CN101747203A - 沼气直接制取碳酸二甲酯副产制液体燃料甲醇的方法 - Google Patents
沼气直接制取碳酸二甲酯副产制液体燃料甲醇的方法 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- GNLJBJNONOOOQC-UHFFFAOYSA-N $l^{3}-carbane;magnesium Chemical compound [Mg]C GNLJBJNONOOOQC-UHFFFAOYSA-N 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
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- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
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- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
本发明公开了沼气清洁利用的新方法,主要是沼气与氯气和空气结合直接制取碳酸二甲酯副产制液体燃料甲醇的技术。利用沼气中的甲烷与氯气和空气中的氧气在Lewis acid催化剂下转化为CH3Cl和水,然后CH3Cl和水在金属离子交换的Y型分子筛催化剂作用下发生卤代烃水解反应生成CH3OH,再利用沼气中的CO2与甲醇生成碳酸二甲酯。本方法利用可再生的沼气为原料直接制取环保型化工产品碳酸二甲酯副产液体燃料甲醇。与沼气燃烧发电技术相比,本技术具有显著的二氧化碳减排效果;与甲烷二氧化碳重整技术相比,本技术反应条件温和;引入空气与甲烷和HCl反应,既可以避免氯离子的排放环境污染,同时又可以促进甲烷转化为CH3Cl;在制备出高附加值产品碳酸二甲酯的同时,获得具有广泛用途的副产品甲醇。
Description
技术领域
本发明属于一种制备碳酸二甲酯的方法,特别是涉及一种沼气直接制取重要有机中间体-碳酸二甲酯副产制液体燃料甲醇的新方法。
背景技术
沼气工程技术是治理有机废弃物污染和开发可再生能源十分有效的技术。目前我国有1000多座中大型沼气工程,厌氧消化装置总容积达70万立方米,而且还具备相当大的开发潜力。
沼气中的主要成分是甲烷和二氧化碳,其中甲烷占60%-70%,二氧化碳占30%-40%,还有少量氢、一氧化碳、硫化氢、氧和氮等气体,目前沼气的利用主要是用来燃烧发电。沼气燃烧会产生大量的温室气体二氧化碳。近年来有部分学者利用甲烷与二氧化碳重整制合成气进一步转化为液体燃料,但是甲烷和二氧化碳均是高惰性气体分子,其活化温度往往在700度以上,在此高温条件下催化剂极易积碳失活,而开发高温抗积碳的催化剂相当困难,因此开发新的工艺十分有必要。利用沼气中的甲烷和氯气反应生成氯甲烷、然后氯甲烷水解生成甲醇、甲醇再与沼气中的二氧化碳生成碳酸二甲酯,是一种新的工艺,反应条件温和,具有重要的现实意义。
碳酸二甲酯(DMC)是近年来受到国内外广泛关注的环保型绿色化工产品,1992年DMC在欧洲通过了非毒性化学品(Nontoxic sub.stance)的注册登记,属于无毒或微毒化工产品。由于其分子中含有CH-、-CO-、CHO-、CHO-、CO-等多种官能团,因而具有良好的反应活性。DMC可在诸多领域全面替代有毒光气、硫酸二甲酯(DMS)、氯甲烷及氯甲酸甲酯等剧毒或致癌物,进行羰基化、甲基化、甲酯化及酯交换等反应,生成多种重要化工产品;另一方面,以DMC为原料可以开发、制备多种高附加值的精细化学品,在医药、农药、合成材料、染料、润滑油添加剂、食品增香剂、电子化学品等领域获得广泛应用;此外,其他用途如溶剂、溶媒和汽油添加剂等也正在或即将实用化。所以,DMC被誉为21世纪有机合成的一个“新基块”,其发展将对我国的煤化工、甲醇化工、Cl化工起到巨大的推动作用。
利用可再生的沼气为原料直接制取环保型化工产品碳酸二甲酯副产液体燃料甲醇,对于环境保护和能源持续再生具有重要意义。
发明内容
1.本发明的目的:
本发明的目的在于提供一种利用可再生的沼气为原料,直接制取环保型化工产品碳酸二甲酯副产液体燃料甲醇的新方法,该方法具有重要的环境保护和能源持续再生意义。
2.本发明实现步骤:
沼气经脱硫后与氯气和空气混合,在Lewis acid催化剂的作用下生成CH3Cl和水,然后将CH3Cl与水在150~500℃条件下反应生成CH3OH,再经除水及未反应完的HCl后,将CO2和甲醇在100~300℃,1~8MPa条件下进行反应生成碳酸二甲酯,同时获得甲醇燃料。
主要反应方程式如下:
CH4+Cl2——→CH3Cl+HCl
2CH4+O2+2HCl——→2CH3Cl+2H2O
CH3Cl+H2O——→CH3OH+HCl
3.与现有技术相比,本发明具有以下优点:
①与沼气燃烧发电技术相比,本技术具有显著的二氧化碳减排效果;
②与甲烷二氧化碳重整技术相比,本技术反应条件温和;
③引入空气与甲烷和HCl反应,既可以避免氯离子的排放环境污染,同时又可以促进甲烷转化为CH3Cl;
④在制备出高附加值产品碳酸二甲酯的同时,获得具有广泛用途的副产品甲醇。
附图说明
图1是本发明的工艺流程图,沼气经脱硫后与氯气和空气混合,在催化剂的作用下高选择性地生成CH3Cl,然后向CH3Cl和CO2的混合气中通入水蒸汽,在金属离子交换的Y型分子筛催化剂的作用下,CH3Cl发生水解反应生成CH3OH,除去杂质及未反应完的HCl和水,再将CO2和CH3OH进行反应生成碳酸二甲酯,未反应完的气体可以循环利用。
具体实施方式
下面以实例进一步说明本发明的实质内容,但本发明的内容并不限于此。
实施例1
沼气经脱硫后与氯气和空气按照体积比2∶1∶1混合,在Lewis acid催化剂的作用下反应生成CH3Cl,然后与水在180℃条件下,NaY催化剂上,反应生成选择性95%的甲醇,除去未反应完的水和HCl后,在150℃、6MPa条件下,甲基镁催化剂上,反应生成选择性85%的DMC。
实施例2
沼气经脱硫后与氯气和空气按照体积比2∶1∶1混合,在Lewis acid催化剂的作用下反应生成CH3Cl,然后与水在280℃条件下,CsY催化剂上,反应生成86%的甲醇,除去未反应完的水和HCl后,在250℃、4MPa条件下,甲基镁催化剂上,反应生成90%DMC。
实施例3
沼气经脱硫后与氯气和空气按照体积比2∶1∶1混合,在Lewis acid催化剂的作用下反应生成CH3Cl,然后与水在380℃条件下,CuY催化剂上,反应生成78%的甲醇,除去未反应完的水和HCl后,在180℃、3MPa条件下,甲基镁催化剂上,反应生成95%DMC。
Claims (2)
1.一种沼气直接制取碳酸二甲酯副产制液体燃料甲醇的方法,其特征在于:以可再生的沼气为原料直接制取环保型有机化工中间体碳酸二甲酯副产液体燃料甲醇,具体包括如下步骤:
沼气先经脱硫后与氯气和空气混合,在催化剂的作用下沼气中的甲烷与氯气反应生成CH3Cl和HCl,空气中的氧气和甲烷及HCl反应生成CH3Cl和水,然后将CH3Cl与水在150~500℃和金属离子交换的Y型分子筛催化剂作用下生成CH3OH,再经除去杂质及未反应完的HCl和水后,将沼气中的CO2和生成的甲醇在温度100~300℃、压力1~8MPa条件下进行反应生成碳酸二甲酯。
2.根据权利要求1所述的一种沼气直接制取碳酸二甲酯副产制液体燃料甲醇的方法,其特征在于:所述的在催化剂的作用下沼气中的甲烷与氯气反应生成CH3Cl和HCl中的催化剂为Lewis acid催化剂,CH3Cl与水反应生成CH3OH所用的金属离子交换的Y型分子筛催化剂为NaY、KY、CsY、MgY、CuY、FeY等金属离子交换的Y型分子筛催化剂。
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CN114735650A (zh) * | 2022-04-27 | 2022-07-12 | 江苏大学 | 基于分形结构的自热型甲醇重整制氢装置及其控制方法 |
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CN114735650B (zh) * | 2022-04-27 | 2023-10-10 | 江苏大学 | 基于分形结构的自热型甲醇重整制氢装置及其控制方法 |
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