CN1389397A - Production process of CS2 and H2S with mixed natural gas of methane and ethane - Google Patents
Production process of CS2 and H2S with mixed natural gas of methane and ethane Download PDFInfo
- Publication number
- CN1389397A CN1389397A CN 02123527 CN02123527A CN1389397A CN 1389397 A CN1389397 A CN 1389397A CN 02123527 CN02123527 CN 02123527 CN 02123527 A CN02123527 A CN 02123527A CN 1389397 A CN1389397 A CN 1389397A
- Authority
- CN
- China
- Prior art keywords
- ethane
- methane
- natural gas
- sulphur
- hydrogen sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000003345 natural gas Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 32
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 25
- 239000005864 Sulphur Substances 0.000 claims description 25
- 235000009508 confectionery Nutrition 0.000 claims description 19
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 15
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 15
- 239000000284 extract Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- XDAHMMVFVQFOIY-UHFFFAOYSA-N methanedithione;sulfane Chemical compound S.S=C=S XDAHMMVFVQFOIY-UHFFFAOYSA-N 0.000 abstract 2
- 238000004939 coking Methods 0.000 description 11
- 238000009826 distribution Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The method for preparing carbon disulfide and hydrogen sulfide by utilizing methane and ethane mixed natural gas includes: selecting mixed gas in which the mole content of methane and ethane is above 97%; according to 1:2-6 of mole ratio of carbon and sulfur in the mixed gas mixing materials; preheating the above-mentioned obtained mixture to 300-500 deg.c in reaction furnace, and under the condition of that gauge pressure is 2-13 kg/cm mixing the methane and ethane mixed natural gas with liquid sulfur, making reaction at 500-750 deg.c, then all the materials are fed into adiabatic reactor, reaction residence time is 1.l5-5 sec., and the gas produced by reaction is undergone the process of sulfur separation and rectification to respectively obtain the pure carbon disulfide and hydrogen sulfide.
Description
Technical field
The present invention provides a kind of method of utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide, use and contain the above methane of 97% (mol ratio) and the blended Sweet natural gas and the sulphur of ethane is raw material, under suitable temperature and the effect of gauge pressure pressure condition, the gas that reaction generates, through the miscible liquid that cooling obtains, after rectifying separation, make the technology of dithiocarbonic anhydride and hydrogen sulfide.
It is raw material that manufacture method of the present invention adopts methane and ethane gas mixture, extends manufacture cycle, and reduces servicing time, and to reducing product cost, the comprehensive utilization of resource reduces environmental pollution and has important social effect and economical effectiveness.
Background technology
As everyone knows, the method for preparing dithiocarbonic anhydride at present is divided into two kinds substantially, is to make with charcoal and sulfur reaction in early days; Another kind is to use purity to prepare dithiocarbonic anhydride greater than 96% methane and sulfur reaction.For example U.S. FMC Corp. prepares dithiocarbonic anhydride with methane more than 96.7% and sulfur reaction, United States Patent (USP) No. 3876753, No. 4057163 and " chemical technology " (Volume Four 376-380 page or leaf), the preparation method of disclosed dithiocarbonic anhydride is that to adopt purity be that raw material and sulfur reaction prepare dithiocarbonic anhydride greater than 96% methane.Its major defect is:
1, purity is greater than 96% methane, and natural raw material can't satisfy its needs at all, must be through purifying, and also process is very complicated, must increase the purification of raw materials device, has not only increased processing step, and has strengthened facility investment and production cost;
2, purity is greater than 96% methane, wherein inevitably also contain the higher hydrocarbons greater than three carbon, higher hydrocarbons is just finished the burnt phenomenon of carbon collection when reacting with sulphur in the reaction process of preparation dithiocarbonic anhydride, a large amount of carbon distributions, coking carbon accumulate in the boiler tube inwall of Reaktionsofen, cause the reaction boiler tube wall thickness to increase, the difficulty of conducting heat, therefore reaction is unstable, and it is wayward, must stop production and remove the knot carbon laydown, cause the production cycle shorter, production efficiency is lower.
Summary of the invention
The inventor creates technical scheme of the present invention through development research and practice chronically.
The purpose of this invention is to provide a kind of method of utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide, contain the above methane of 97% (mol ratio) and the gas mixture and the sulphur of ethane is raw material by using, the gas that reaction generates under suitable temperature and gauge pressure pressure condition, the miscible liquid that obtains through cooling, after rectifying separation, make the technology of dithiocarbonic anhydride and hydrogen sulfide, overcome the drawback of prior art, reach the purpose that extends manufacture cycle, reduces product cost, reduces servicing time and enhance productivity.
The object of the present invention is achieved like this: a kind of method of utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide, it is characterized in that: it comprises the steps:
(1) select materials:
The molar content of choosing methane and ethane is blended Sweet natural gas and the sulphur raw material more than 97%;
(2) batching:
Mol ratio according to carbon in this gas mixture and sulphur is 1: the proportioning raw materials of 2-6 is prepared burden;
(3) preheating:
Described batching is preheated to 300-500 ℃ in Reaktionsofen;
(4) hybrid reaction: at gauge pressure pressure is under the 2-13Kg/Cm condition, the gas mixture raw material is mixed with Molten sulphur, controlled temperature reacts under 500-750 ℃ of condition, and all process stream enters in the adiabatic reactor then, and reaction time is 1.5-5 second;
(5) sulphur content from:
The gas that reaction is generated through sulphur content from, remove excessive sulphur;
(6) rectifying and collect product respectively:
Through rectifying, collect purified dithiocarbonic anhydride and hydrogen sulfide product respectively.
The methane in this gas mixture raw material and the content of ethane are proportioning arbitrarily.This gas mixture raw material is directly Sweet natural gas to be imported in the rectifying tower, extract wherein methane and the fraction of ethane.This gas mixture raw material is manually formulated, and the methane wherein and the molar content of ethane are more than 97%.The mol ratio of the sulphur in this proportioning raw materials is excessive 5-20%.
Major advantage of the present invention is:
1, raw material of the present invention is to use and contains the above methane of 97% (molar content) and the gas mixture of ethane is a raw material, is raw material than the methane that uses purity greater than 96%, has reduced ingredient requirement, greatly reduces raw materials cost;
2, the present invention uses and contains the above methane of 97% (molar content) and the gas mixture of ethane is raw material, reduce the content that wherein contains greater than the higher hydrocarbons of three carbon, greatly reduce the boiler tube knot carbon of Reaktionsofen, make heat transfer smooth and easy, make the easier control of production process, improved the security of suitability for industrialized production greatly, and prolonged the production cycle, reduced production cost, so just provide a kind of more economical, safer manufacturing process for carbon disulphide manufacture.
Further specify below in conjunction with preferred embodiment.
Description of drawings
Fig. 1 is a manufacturing process synoptic diagram of the present invention.
Embodiment
Consult shown in Figure 1ly, the method for utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide of the present invention comprises the steps:
(1) select materials:
The molar content of choosing methane and ethane is blended Sweet natural gas and the sulphur raw material more than 97%;
(2) batching:
Mol ratio according to carbon in this gas mixture and sulphur is 1: the proportioning raw materials of 2-6 is prepared burden, and the mol ratio of sulphur wherein is excessive 5-20%.
(3) preheating:
Described batching is preheated to 300-500 ℃ in Reaktionsofen;
(4) hybrid reaction: at gauge pressure pressure is under the 2-13Kg/Cm condition, the gas mixture raw material is mixed with Molten sulphur, controlled temperature reacts under 500-750 ℃ of condition, all process stream enters in the adiabatic reactor then, reaction time is 1.5-5 second, increase the reaction times, obtained bigger reaction conversion ratio;
(5) sulphur content from:
The gas that reaction is generated through sulphur content from, remove excessive sulphur;
(6) rectifying and collect product respectively:
Through rectifying, collect purified dithiocarbonic anhydride and hydrogen sulfide product respectively.
Since wherein sulphur content from distillation technology be technology well known in the art, so do not describe in detail.
Experimental results show that: methane in the gas mixture raw material that the present invention uses and ethane content are proportioning arbitrarily, and methane wherein and ethane content does not separately influence for the present invention in other words.The methane in the gas mixture raw material and the molar content of ethane are that the raw material more than 97% is obtained, most convenient and inexpensive method are that Sweet natural gas is imported in the rectifying tower, extract the wherein fraction of methane and ethane, requiring wherein, the molar content of methane and ethane is more than 97%; In fact, the methane in the Sweet natural gas that has and the molar content of ethane have reached more than 97%, can not need rectifying, directly use, and greatly reduce production costs, and have cheap and advantage easily.
Certainly, wherein inevitably contain the above high carbon component of a spot of three carbon, they are: propane, butane, pentane, hexane or heptane, because the composition of the Sweet natural gas of different areas there are differences, if the methane in the methane that extracts and the fraction of ethane and the molar content of ethane are lower than 97%, can regulate by the method for artificial preparation, make wherein methane and the molar content of ethane be more than 97%.Because distillation technology is a technology well known in the art, so the present invention does not describe in detail.
Prove by a large amount of experimental studies: the high-carbon components contents in the gas mixture raw material causes very big influence to carbon distribution coking in the production unit boiler tube, the content that contains the above high carbon component of three carbon wherein is low more, its carbon distribution coking thickness in boiler tube is few more, below describes by concrete experimental example:
1, when using the high-carbon component greater than 4% methane and ethane gas mixture, the carbon distribution coking thickness can reach 20-30mm in the boiler tube in one month, and at this moment temperature of reaction has been difficult to control, must stop and overhaul, can produce after removing the carbon distribution coking, the production cycle is one month;
When 2, using the high-carbon component as the methane of 3-4% and ethane gas mixture, collection carbon coking thickness can reach 10-15mm in 3 months boiler tubes.Also must stop and overhaul, can produce after removing the carbon distribution coking, the production cycle is 3 months;
When 3, using the high-carbon component as the methane of 2-3% and ethane gas mixture, collection carbon coking thickness can reach 5-15mm in the boiler tube in 1 year, needs to stop and overhauls, and can produce after removing the carbon distribution coking, and the production cycle is 1 year;
When 4, using the high-carbon component to be methane 2% below and ethane gas mixture, used continuously 1 year, collection carbon coking phenomenon does not have (below 1mm) substantially in the boiler tube, still can continue use, and the production cycle is more than 1 year.
Can illustrate by above-mentioned experiment, it is 97% above gas mixture that method of the present invention is used the molar content of methane and ethane, can greatly reduce carbon distribution coking drawback in the boiler tube, make heat transfer smooth and easy, make the easier control of production process, improved the security of suitability for industrialized production greatly, and reduced production cost, so just provide a kind of more economical, safer manufacturing process for carbon disulphide manufacture.
Claims (5)
1, a kind of method of utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide, it is characterized in that: it comprises the steps:
(1) select materials:
The molar content of choosing methane and ethane is blended Sweet natural gas and the sulphur raw material more than 97%;
(2) batching:
Mol ratio according to carbon in this gas mixture and sulphur is 1: the proportioning raw materials of 2-6 is prepared burden;
(3) preheating:
Described batching is preheated to 300-500 ℃ in Reaktionsofen;
(4) hybrid reaction: at gauge pressure pressure is under the 2-13Kg/Cm condition, the gas mixture raw material is mixed with Molten sulphur, controlled temperature reacts under 500-750 ℃ of condition, and all process stream enters in the adiabatic reactor then, and reaction time is 1.5-5 second;
(5) sulphur content from:
The gas that reaction is generated through sulphur content from, remove excessive sulphur;
(6) rectifying and collect product respectively:
Through rectifying, collect purified dithiocarbonic anhydride and hydrogen sulfide product respectively.
2, the method for utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide according to claim 1 is characterized in that: the methane in this gas mixture raw material and the content of ethane are proportioning arbitrarily.
3, the method for utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide according to claim 1, it is characterized in that: this gas mixture raw material is directly Sweet natural gas to be imported in the rectifying tower, extract wherein methane and the fraction of ethane.
4, the method for utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide according to claim 1, it is characterized in that: this gas mixture raw material is manually formulated, the methane wherein and the molar content of ethane are more than 97%.
5, the method for utilizing methane and ethane blended Sweet natural gas to make dithiocarbonic anhydride and hydrogen sulfide according to claim 1, it is characterized in that: the mol ratio of the sulphur in this proportioning raw materials is excessive 5-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02123527 CN1220626C (en) | 2002-07-02 | 2002-07-02 | Production process of CS2 and H2S with mixed natural gas of methane and ethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02123527 CN1220626C (en) | 2002-07-02 | 2002-07-02 | Production process of CS2 and H2S with mixed natural gas of methane and ethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1389397A true CN1389397A (en) | 2003-01-08 |
| CN1220626C CN1220626C (en) | 2005-09-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02123527 Expired - Lifetime CN1220626C (en) | 2002-07-02 | 2002-07-02 | Production process of CS2 and H2S with mixed natural gas of methane and ethane |
Country Status (1)
| Country | Link |
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| CN (1) | CN1220626C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007131977A1 (en) * | 2006-05-16 | 2007-11-22 | Shell Internationale Research Maatschappij B.V. | A process for the manufacture of carbon disulphide |
| WO2007131976A1 (en) * | 2006-05-16 | 2007-11-22 | Shell Internationale Research Maatschappij B.V. | A process for the manufacture of carbon disulphide |
| CN100404415C (en) * | 2006-09-18 | 2008-07-23 | 孔庆然 | Preparation method for carbon bisulfide |
| CN105727687A (en) * | 2015-06-01 | 2016-07-06 | 代元军 | Desorption gas recycling apparatus and desorption gas recycling method for pressure swing adsorption apparatus |
| CN107010606A (en) * | 2017-04-28 | 2017-08-04 | 湖北兴发化工集团股份有限公司 | The technique that production methyl mercaptan and/or dimethyl sulfide intermediate raw material are prepared using natural gas |
| CN108128776A (en) * | 2017-04-14 | 2018-06-08 | 阳城县瑞兴化工有限公司 | It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide |
| CN108483446A (en) * | 2018-04-10 | 2018-09-04 | 上海东庚设备工程技术有限公司 | The separation method and system of excessive sulphur during a kind of carbon disulphide production |
| CN114906849A (en) * | 2022-06-23 | 2022-08-16 | 上海德迈世欧科技有限公司 | Process for the preparation of hydrogen sulphide and carbon disulphide |
-
2002
- 2002-07-02 CN CN 02123527 patent/CN1220626C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007131977A1 (en) * | 2006-05-16 | 2007-11-22 | Shell Internationale Research Maatschappij B.V. | A process for the manufacture of carbon disulphide |
| WO2007131976A1 (en) * | 2006-05-16 | 2007-11-22 | Shell Internationale Research Maatschappij B.V. | A process for the manufacture of carbon disulphide |
| EA014708B1 (en) * | 2006-05-16 | 2011-02-28 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | A process for the manufacture of carbon disulphide |
| CN101443269B (en) * | 2006-05-16 | 2012-06-27 | 国际壳牌研究有限公司 | A process for the manufacture of carbon disulphide |
| US8722006B2 (en) | 2006-05-16 | 2014-05-13 | Shell Oil Company | Process for the manufacture of carbon disulphide |
| CN100404415C (en) * | 2006-09-18 | 2008-07-23 | 孔庆然 | Preparation method for carbon bisulfide |
| CN105727687A (en) * | 2015-06-01 | 2016-07-06 | 代元军 | Desorption gas recycling apparatus and desorption gas recycling method for pressure swing adsorption apparatus |
| CN108128776A (en) * | 2017-04-14 | 2018-06-08 | 阳城县瑞兴化工有限公司 | It is a kind of using coal bed gas as the method for Material synthesis carbon disulfide |
| CN107010606A (en) * | 2017-04-28 | 2017-08-04 | 湖北兴发化工集团股份有限公司 | The technique that production methyl mercaptan and/or dimethyl sulfide intermediate raw material are prepared using natural gas |
| CN108483446A (en) * | 2018-04-10 | 2018-09-04 | 上海东庚设备工程技术有限公司 | The separation method and system of excessive sulphur during a kind of carbon disulphide production |
| CN108483446B (en) * | 2018-04-10 | 2021-12-10 | 上海东庚化工技术有限公司 | Method and system for separating excessive sulfur in carbon disulfide production process |
| CN114906849A (en) * | 2022-06-23 | 2022-08-16 | 上海德迈世欧科技有限公司 | Process for the preparation of hydrogen sulphide and carbon disulphide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1220626C (en) | 2005-09-28 |
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Application publication date: 20030108 Assignee: Cangzhou Ruixing Chemical Co.,Ltd. Assignor: LIAOYANG RUIXING CHEMICAL Co.,Ltd. Contract record no.: 2014130000167 Denomination of invention: Production process of CS2 and H2S with mixed natural gas of methane and ethane Granted publication date: 20050928 License type: Exclusive License Record date: 20141231 |
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Address after: 111004 iron west road, Tai Zi River District, Liaoyang, Liaoning Province, No. 8 Patentee after: LIAONING RUIXING CHEMICAL GROUP Co.,Ltd. Address before: 111004 iron west road, Baita District, Liaoyang, Liaoning Province, No. 8 Patentee before: LIAOYANG RUIXING CHEMICAL Co.,Ltd. |
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Application publication date: 20030108 Assignee: LIAOYANG RUIXING CHEMICAL Co.,Ltd. Assignor: Liaoning Ruixing Chemical Group Co.,Ltd. Contract record no.: 2018210000014 Denomination of invention: Production process of CS2 and H2S with mixed natural gas of methane and ethane Granted publication date: 20050928 License type: Common License Record date: 20180522 |
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Application publication date: 20030108 Assignee: Sichuan Yali Technology Co.,Ltd. Assignor: LIAOYANG RUIXING CHEMICAL Co.,Ltd. Contract record no.: 2018990000214 Denomination of invention: Production process of CS2 and H2S with mixed natural gas of methane and ethane Granted publication date: 20050928 License type: Common License Record date: 20180813 |
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