasonably proportioning waste contacts and slurry slag, firstly pumping into a reactor 2 after passing through a mechanical activation device 1, adding 10% of waste hydrochloric acid in the production process of organic silicon, and blowing an oxidizing atmosphere in the air control process under the condition of stirring, wherein the amount of air blown by the oxidizing atmosphere is as follows: 10L/H, slowly adding an additive A and an additive B, wherein the additive A is a dispersing agent, and the addition amount of the additive A is 50kg per ton of material; the additive B is a surfactant, the addition amount of the additive B is 10kg per ton of the material, and the filtering can be carried out after 2 hours of leaching;

2) and (3) leachate treatment: adding 1 time of reduced iron powder of copper into the leachate to replace the copper, filtering to obtain a sponge copper product, adding a neutralizing agent into the replaced leachate to recover valuable elements such as iron, zinc and the like, wherein the neutralizing agent is sodium carbonate or caustic soda, and piling up or selling iron ore concentrate obtained by filtering;

Example 4

1) feeding and filtering: obtaining copper-containing silicon powder about 8% with useless contact and thick liquid sediment through reasonable batching, earlier through mechanical activation device 1 back, pump into reactor 2, add the waste hydrochloric acid of 15% in the organosilicon production process, under the circumstances of stirring, the oxidizing atmosphere of air control process is blown in to the oxidizing atmosphere, and the volume that the air was blown in to the oxidizing atmosphere is: 50L/H, slowly adding an additive A and an additive B, wherein the additive A is a dispersing agent, and the addition amount of the additive A is 50kg per ton of material; the additive B is a surfactant, the addition amount of the additive B is 10kg per ton of the material, and the filtering can be carried out after 3 hours of leaching;

2) and (3) leachate treatment: adding 2 times of reduced iron powder of copper into the leachate to replace the copper, filtering to obtain a sponge copper product, adding a neutralizing agent into the replaced leachate to recover valuable elements such as iron, zinc and the like, wherein the neutralizing agent is sodium carbonate or caustic soda, and piling up or selling iron ore concentrate obtained by filtering;

Example 5

1) feeding and filtering: obtaining about 10% copper-containing silicon powder with useless contact and thick liquid sediment through reasonable batching, earlier through mechanical activation device 1 back, pump into reactor 2, add 20% waste hydrochloric acid in the organosilicon production process, under the circumstances of stirring, the oxidizing atmosphere of air control process is blown in to the oxidizing atmosphere, and the volume of air is blown in to the oxidizing atmosphere: 100L/H, slowly adding an additive A and an additive B, wherein the additive A is a dispersing agent, and the addition amount of the additive A is 50kg per ton of material; the additive B is a surfactant, the addition amount of the additive B is 10kg per ton of the material, and the filtering can be carried out after leaching for 4 hours;

2) and (3) leachate treatment: adding 3 times of reduced iron powder of copper into the leachate to replace the copper, filtering to obtain a sponge copper product, adding a neutralizing agent into the replaced leachate to recover valuable elements such as iron, zinc and the like, wherein the neutralizing agent is sodium carbonate or caustic soda, and piling up or selling iron ore concentrate obtained by filtering;

Experimental analysis:

1. results of toxicity test before calcination

The leaching toxicity test is carried out by adopting the HJ/T299-2007 standard (sulfuric acid-nitric acid method), and the contents of copper and zinc in the solution reach the standard requirement of less than 100 mg/l.

TABLE 1 toxicity test results

2. Post calcination leach toxicity test

After the copper is extracted from the waste contacts and the pulp slag, the waste contacts and the pulp slag are calcined for 2 hours at 1100 ℃ under the oxidation condition, the materials are still loose and powdery, the caking phenomenon is avoided, the burning loss of the pulp slag is 13.77 percent, and the burning loss of the waste contacts is 0.61 percent. The leaching toxicity test is carried out by adopting the HJ/T299-2007 standard (sulfuric acid-nitric acid method), and the contents of copper, zinc, lead, chromium, cadmium, nickel and the like all reach the standard requirements. The detailed results are as follows:

TABLE 2 calcined silica fume leaching toxicity test results

Unit: mg/l

Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.

Claims

1. The waste contact body and slurry treatment system produced in the process of organosilicon production, characterized in that it comprises a mechanical activation device (1), a reactor (2), a washing reactor (3), a replacement reactor (4), Rotary kiln (5), hydrolysis reactor (6) and crystallization evaporation device (7), the feed end of the mechanical activation device (1) is connected with the material and the outlet of waste hydrochloric acid, and the discharge end is connected with the reactor (2), the reactor (2) are respectively connected with the washing reactor (3) and the replacement reactor (4), the washing reactor (3) is connected with the rotary kiln (5), the replacement reactor (4) is connected with the hydrolysis reactor (6), and the hydrolysis reactor (4) is connected with the hydrolysis reactor (6). The end of the reactor (6) is connected with a crystallization evaporation device (7);

The treatment process of waste contact body and slurry produced in the production process of organic silicon includes the following steps:

1) Feeding and filtration: Pass the waste contact body and slurry through reasonable ingredients to obtain copper-containing 6-10% copper-containing silicon powder. After passing through the mechanical activation device (1), it is pumped into the reactor (2), and organic The 10-20% waste hydrochloric acid in the silicon production process is blown into the oxidizing atmosphere of the air control process under stirring. The amount of air blown into the oxidizing atmosphere is: 10-100L/H, slowly add Additive A and Additive B , Additive A is a dispersant, and the amount of Additive A is 50kg per ton of material; Additive B is a surfactant, and the amount of Additive B is 10kg per ton of material, and it can be filtered after leaching for 2-4 hours;

2) Leachate treatment: Add 1-3 times reduced iron powder of copper to the leaching solution to replace copper, filter to obtain sponge copper product, add neutralizer to recover iron and zinc valuable elements after replacement, neutralizer is soda ash or caustic soda, filter Received iron ore concentrate for stockpiling or takeaway;

3) Treatment of leached silicon powder: The leached silicon powder is washed and filtered by waste hydrochloric acid for a second time, and then washed with clean water, which can meet the general solid waste requirements of HJ/T 300-2007 and HJ/T 299-2007, and can be used as building materials Sales;

4) Waste hydrochloric acid treatment: After copper extraction and neutralization, the used waste hydrochloric acid mainly contains sodium chloride, which is processed or concentrated and crystallized to produce sodium chloride in the wastewater treatment system of the silicone project, and the sodium and chlorine elements are also electrolytically recovered;

5) Hydrogen chloride flue gas treatment: a very small amount of hydrogen chloride flue gas is generated, which is absorbed by the absorption tower with clean water, and then emptied to meet the environmental protection emission standards, and the absorption liquid is returned to the process.

2. The system for treating waste contact bodies and slag produced in the process of organosilicon production according to claim 1, characterized in that: a pipeline connecting the washing reactor (3) and the rotary kiln (5) is provided with a circulation pipeline, The end of the circulation pipe is connected between the mechanical activation device (1) and the reactor (2).