CN114538494B - BaC (BaC) 2 Recycling method of barium-based compound in acetylene production process - Google Patents
BaC (BaC) 2 Recycling method of barium-based compound in acetylene production process Download PDFInfo
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- CN114538494B CN114538494B CN202210258190.1A CN202210258190A CN114538494B CN 114538494 B CN114538494 B CN 114538494B CN 202210258190 A CN202210258190 A CN 202210258190A CN 114538494 B CN114538494 B CN 114538494B
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- barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/186—Strontium or barium carbonate
- C01F11/188—Barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/935—Carbides of alkali metals, strontium, barium or magnesium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10H—PRODUCTION OF ACETYLENE BY WET METHODS
- C10H19/00—Other acetylene gas generators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a BaC 2 A recycling method of barium-based compounds in acetylene production process. The method comprises the following steps: step 1, adding hot water into the barium-rich residue formed by preparing acetylene by dry gas generation, and fully stirring to prepare Ba (OH) 2 Taking hot slurry with the content of 20-65wt% as filtering stock solution; the barium-rich hot slurry formed by the wet-process gas generation and acetylene preparation is directly used as a filtering stock solution; step 2, performing hot filtration on the filtering stock solution to obtain Ba (OH) 2 Solution, to hot filtration of the obtained Ba (OH) 2 CO is introduced into the solution 2 Carbonizing to form BaCO 3 Slurry as synthetic BaC 2 Is recycled. The invention is realized by the method for BaC 2 The barium slag or the barium slurry generated after the acetylene is prepared by gas generation is separated and purified, so that the maximum cyclic utilization of the barium resource is realized, and simultaneously, CO can be absorbed in the process 2 The process of preparing the calcium carbide acetylene from the coal is changed into a green process with carbon emission and zero solid waste emission.
Description
Technical Field
The invention belongs to the technical field of acetylene production, and in particular relates to a BaC 2 A recycling method of barium-based compounds in acetylene production process.
Background
The current state of the energy structure of 'rich coal and lean oil' in China determines the importance of coal chemical industry in industrial production in China, and calcium carbide (CaC) is produced from coal 2 ) The technology is an important component of the coal chemical industry in China, and is mainly used for producing raw material acetylene of important chemicals such as polyvinyl chloride (PVC), 1, 4-Butanediol (BDO) and the like. The market demand of the calcium carbide is vigorous, and the yield of the calcium carbide reaches 2888 ten thousand tons nationally 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.
BaC 2 As an ionic metal carbide, carbon is represented by C 2 2- In the form of ions, with CaC 2 The crystal structure of the catalyst is consistent, and the catalyst can react with water to generate acetylene. 1900, british patent GB19000782A suggests that barium, strontium or calcium carbide can be prepared by heating barium sulfide or strontium sulfide or a mixture of 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 by adopting high-pressure high-temperature treatment after compression molding of graphite and a barium source. Chinese patent 202010777618.4 discloses a method using BaC 2 Novel method for preparing coal-based acetylene and co-producing carbon monoxide by replacing calcium carbide 2 The synthesis temperature is lower than the synthesis temperature of calcium carbide, and the energy is saved.
But BaC 2 BaC as intermediate for preparing acetylene from coal 2 The problem to be solved is how to use the barium-rich slag and slurry produced after acetylene is prepared by water gas generation. On one hand, barium is a heavy metal element, and a few barium-containing compounds have toxicity, and on the other hand, barium carbonate is expensive and must be recycled to control the process cost. Thus, baC 2 The recovery and reutilization of Ba resource in the barium-containing solution after gas generation is BaC 2 Replacement of CaC 2 A key link of a new technology for preparing acetylene from coal.
Disclosure of Invention
The invention aims to provide a BaC 2 The cyclic utilization method of barium-based compound in acetylene production process is BaC 2 Replacement of CaC 2 The barium resource reutilization of the new technology for preparing acetylene by coal provides a new solution.
The technical scheme adopted by the invention for achieving the purpose is as follows:
BaC (BaC) 2 Method for recycling barium-based compound in acetylene production process, which is to BaC 2 The method comprises the following steps of:
step 1, adding water into the barium-rich residue formed by preparing acetylene by dry gas generation, and fully stirring to prepare Ba (OH) 2 Taking hot slurry with the content of 20-65wt% as filtering stock solution; the barium-rich hot slurry formed by the wet-process gas generation and acetylene preparation is directly used as a filtering stock solution;
step 2, willPerforming hot filtration on the filtered stock solution to obtain Ba (OH) 2 Solution, to hot filtration of the obtained Ba (OH) 2 CO is introduced into the solution 2 Carbonizing to form BaCO 3 Slurry as synthetic BaC 2 Is recycled.
In the cyclic process of the present invention, ba (OH) 2 Introducing the solution into CO 2 Conversion to BaCO 3 Post-slurry recycling is critical due to Ba (OH) obtained after hot filtration 2 The solution is easy to crystallize, and hydrated barium hydroxide is formed in the crystallization process, and the existence of crystal water can cause the synthesis of BaC 2 The energy consumption and the loss of carbon sources in the process are increased, and meanwhile, the problems of uneven raw material mixing, difficult molding and the like are caused, so that the quality of the product is seriously influenced. Ba (OH) 2 Conversion of the solution to BaCO 3 The recycling of the slurry after it is used can avoid the above problems.
As a preferred embodiment, ba (OH) in said step 1 2 The temperature of the hot slurry in the amount of 20-65wt% is not lower than 70 ℃.
As a preferred embodiment, the BaC 2 The barium-rich residue and slurry produced after gas generation are directly used without cooling.
As a preferred embodiment, in the hot filtration operation in the step 2, the filter cake is rinsed 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 then used as a raw material of the radiation-proof cement.
As a preferred embodiment, baCO is formed in said step 2 3 After the slurry, part of supernatant liquid is settled and separated to obtain BaCO 3 Thick paste, baCO 3 Mixing the thick slurry with a carbon source, granulating by a wet method, and then using the mixture for BaC 2 Is a synthesis of (a).
As a preferred embodiment, the BaCO 3 The water content of the thick paste is not higher than 25%, baCO 3 Mixing thick slurry with a carbon source, and preparing the carbon-barium composite material by a wet method, wherein the molar ratio of the carbon-barium composite material is 3-5: 1.
As a preferred embodiment, the barium source carried away by the filter residue after the hot filtration in step 2 results in BaC 2 The loss of barium in the acetylene production process is supplemented by adding an extra barium source, and the dosage of the supplemented barium is equivalent to the quantity of the barium taken away by filter residues.
As a preferred embodiment, the amount of supplemental barium is not more than 10% of the amount of primary barium when the carbon source ash is used below 15% and the Si content in the ash is below 6%. Further preferably, the supplemental barium amount is no more than 7% of the initial barium amount.
Compared with the prior art, the invention has the following beneficial effects:
1, compared with the existing BaC 2 Compared with the acetylene production technology, the invention has the advantages that the prior BaC 2 On the basis of the acetylene production process, a novel coal-to-acetylene process with carbon emission and zero solid waste emission for recycling the barium-based compound is provided, the full utilization of barium resources is basically realized, the pollution of barium can be reduced, the economic benefit and the social benefit of the coal-to-acetylene can be improved, and the novel coal-to-acetylene technology is a recycling economy type novel coal-to-acetylene technology.
2, the invention is realized by the method of BaC 2 The barium slag or the barium slurry generated after the gas generation and the acetylene preparation are separated and purified, so that the maximum cyclic utilization of the barium resource in the coal-based acetylene synthesis process can be realized, and simultaneously, CO can be absorbed in the process 2 The process of preparing the calcium carbide acetylene from the coal is changed into a green process with carbon emission and zero solid waste emission. A small amount of insoluble barium slag which cannot be recycled can be used as a raw material for producing the radiation-proof special cement.
Drawings
FIG. 1 is a BaC of the present invention 2 And (3) a process flow chart for recycling the barium-based compound in the acetylene production process.
Detailed Description
The following describes the technical scheme of the present invention in detail by referring to examples. The reagents and biological materials used hereinafter are commercial products unless otherwise specified.
Example 1
BaC (BaC) 2 The method for recycling the barium-based compound in the acetylene production process comprises the following steps:
wet-process gas generation to prepare acetylene and by-productAdding water into the barium-rich slurry to prepare hot slurry with the temperature of about 80 ℃ and the water content of 70 percent, filtering while the hot slurry is hot to obtain a filter cake and a hot solution formed by combining the filtering mother liquor and the leaching solution. Drying the filter cake and bagging 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 CO 2 In a carbonization kettle, baCO is obtained 3 Is a suspension of (a) and (b); baCO is carried out 3 Pumping the suspension into a settling tank to obtain BaCO with water content of about 18% 3 Thick stock and supernatant. The BaCO is processed 3 Sending the thick slurry into a granulating process, wherein the molar ratio of the thick slurry to the semi coke powder is 3-5: 1, mixing, and carrying out wet granulation to prepare BaC 2 The component analysis of the synthesized raw material pellets, semi-coke is shown in tables 1 and 2. Returning the supernatant to the gas generating process, and mixing with gas generating water. Per ton BaC 2 About 90 kg of barium-based raw material for byproduct radiation-proof cement can be supplemented with BaCO to avoid the reduction of the barium-based raw material caused by the loss of barium slag during secondary circulation 3 About 25 kg.
TABLE 1 Industrial analysis of semi coke
| Project | Ash (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 semi coke
Example 2
BaC (BaC) 2 The recycling method of the barium-based compound in the acetylene production process specifically comprises the following steps:
adding hot water into the barium slag with the water content of about 30% of the byproduct in the dry-process gas-generating acetylene production process to prepare hot slurry with the water content of 70% and the temperature of about 80 ℃. Filtering the hot slurry to obtain a filter cake, and combining the filtered mother liquor and the leaching solution into a hot solution; the filter cake is dried and then is packed to be used as the raw material of the radiation-proof cement, and each ton of BaC 2 About 90 kg of a barium-based raw material for the byproduct dry-based radiation-proof cement. Maintaining the temperature of the hot solution at about 80deg.C, and pumping CO 2 In the carbonization tower, baCO is obtained 3 Turbid liquid; baCO is carried out 3 Pumping the turbid liquid into a settling tank to obtain BaCO with water content of about 18% 3 Thick stock. The BaCO is processed 3 The slurry is sent into a granulating process, mixed with the semi coke powder, and the molar ratio of carbon to barium is 3-5: 1 wet granulation to prepare BaC 2 Synthetic raw material pellets.
The foregoing 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 scope of the technical solution of the present invention, and any changes and modifications are within the scope of the present invention.
Claims (4)
1. BaC (BaC) 2 Method for recycling barium-based compound in acetylene production process, which is to BaC 2 The method is characterized by comprising the following steps of:
step 1, adding water into the barium-rich residue formed by preparing acetylene by dry gas generation, and fully stirring to prepare Ba (OH) 2 Taking hot slurry with the content of 20-65wt% as filtering stock solution;
ba (OH) in said step 1 2 The temperature of the hot slurry with the content of 20-65wt% is not lower than 70 ℃;
step 2, performing hot filtration on the filtering stock solution to obtain Ba (OH) 2 Solution, to hot filtration of the obtained Ba (OH) 2 CO is introduced into the solution 2 Carbonizing to form BaCO 3 Slurry as synthetic BaC 2 Is recycled; baCO is formed in the step 2 3 After the slurry, part of supernatant liquid is settled and separated to obtain BaCO 3 Thick paste, baCO 3 Mixing the thick slurry with a carbon source, granulating by a wet method, and then using the mixture for BaC 2 Is the synthesis of BaCO 3 The water content of the thick paste is not higher than 25%, baCO 3 Mixing thick slurry with a carbon source, and preparing the carbon-barium composite material by a wet method, wherein the molar ratio of the carbon-barium composite material is 3-5: 1, wherein the barium source carried away by the filter residue after the hot filtration in the step 2 leads to BaC 2 The loss of barium in the acetylene production process is supplemented by adding an extra barium source, the supplementing barium dosage is equivalent to the quantity of barium taken away by filter residues, and when the ash content of the carbon source is lower than 15 percent and the Si content in the ash is lower than 6 percent, the supplementing barium dosage is not more than 10 percent of the primary barium dosage;
and (2) drying filter residues after the hot filtration in the step (2) to serve as a raw material of the radiation-proof cement.
2. The BaC of claim 1 2 The recycling method of the barium-based compound in the acetylene production process is characterized by comprising the following steps of: baC (BaC) 2 The barium-rich residue and slurry produced after gas generation are directly used without cooling.
3. The BaC of claim 1 2 The recycling method of the barium-based compound in the acetylene production process is characterized by comprising the following steps of: in the hot filtration operation in the step 2, water with the temperature not lower than 80 ℃ is used for flushing the filter cake.
4. As claimed in claim 1Said BaC 2 The recycling method of the barium-based compound in the acetylene production process is characterized by comprising the following steps of: the supplemental barium amount is no more than 7% of the primary barium amount.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR682479A (en) * | 1928-11-21 | 1930-05-28 | Internat Ind & Chemical Compan | Preparation of barium carbide and application to the continuous production of acetylene and barium hydrate |
| DE517993C (en) * | 1928-11-29 | 1931-02-13 | Internat Ind & Chemical Compan | Manufacture of barium carbide and acetylene |
| CN101045950A (en) * | 2006-03-27 | 2007-10-03 | 宝山钢铁股份有限公司 | Process of treating BaO stainless steel oxidation dephosphorizing slag |
| CN114057194A (en) * | 2020-08-05 | 2022-02-18 | 中国科学院上海高等研究院 | Method for preparing barium carbide and producing acetylene |
-
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- 2022-03-16 CN CN202210258190.1A patent/CN114538494B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR682479A (en) * | 1928-11-21 | 1930-05-28 | Internat Ind & Chemical Compan | Preparation of barium carbide and application to the continuous production of acetylene and barium hydrate |
| DE517993C (en) * | 1928-11-29 | 1931-02-13 | Internat Ind & Chemical Compan | Manufacture of barium carbide and acetylene |
| CN101045950A (en) * | 2006-03-27 | 2007-10-03 | 宝山钢铁股份有限公司 | Process of treating BaO stainless steel oxidation dephosphorizing slag |
| CN114057194A (en) * | 2020-08-05 | 2022-02-18 | 中国科学院上海高等研究院 | Method for preparing barium carbide and producing acetylene |
Non-Patent Citations (1)
| Title |
|---|
| 天津化工研究院等编.《无机盐工业手册（上）》.化学工业出版社,1996,(第2版),第238页. * |
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