磷改性催化剂一步合成二甲醚研究
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摘要
规模化生产“绿色能源”——二甲醚(DME)所采用的方法都是通过煤气化制备得到高氢碳比的合成气进行甲醇合成,再经甲醇脱水的两步法制备得到二甲醚,在动力学和热力学方面都不是最经济的。一步法合成二甲醚的研究成果表明,使用双功能催化剂可提高一氧化碳和氢气的单程转化率,但存在催化剂中两功能团活性温度不一致,使其活性不能最大限度的发挥作用等问题。其次,制备二甲醚的原料几乎都采用煤或天然气等资源为基础原料,在生产清洁能源时还是消耗大量化石燃料(能源),最终也会使得这些地球上仅有的不可再生化石燃料资源的枯竭。另一方面,在冶金和化工等行业大量采用以煤、焦炭、天然气等作为还原剂进行金属和非金属的直接还原工艺的冶炼技术,副产大量的含高浓度一氧化碳的尾气,如黄磷炉尾气、密封电石炉气、氧气顶吹炼钢转炉尾气、炼油尾气、天然气部分氧化尾气、合成氨铜洗弛放气等,至今多数都采用燃烧利用部分热能,或进行火炬燃烧后转化成二氧化碳排入大气,既造成环境的污染,又是对碳资源的浪费。如何充分利用这些含一氧化碳宝贵资源的气体,减少排放,缓减能源短缺和燃料排放引起的环境恶化,对实现当今能源与环境协调发展和我国节能减排的目标至关重要。
本研究在国内率先开展用含一氧化碳尾气为基本原料合成清洁燃料二甲醚,选择黄磷生产过程中排放的含高浓度一氧化碳气源,模拟黄磷尾气经部分变换制备得到含CO2高碳氢比合成气为原料,在浆态床中一步合成二甲醚工艺；通过双功能催化剂的磷改性,提高催化活性、二甲醚选择性和CO2利用率；研究新型催化剂一步合成二甲醚的热力学和动力学理论,为实现黄磷尾气等含一氧化碳尾气的资源化利用奠定理论基础。
由磷酸浸渍法改性γ-Al203用作甲醇催化剂是一有效的方法。改性催化剂经FT-IR和X射线粉末衍射仪分析,证明磷改性使γ-Al203分子结构中增加了O=P—O键,导致催化剂γ-Al203表面的酸碱对增加,脱水性能增强。得到的P改性甲醇脱水催化剂P-γ-Al2O3与商业化铜基合成甲醇催化剂C301制备得到的新型双功能催化剂,应用于含CO2的富碳合成气在浆态床中一步合成DME,其催化活性增强,使生成的CO2的量明显减少,即可抑制CO变换生成CO2的反应,提高总碳的利用率和二甲醚的选择性。
通过较为详细地研究三相床中的反应工艺条件以及传质、原料气中二氧化碳含量等对一步合成二甲醚反应的影响。得到在浆态床中使用磷改性双功能催化剂(C301/P-γ-Al2O3)一步合成DME的优化工艺条件为：反应温度250-270℃,系统压力4.3MPa,空速为600mL/h·gcat,H2比(CO+CO2)约1.5,惰性溶剂量150ml,催化剂用量7.3%,反应器的搅拌转速750r/min,其反应结果为CO转化率可以达到95%以上,DME选择性大于60%,远高于未改性的34.61%,反应产物中几乎不含甲醇,C02生成量很少。并且合成气中一定量CO2的存在,可抑制水煤气变换反应,提高DME选择性；但CO2量过高,会与CO在催化剂表面竞争吸附,致使反应速率降低。
对含C02的合成气一步合成二甲醚反应系统进行热力学理论分析计算表明：所有主副反应均为放热反应,随着温度的升高,各反应式的平衡常数都是降低的,温度的升高,对甲醇合成的平衡常数降低影响最大,而对CO变换影响居中,对二甲醚合成的影响相对较小。在浆态床温度约为250℃,DME平衡选择性和收率分别可达94.5%和70%,此时总碳转化率可以达到72%,远超过合成甲醇时的碳转化率。证明含C02合成气直接制二甲醚工艺路线可以克服合成气制甲醇反应中出现的化学平衡限制。
磷改性的双功能催化剂体系催化含CO2富碳合成气一步合成二甲醚动力学机理可以是：甲醇的形成是首先经过吸附态的CO或C02与相邻的吸附态的羟基或H直接发生反应生成甲酸盐中间体,再通过连续加氢的形式生成甲醇盐和甲醇,即CO和C02均是甲醇合成的碳源；而DME的合成则是经过分子吸附态甲醇与邻近的解离吸附态甲醇相互作用的结果；副反应CO水汽变换是由合成甲醇生成的甲酸盐中间体被还原成吸附态的二氧化碳,氢的生成可以看作是氢解离吸附的逆反应。由此推导的磷改催化体系在浆态床中一步合成二甲醚动力学模型可以由甲醇合成机理速率方程、甲醇脱水机理速率方程和水汽变换机理速率方程表示。通过实验确定的模型参数和动力学模型经实验检验,其模型计算值与实验值数据吻合较好。
另外,新建立的由Prorapak Q填充柱和5A分子筛填充柱双柱串联,两次进TCD检测器的气相色谱分析方法,解决了需多次取样,在单一色谱柱中多次进样分析带来换算困难的难题和准确性,实现产品混合气一次进样即可进行组分的在线全分析。
The scale method for synthesis dimethyl ether (DME) is two-step method, ie. First, methanol is synthesized from the syngas, then the methanol dehydrate to DME. The process of two-step method for synthesis DME is not economic in kinetics and thermodynamics. The results from process by single-step synthesis DME in single reactor indicated:a double function catalyst had been increnced the conversion rate of CO and H2, but there is a problem that the activity temperature of synthesis methanol from syngas and methanol dehydration to DME is different in the catalyst system, and the activation of catalyst can not exert its catalysis maximum. Secondly, the basic material to synthesize cleanliness energy sources, DME, is from coal or nature gas, and it will consume the fossil energy sources in the Earth. But there are a large of tail gas contained high concentration CO to be discharge to air from the plant, which produce metal and nonmetallic with coal/coke or nature gas for reducer agent in the metallurgy and chemical industry, for example, yellow phosphorus tail gas, airproof calcium carbide tail gas, steel-making converter tail gas, oil refining tail gas, tail gas from portion oxidation of nature gas, copper wash relax gas of synthesis ammonia and so on. The usual treatment method about this kind tail gas is burning them and using portion heat, or burning by torch, which result is conversion the CO to CO2 to vent into air. How to using the invaluablener resource gas contained CO, reducing discharge, ease off the conflict of scarce energy sources and aggravating environment worsening, realizing saving energy and reducing pollution is very important in China.
There are summarized about the synthesis technique and reaction mechanism of DME at home and abroad to be discussed and the research harvest about technological progress and basic theory of single-step synthesis DME from syngas was presented emphatically in this paper. This thesis discuss the single-step process for synthesis DME by modified bifunctional the catalysis in a slurry reactor, using the simulation syngas with high rate of CO/H2 contained CO2 from the yellow phosphorus tail gas via portion water-shift. The research included the phosphorus modified of catalysis, optimization of the technology condition in a slurry reactor, and study of the process dynamics and thermodynamics.
A new modified bifunctional catalyst (C301/P-γ-Al2O3) is preparation with basic Cu (C301) catalyst for synthesis Methanol and modified dehydrate catalyst (P-γ-Al2O3) with H3PO4 dipping and calcinations. There are new O=P—O bond to be found in the modifiedγ-Al2O3 by analyse with FT-IR and X-ray diffraction, and it increase the pair acid-alkali in dehydrate catalyzer. And the modified bifunctional catalyst(C301/P-γ-Al2O3) enhance the capability of methanol conversion to DME, and increas the conversion rate of total Carbon and selectivity of DME, and restrain the by-reaction from CO to CO2.
A optimum technology reaction conditions are obtained after study the transfer and reaction condition with the modified bifunctional catalyst (C301/P-γ-Al2O3) in slurry bed, namely,250-270℃of system temperature,4.3MPa of the system pressure,600mL/h·gcat of space time, H2/(CO+CO2)≈1.5,150ml of the inert solvent,7.3% of the catalyst to the solvent,750r/min of the stirrer rotate speed. When the modified catalyst was used for synthesis DME in slurry bed reactor from the rich carbon syngas cantained CO2, the conversion rate of CO achieved 95.90% and selectivity of DME is 60%., which is outclass the 34.61% of the selectivity in using the non-modified catalyst system. And it is ture that the production ratio of CO2 is reduced evidently, the methanol is little or none in production system.
The relation equations about reaction heat and reaction balance constant with the system temperature were built by process thermodynamics analysis. The all reactions are exothermic reaction, and their balance constant will reduce when the reaction temperature increase, and the balance constant for methanol synthesis is most sensitivity, the CO/H2O shift reaction is secondly. The calculated value of total carbon and selectivity of DME are 72% and 95.4% by Matlab software from optimum equation about rich carbon syngas contained CO2 at 250℃, which closed to the experiment value. The calculate results prove single-step synthesis DME technology by P modified bifunctional catalyst (C301/P-y-Al2O3) from syngas contained CO2 will overcome the problem of the restriction of chemistry reaction balance.
The kinetics modeling basic rich carbon syngas contained CO2 synthesis DME with the modified bifunctional catalyst(C301/P-y-Al2O3) in slurry bed reactor can be express with the combination of reaction rate equations about:1)syngas to methanol,2) methanol dehydrate to DME, and 3) CO-H2O shift to CO2. The reaction process mechanism is that CO and CO2 all are the Carbon resource to synthesis Methanol, the middle process include: 1) adsorbed CO/CO2 convert to intermediate, formate, and it continuous add H with adsorbed OH/H to methanol; 2) adsorbed methanol and isolate adsorbed methanol convert to DME; 3) the by-reaction are form by formate deoxidized to CO2 and adsorbed H convert to H2.
The calculation data with kinetics model have a good inosculated with check-up by experimentation. It is be found that the CO2 in syngas can restrain the CO-H2O shift reaction, and increase the selectivity of DME. But excessive CO2 will be competed adsorption on the face of catlyzer with CO, and it will result the reaction rate decrease.
A new analysis system with GC for analyzing complexity production gas in the single-step synthesis DME system was built, which change the side-by-side double column to tandem Prorapak Q and molecule sieve filled column, and the sample pass though the TCD detector twice. The analysis system and method have solved the problem which need sampling and insert sample time after time in experiment, and the trouble for conversion data, and it is make the analyzing reaction gas quickly and easy on-line.
Anyway, using the resource for the tail gas contained high concentration CO to synthesis DME is an excellent path, which achieve saving energy, lowering energy consumption and reducing pollutants discharge. The modified of bifunctional catalyst by P can improved the matching temperature of the function group; and has a application worth practicality for synthesis DME from rich carbon syngas cantained CO2 in slurry bed; And the theorys about kinetics and thermodynamics have a guidance significance for scale in the industry.
本研究在国内率先开展用含一氧化碳尾气为基本原料合成清洁燃料二甲醚,选择黄磷生产过程中排放的含高浓度一氧化碳气源,模拟黄磷尾气经部分变换制备得到含CO2高碳氢比合成气为原料,在浆态床中一步合成二甲醚工艺；通过双功能催化剂的磷改性,提高催化活性、二甲醚选择性和CO2利用率；研究新型催化剂一步合成二甲醚的热力学和动力学理论,为实现黄磷尾气等含一氧化碳尾气的资源化利用奠定理论基础。
由磷酸浸渍法改性γ-Al203用作甲醇催化剂是一有效的方法。改性催化剂经FT-IR和X射线粉末衍射仪分析,证明磷改性使γ-Al203分子结构中增加了O=P—O键,导致催化剂γ-Al203表面的酸碱对增加,脱水性能增强。得到的P改性甲醇脱水催化剂P-γ-Al2O3与商业化铜基合成甲醇催化剂C301制备得到的新型双功能催化剂,应用于含CO2的富碳合成气在浆态床中一步合成DME,其催化活性增强,使生成的CO2的量明显减少,即可抑制CO变换生成CO2的反应,提高总碳的利用率和二甲醚的选择性。
通过较为详细地研究三相床中的反应工艺条件以及传质、原料气中二氧化碳含量等对一步合成二甲醚反应的影响。得到在浆态床中使用磷改性双功能催化剂(C301/P-γ-Al2O3)一步合成DME的优化工艺条件为：反应温度250-270℃,系统压力4.3MPa,空速为600mL/h·gcat,H2比(CO+CO2)约1.5,惰性溶剂量150ml,催化剂用量7.3%,反应器的搅拌转速750r/min,其反应结果为CO转化率可以达到95%以上,DME选择性大于60%,远高于未改性的34.61%,反应产物中几乎不含甲醇,C02生成量很少。并且合成气中一定量CO2的存在,可抑制水煤气变换反应,提高DME选择性；但CO2量过高,会与CO在催化剂表面竞争吸附,致使反应速率降低。
对含C02的合成气一步合成二甲醚反应系统进行热力学理论分析计算表明：所有主副反应均为放热反应,随着温度的升高,各反应式的平衡常数都是降低的,温度的升高,对甲醇合成的平衡常数降低影响最大,而对CO变换影响居中,对二甲醚合成的影响相对较小。在浆态床温度约为250℃,DME平衡选择性和收率分别可达94.5%和70%,此时总碳转化率可以达到72%,远超过合成甲醇时的碳转化率。证明含C02合成气直接制二甲醚工艺路线可以克服合成气制甲醇反应中出现的化学平衡限制。
磷改性的双功能催化剂体系催化含CO2富碳合成气一步合成二甲醚动力学机理可以是：甲醇的形成是首先经过吸附态的CO或C02与相邻的吸附态的羟基或H直接发生反应生成甲酸盐中间体,再通过连续加氢的形式生成甲醇盐和甲醇,即CO和C02均是甲醇合成的碳源；而DME的合成则是经过分子吸附态甲醇与邻近的解离吸附态甲醇相互作用的结果；副反应CO水汽变换是由合成甲醇生成的甲酸盐中间体被还原成吸附态的二氧化碳,氢的生成可以看作是氢解离吸附的逆反应。由此推导的磷改催化体系在浆态床中一步合成二甲醚动力学模型可以由甲醇合成机理速率方程、甲醇脱水机理速率方程和水汽变换机理速率方程表示。通过实验确定的模型参数和动力学模型经实验检验,其模型计算值与实验值数据吻合较好。
另外,新建立的由Prorapak Q填充柱和5A分子筛填充柱双柱串联,两次进TCD检测器的气相色谱分析方法,解决了需多次取样,在单一色谱柱中多次进样分析带来换算困难的难题和准确性,实现产品混合气一次进样即可进行组分的在线全分析。
The scale method for synthesis dimethyl ether (DME) is two-step method, ie. First, methanol is synthesized from the syngas, then the methanol dehydrate to DME. The process of two-step method for synthesis DME is not economic in kinetics and thermodynamics. The results from process by single-step synthesis DME in single reactor indicated:a double function catalyst had been increnced the conversion rate of CO and H2, but there is a problem that the activity temperature of synthesis methanol from syngas and methanol dehydration to DME is different in the catalyst system, and the activation of catalyst can not exert its catalysis maximum. Secondly, the basic material to synthesize cleanliness energy sources, DME, is from coal or nature gas, and it will consume the fossil energy sources in the Earth. But there are a large of tail gas contained high concentration CO to be discharge to air from the plant, which produce metal and nonmetallic with coal/coke or nature gas for reducer agent in the metallurgy and chemical industry, for example, yellow phosphorus tail gas, airproof calcium carbide tail gas, steel-making converter tail gas, oil refining tail gas, tail gas from portion oxidation of nature gas, copper wash relax gas of synthesis ammonia and so on. The usual treatment method about this kind tail gas is burning them and using portion heat, or burning by torch, which result is conversion the CO to CO2 to vent into air. How to using the invaluablener resource gas contained CO, reducing discharge, ease off the conflict of scarce energy sources and aggravating environment worsening, realizing saving energy and reducing pollution is very important in China.
There are summarized about the synthesis technique and reaction mechanism of DME at home and abroad to be discussed and the research harvest about technological progress and basic theory of single-step synthesis DME from syngas was presented emphatically in this paper. This thesis discuss the single-step process for synthesis DME by modified bifunctional the catalysis in a slurry reactor, using the simulation syngas with high rate of CO/H2 contained CO2 from the yellow phosphorus tail gas via portion water-shift. The research included the phosphorus modified of catalysis, optimization of the technology condition in a slurry reactor, and study of the process dynamics and thermodynamics.
A new modified bifunctional catalyst (C301/P-γ-Al2O3) is preparation with basic Cu (C301) catalyst for synthesis Methanol and modified dehydrate catalyst (P-γ-Al2O3) with H3PO4 dipping and calcinations. There are new O=P—O bond to be found in the modifiedγ-Al2O3 by analyse with FT-IR and X-ray diffraction, and it increase the pair acid-alkali in dehydrate catalyzer. And the modified bifunctional catalyst(C301/P-γ-Al2O3) enhance the capability of methanol conversion to DME, and increas the conversion rate of total Carbon and selectivity of DME, and restrain the by-reaction from CO to CO2.
A optimum technology reaction conditions are obtained after study the transfer and reaction condition with the modified bifunctional catalyst (C301/P-γ-Al2O3) in slurry bed, namely,250-270℃of system temperature,4.3MPa of the system pressure,600mL/h·gcat of space time, H2/(CO+CO2)≈1.5,150ml of the inert solvent,7.3% of the catalyst to the solvent,750r/min of the stirrer rotate speed. When the modified catalyst was used for synthesis DME in slurry bed reactor from the rich carbon syngas cantained CO2, the conversion rate of CO achieved 95.90% and selectivity of DME is 60%., which is outclass the 34.61% of the selectivity in using the non-modified catalyst system. And it is ture that the production ratio of CO2 is reduced evidently, the methanol is little or none in production system.
The relation equations about reaction heat and reaction balance constant with the system temperature were built by process thermodynamics analysis. The all reactions are exothermic reaction, and their balance constant will reduce when the reaction temperature increase, and the balance constant for methanol synthesis is most sensitivity, the CO/H2O shift reaction is secondly. The calculated value of total carbon and selectivity of DME are 72% and 95.4% by Matlab software from optimum equation about rich carbon syngas contained CO2 at 250℃, which closed to the experiment value. The calculate results prove single-step synthesis DME technology by P modified bifunctional catalyst (C301/P-y-Al2O3) from syngas contained CO2 will overcome the problem of the restriction of chemistry reaction balance.
The kinetics modeling basic rich carbon syngas contained CO2 synthesis DME with the modified bifunctional catalyst(C301/P-y-Al2O3) in slurry bed reactor can be express with the combination of reaction rate equations about:1)syngas to methanol,2) methanol dehydrate to DME, and 3) CO-H2O shift to CO2. The reaction process mechanism is that CO and CO2 all are the Carbon resource to synthesis Methanol, the middle process include: 1) adsorbed CO/CO2 convert to intermediate, formate, and it continuous add H with adsorbed OH/H to methanol; 2) adsorbed methanol and isolate adsorbed methanol convert to DME; 3) the by-reaction are form by formate deoxidized to CO2 and adsorbed H convert to H2.
The calculation data with kinetics model have a good inosculated with check-up by experimentation. It is be found that the CO2 in syngas can restrain the CO-H2O shift reaction, and increase the selectivity of DME. But excessive CO2 will be competed adsorption on the face of catlyzer with CO, and it will result the reaction rate decrease.
A new analysis system with GC for analyzing complexity production gas in the single-step synthesis DME system was built, which change the side-by-side double column to tandem Prorapak Q and molecule sieve filled column, and the sample pass though the TCD detector twice. The analysis system and method have solved the problem which need sampling and insert sample time after time in experiment, and the trouble for conversion data, and it is make the analyzing reaction gas quickly and easy on-line.
Anyway, using the resource for the tail gas contained high concentration CO to synthesis DME is an excellent path, which achieve saving energy, lowering energy consumption and reducing pollutants discharge. The modified of bifunctional catalyst by P can improved the matching temperature of the function group; and has a application worth practicality for synthesis DME from rich carbon syngas cantained CO2 in slurry bed; And the theorys about kinetics and thermodynamics have a guidance significance for scale in the industry.
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