CN114538494A

CN114538494A - BaC2Recycling method of barium-based compound in acetylene preparation process

Info

Publication number: CN114538494A
Application number: CN202210258190.1A
Authority: CN
Inventors: 赵虹; 姜标; 李淼; 陈思远
Original assignee: Shanghai Advanced Research Institute of CAS
Current assignee: Shanghai Advanced Research Institute of CAS
Priority date: 2022-03-16
Filing date: 2022-03-16
Publication date: 2022-05-27
Anticipated expiration: 2042-03-16
Also published as: CN114538494B

Abstract

The invention discloses a BaC₂A recycling method of barium-based compounds in the acetylene preparation process. The method comprises the following processes: step 1, adding hot water into barium-rich residue formed in the preparation of acetylene by dry gas generation, and fully stirring to prepare Ba (OH)₂Taking the hot slurry with the content of 20-65 wt% as a filtering stock solution; directly taking barium-rich hot slurry formed by preparing acetylene by wet gas generation as a filtering stock solution; step 2, heat filtering the filtering stock solution to obtain Ba (OH)₂Solution, Ba (OH) obtained by hot filtration₂Introducing CO into the solution₂Carbonizing to form BaCO₃Slurry as synthetic BaC₂The raw materials are recycled. The invention is through the pair of BaC₂The barium slag or barium slurry generated after the acetylene is prepared by gas generation is separated and purified, thereby realizing the maximum recycling of barium resourcesCan absorb CO during the process₂The process for preparing the acetylene by using the coal is changed into a green process with negative carbon emission and zero solid waste emission.

Description

BaC2Recycling method of barium-based compound in acetylene preparation process

Technical Field

The invention belongs to the technical field of acetylene production, and particularly relates to BaC₂A recycling method of barium-based compounds in the acetylene preparation process.

Background

The current energy structure situation of 'rich coal and lean oil' in China determines the important position of coal chemical industry in industrial production in China, and calcium carbide (CaC) is prepared from coal₂) The technology is an important component of coal chemical industry in China, and is mainly used for producing acetylene as a raw material of important chemicals such as polyvinyl chloride (PVC), 1, 4-Butanediol (BDO) and the like. The calcium carbide market demand is vigorous, and the national calcium carbide yield reaches 2888 ten thousand tons in 2020. The traditional calcium carbide production technology has the defects of high temperature, high energy consumption, high pollution and high carbon emission, and does not meet the development requirements of energy conservation and emission reduction.

BaC₂As an ionic metal carbide, carbon is represented by C₂ ^2-In ionic form, with CaC₂The crystal structure of the catalyst is consistent, and the catalyst can react with water to generate acetylene. In 1900, british patent GB19000782A proposed that carbides of barium, strontium or calcium could be prepared by heating a mixture of barium or strontium sulfide or calcium sulfide and carbon; these metal carbides react with water to produce acetylene. Chinese patent 200810233478.3 proposes a method for preparing a barium carbide electrolyte block material prepared by high pressure and high temperature treatment after compression molding of graphite and a barium source. Chinese patent 202010777618.4 discloses a BaC₂The new method for preparing coal-based acetylene and co-producing carbon monoxide by replacing calcium carbide is characterized by that BaC₂The synthesis temperature of the calcium carbide is lower than that of the calcium carbide, and the energy is saved.

But BaC₂BaC as an intermediate for coal-to-liquids acetylene₂How to utilize barium-rich slag and slurry generated after the acetylene is prepared by water-blown gasification becomes a problem to be solved. On one hand, barium is a heavy metal element, so that a compound containing no barium has toxicity, and on the other hand, barium carbonate is expensive and needs to be recycled to control the process cost. Thus, BaC₂The Ba resource in the barium-containing solution after gas generation is recycled and reused as BaC₂Replacement of CaC₂A key link of a new technology for preparing acetylene from coal is carried out.

Disclosure of Invention

Hair brushIt is an object of the invention to provide a BaC₂The recycling method of the barium-based compound in the acetylene preparation process is BaC₂Replacement of CaC₂The new solution is provided for recycling the barium resource of the new technology for preparing acetylene from coal.

The technical scheme adopted by the invention for realizing the purpose is as follows:

BaC₂A process for cyclic utilization of barium-base compound in preparing acetylene features that BaC is used₂The method for recycling the barium-rich slurry or residue after gas generation comprises the following steps:

step 1, adding water into barium-rich residue formed in preparation of acetylene by dry gas generation, and fully stirring to prepare Ba (OH)₂Taking the hot slurry with the content of 20-65 wt% as a filtering stock solution; directly taking barium-rich hot slurry formed by preparing acetylene by wet gas generation as a filtering stock solution;

step 2, heat filtering the filtering stock solution to obtain Ba (OH)₂Solution, Ba (OH) obtained by hot filtration₂Introducing CO into the solution₂Carbonizing to form BaCO₃Slurry as synthetic BaC₂The raw materials are recycled.

In the cyclic process of the invention, Ba (OH)₂Introducing CO into the solution₂Conversion to BaCO₃Post-slurry recycle is critical due to the Ba (OH) obtained after hot filtration₂The solution is easy to crystallize, hydrated barium hydroxide is formed in the crystallization process, and the existence of the crystallization water can cause the synthesis of BaC₂The increase of energy consumption and the loss of carbon source in the process can cause the problems of uneven mixing of raw materials, difficult forming and the like, and the quality of the product is seriously influenced. A general reaction of Ba (OH)₂Conversion of the solution to BaCO₃The above problems can be avoided by recycling the slurry.

As a preferred embodiment, Ba (OH) in said step 1₂The temperature of the hot slurry with the content of 20-65 wt% is not lower than 70 ℃.

As a preferred embodiment, the bacs₂The barium-rich residue and slurry produced after gas evolution can be directly used without cooling.

As a preferred embodiment, in the hot filtering operation in the step 2, the filter cake is washed with water having a temperature of not less than 80 ℃.

As a preferred embodiment, the filter residue after the hot filtration in the step 2 is dried and used as a raw material of the radiation-proof cement.

As a preferred embodiment, BaCO is formed in step 2₃After the slurry is settled and separated, partial supernatant is obtained₃Thick paste, BaCO₃Mixing the thick slurry with a carbon source, and carrying out wet granulation to be used for BaC₂And (4) synthesizing.

As a preferred embodiment, the BaCO₃The water content of the thick paste is not higher than 25 percent, and BaCO₃Mixing the thick slurry with a carbon source, and preparing the carbon-barium mixture by a wet method, wherein the molar ratio of carbon to barium is 3-5: 1, and (3) mixing ball material.

As a preferred embodiment, the barium source taken away by the filter residue after the hot filtration in the step 2 causes BaC₂The loss of barium in the acetylene preparation process is supplemented by adding an additional barium source, and the amount of the supplemented barium is equivalent to the amount of the barium taken away by filter residue.

As a preferred embodiment, when the carbon source used has an ash content of less than 15% and an Si content of less than 6% in the ash, the amount of barium supplied does not exceed 10% of the first barium amount. Further preferably, the supplemental barium amount is no more than 7% of the first barium amount.

Compared with the prior art, the invention has the following beneficial effects:

1, with existing BaC₂Compared with the prior art for preparing acetylene, the invention has the advantages that the prior BaC₂On the basis of the acetylene preparation process, a new coal-to-acetylene process with negative carbon emission and zero solid waste emission for recycling barium-based compounds is provided, the full utilization of barium resources is basically realized, the barium pollution can be reduced, the economic benefit and the social benefit of the coal-to-acetylene are improved, and the method is a novel coal-to-acetylene technology with recycling economy.

2, the invention is through the pair of BaC₂The barium slag or barium slurry generated after the acetylene is prepared by gas generation is separated and purified, so that the maximum cyclic utilization of barium resources in the coal-based acetylene synthesis process can be realized, and CO can be absorbed in the process₂Preparing calcium carbide B from coalThe alkyne process becomes a green process with negative carbon emission and zero solid waste emission. A small amount of insoluble barium slag which can not be recycled can be used as a raw material for producing the radiation-proof special cement.

Drawings

FIG. 1 shows BaC in the present invention₂A process flow chart of recycling barium-based compounds in the acetylene preparation process.

Detailed Description

The technical solution of the present invention will be described in detail with reference to examples. The reagents and biomaterials used below were all commercial products unless otherwise specified.

Example 1

BaC₂The recycling method of the barium-based compound in the acetylene preparation process is shown in figure 1, and the process specifically comprises the following steps:

adding water into the barium-rich slurry which is the byproduct of preparing acetylene by wet gasification to prepare hot slurry with the temperature of about 80 ℃ and the water content of 70 mass percent, and filtering while the hot slurry is hot to obtain a filter cake and a hot solution which is formed by combining the filtered mother liquor and the leacheate. Drying and bagging the filter cake to be used as a barium-based raw material of the radiation-proof cement; the hot solution was incubated to maintain the temperature at 70 ℃. Pumping the hot solution into CO₂In a carbonization kettle, BaCO is obtained₃The suspension of (4); mixing BaCO₃Pumping the suspension into a settling tank to obtain BaCO with water content of about 18%₃Thick slurry and supernatant. Mixing the BaCO with the mixture₃And (3) feeding the thick slurry into a granulation process, wherein the thick slurry and semi-coke powder are mixed according to the carbon-barium molar ratio of 3-5: 1 mixing, and carrying out wet granulation to prepare BaC₂The compositional analysis of the synthesized raw material pellets, semi coke, is shown in tables 1 and 2. Returning the supernatant to the gas forming process and adding gas forming water. Per ton of BaC₂About 90 kg of barium-based raw material for the byproduct radiation-proof cement, and can supplement BaCO for avoiding the reduction of barium-based raw material caused by barium residue loss during secondary circulation₃About 25 kg.

TABLE 1 Industrial analysis of semi-coke

Item	Ash content (A)_ad)	Moisture (M)_ad)	Volatile component (V)_ad)	Fixed carbon (Fc)_ad)
					Content w. -%)	7.08	3.04	8.64	81.24

TABLE 2 ash composition of Ramsbottom coal

Example 2

BaC₂The recycling method of the barium-based compound in the acetylene preparation process specifically comprises the following steps:

hot water is added into barium slag with the water content of about 30 percent by mass of the byproduct for preparing acetylene by dry-method gas generation to prepare hot slurry with the water content of 70 percent and the temperature of about 80 ℃. Filtering the hot slurry while the hot slurry is hot to obtain a filter cake, and combining the filtered mother liquor and the leacheate into a hot solution; the filter cake is dried and then packaged to be used as a raw material of radiation-proof cement, and each ton of BaC₂The barium-based raw material for the byproduct dry-based radiation-proof cement is about 90 kg. Keeping the temperature of the hot solution at about 80 ℃ and pumping in CO₂In a carbonization tower, BaCO is obtained₃Turbid liquid; mixing BaCO₃Pumping the turbid liquid into a settling tank to obtain BaCO with the water content of about 18%₃And (5) thick slurry. Mixing the BaCO with the mixture₃And (3) feeding the slurry into a granulation process, mixing the slurry with semi-coke powder, and mixing the slurry with carbon and barium according to a carbon-to-barium molar ratio of 3-5: 1 wet granulation to prepare BaC₂Synthesized raw material pellets.

The above description is only a part of the preferred embodiments of the present invention, and the present invention is not limited to the contents of the embodiments. It will be apparent to those skilled in the art that various changes and modifications can be made within the spirit of the invention, and any changes and modifications made are within the scope of the invention.

Claims

1. BaC₂A process for cyclic utilization of barium-base compound in preparing acetylene features that BaC is used₂The method is characterized in that slurry or residue rich in barium after gas generation is recycled, and the method comprises the following steps:

step 1, adding water into barium-rich residue formed in the process of preparing acetylene by dry-method gas generation, and fully stirring to prepare Ba (OH)₂Taking the hot slurry with the content of 20-65 wt% as a filtering stock solution; directly taking barium-rich hot slurry formed by preparing acetylene by wet gas generation as a filtering stock solution;

2. The BaC of claim 1₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: ba (OH) in the step 1₂The temperature of the hot slurry with the content of 20-65 wt% is not lower than 70 ℃.

3. The BaC of claim 1₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: BaC₂The barium-rich residue and slurry produced after gas evolution can be directly used without cooling.

4. The BaC of claim 1₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: and in the hot filtering operation in the step 2, washing the filter cake with water at the temperature of not lower than 80 ℃.

5. The BaC of claim 1₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: and (3) drying the filter residue after the hot filtration in the step (2) to obtain a raw material of the radiation-proof cement.

6. The BaC of claim 1₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: BaCO formation in step 2₃After the slurry is settled and separated, partial supernatant is obtained₃Thick paste, BaCO₃Mixing the thick slurry with a carbon source, and carrying out wet granulation to be used for BaC₂And (4) synthesizing.

7. The BaC of claim 6₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: the BaCO₃The water content of the thick paste is not higher than 25 percent, and BaCO₃Mixing the thick slurry with a carbon source, and preparing the carbon-barium mixture by a wet method, wherein the molar ratio of carbon to barium is 3-5: 1, and (3) mixing ball material.

8. The BaC of claim 1₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: the barium source taken away by the filter residue after the hot filtration in the step 2 causes BaC₂The loss of barium in the acetylene preparation process is supplemented by adding an additional barium source, and the amount of the supplemented barium is equivalent to the amount of the barium taken away by filter residue.

9. The BaC of claim 8₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: when the ash content of the carbon source is lower than 15 percent and the Si content in the ash content is lower than 6 percent, the supplemented barium content is not more than 10 percent of the first barium content.

10. The BaC of claim 9₂The recycling method of the barium-based compound in the acetylene preparation process is characterized by comprising the following steps: the amount of the supplemented barium does not exceed 7% of the amount of the first barium.