synthesis gas production using steam hydrogasification and steam reforming
盐酸,甲醇,氯化苄生产工艺流程
盐酸,甲醇,氯化苄生产工艺流程The production process of hydrochloric acid, methanol, and benzyl chloride is a complex and important industrial process that involves several steps. Hydrochloric acid is typically produced by the reaction of salt and sulfuric acid, while methanol is usually derived from the synthesis gas produced from natural gas. Benzyl chloride, on the other hand, is typically produced by the chlorination of benzene. Each of these processes requires careful attention to detail and strict adherence to safety protocols to ensure the highest quality and purity of the final product.盐酸、甲醇和氯化苄的生产工艺流程是一个复杂而重要的工业过程，涉及多个步骤。
通常，盐酸是通过盐和硫酸的反应产生的，而甲醇通常来自于天然气产生的合成气体。
另一方面，氯化苄通常是通过苯的氯化反应产生的。
这些过程每一个都需要仔细的注意细节和严格遵守安全协议，以确保最终产品的最高质量和纯度。
The production of hydrochloric acid involves the reaction of salt (sodium chloride) with sulfuric acid to produce hydrogen chloride gas. This gas is then dissolved in water to form hydrochloric acid. Thereaction between salt and sulfuric acid is exothermic, meaning it releases heat, so careful control of temperature is required to prevent overheating and ensure a safe and efficient reaction.盐酸的生产涉及盐（氯化钠）和硫酸的反应，产生氯化氢气体。
PROII常用热力学方程的选择
PROII常用热力学方程的选择SRK方程：用于气体及炼油过程，可计算K值，焓，熵，气体密度，液体密度（不好），通常不用于高度非理想体系，支持自由水，不支持VLLE。
PR方程：主炼油过程，可计算K值，焓，熵，气体密度，不适用于高度非理想体系，支持自由水，不支持VLLE。
修正的SRK及PR方程：可计算K值，焓，熵，气体密度，适用于非理想体系，不支持自由水，可用于VLLE。
Uniwaals方程：可计算K值，焓，熵，气液体密度，如果基团贡献参数由数据库或用户提供时，可很好地用于高度非理想体系。
用于低中压系统，不支持自由水，支持VLLE。
BWRS方程：可计算K值，焓，熵，气液体密度，可用于炼油厂的轻重烃组分。
但不支持严格的双液相行为。
支持自由水，不支持VLLE。
六聚物方程：适用于HF烷基化及致冷剂合成，可计算K值，焓，熵，气体密度，支持严格的双液相行为。
适用于仅一个六聚物组分且无水。
LKP方程：可计算K值，焓，熵，气液体密度，主要用于轻烃及含大量氢气的重整系统。
可用于VLLE 体系，不适用于自由水。
NRTL液体活度方程：用于VLE或VLLE体系，不支持自由水。
通常用于非理想体系，特别是不混合体系。
用于计算K值。
Uniquac液体活度方程：用于VLE或VLLE体系，不支持自由水。
通常用于高度非理想体系，特别是不混合体系。
用于计算K值。
Unifac液体活度方程：用于VLE或VLLE体系，不支持自由水。
Unifac基团贡献法通常用于低压、非理想体系。
通常限制组分少于１０，或较少的基团，且系统含有低分子量的聚合物。
计算K值。
修正的Unifac液体活度方程：用于VLE或VLLE体系，不支持自由水。
Unifac基团贡献法通常用于低压、非理想体系。
通常限制组分少于１０，或较少的基团，且系统含有低分子量的聚合物。
计算K值。
Wilson方程：用于VLE体系，不支持自由水。
适用于轻度非理想体系。
计算K值。
Van laar方程：用于VLE及VLLE体系，不支持自由水。
催化生物质气化制氢英文
催化生物质气化制氢英文The biomass gasification for hydrogen production is a process that involves converting biomass into hydrogen gas through a series of chemical reactions. This is achieved through a thermochemical process called gasification, which involves heating the biomass in a controlled environment with a restricted air supply to produce a mixture of hydrogen, carbon monoxide, carbon dioxide, and methane.The gasification process can be catalyzed by using various catalysts, such as nickel, cobalt, or iron-based catalysts, to improve the efficiency and selectivity of the reactions. These catalysts can help in breaking down the biomass into smaller molecules and promoting the formation of hydrogen gas.The biomass feedstock used for gasification can include a variety of organic materials, such as wood, agricultural residues, energy crops, and municipal solid waste. These feedstocks are first dried and then converted into a gaseous mixture of hydrogen and other gases through the gasification process.The produced gas, also known as syngas, can be further processed to separate and purify the hydrogen gas. This can be achieved through processes such as water-gas shift reaction, pressure swing adsorption, or membrane separation to obtain high-purity hydrogen gas.The hydrogen gas produced from biomass gasification can be used for various applications, including fuel cells, industrial processes, and transportation. It is considered a sustainable and renewable energy source since biomass feedstock can be replenished through agricultural and forestry practices.In conclusion, biomass gasification for hydrogen production is a promising technology that can help in the transition towards a sustainable energy future. Byutilizing biomass as a feedstock, this process can provide a renewable and environmentally friendly source of hydrogen gas.生物质气化制氢是一种通过一系列化学反应将生物质转化为氢气的过程。
中压法合成甲醇工艺流程
中压法合成甲醇工艺流程英文回答：The process of methanol synthesis using the medium pressure method involves several steps. First, natural gas or methane is converted into synthesis gas, which is a mixture of carbon monoxide and hydrogen. This can be done through steam reforming or partial oxidation of methane. Steam reforming involves reacting methane with steam in the presence of a catalyst to produce carbon monoxide and hydrogen. Partial oxidation, on the other hand, involves reacting methane with oxygen or air to produce carbon monoxide and hydrogen.Once the synthesis gas is obtained, it is then subjected to the methanol synthesis step. This step involves the reaction of carbon monoxide and hydrogen in the presence of a catalyst, typically a copper-based catalyst, at high pressure and temperature. The reaction is exothermic, meaning it releases heat. The catalyst helps tofacilitate the reaction and increase the rate of methanol formation.After the methanol synthesis step, the crude methanol is obtained. This crude methanol contains impurities and needs to be purified. The purification process involves several steps, including distillation, absorption, and catalytic conversion. Distillation is used to separate methanol from other components, while absorption helps to remove impurities such as water and higher alcohols. Catalytic conversion is then used to remove traceimpurities and improve the purity of the methanol.Finally, the purified methanol can be further processed or used as a fuel or chemical feedstock. It can be used as a fuel in vehicles or as a raw material for the production of formaldehyde, acetic acid, and other chemicals.中文回答：中压法合成甲醇工艺流程涉及几个步骤。
沼气制甲醇工艺流程
沼气制甲醇工艺流程英文回答：The process of producing methanol from biogas involves several steps. First, the biogas, which is primarily composed of methane (CH4) and carbon dioxide (CO2), is purified to remove impurities such as hydrogen sulfide (H2S) and moisture. This is typically done using a scrubbing system or activated carbon filters.Once the biogas is purified, it is then converted into synthesis gas, or syngas, through a process called steam reforming. In this process, the biogas is mixed with steam and heated to high temperatures, typically around 800-900 degrees Celsius, in the presence of a catalyst. This causes the methane in the biogas to react with steam, producing carbon monoxide (CO) and hydrogen (H2).The next step is the conversion of syngas into methanol. This can be done through catalytic synthesis, where thesyngas is passed over a catalyst, typically a mixture of copper, zinc, and aluminum oxides. The catalyst promotes the reaction between carbon monoxide and hydrogen to form methanol (CH3OH). The reaction takes place at high pressures and temperatures, typically around 50-100 atmospheres and 200-300 degrees Celsius.After the methanol is produced, it needs to be purified to remove any impurities. This is typically done through distillation, where the methanol is heated and the vapors are condensed and collected. The distillation process helps separate the methanol from any remaining water, as well as any other byproducts or impurities.Once the methanol is purified, it can be used as a fuel or as a chemical feedstock for the production of other chemicals. It is a versatile compound that has many applications, including as a solvent, antifreeze, and as a raw material for the production of plastics, paints, and pharmaceuticals.中文回答：制取甲醇的沼气工艺涉及几个步骤。
合成气制二甲醚工艺流程
合成气制二甲醚工艺流程（中英文实用版）英文文档：Synthesis Gas to Dimethyl Ether Process FlowThe synthesis gas to dimethyl ether (DME) process is a significant industrial method for converting synthetic gas, a mixture of carbon monoxide and hydrogen, into DME, a clean-burning alternative fuel.This process involves several key steps, including syngas production, purification, conversion to DME, and product recovery.The first step in the process is the production of syngas, which is typically generated from natural gas, coal, or biomass through steam reforming or other gasification processes.Once produced, the syngas is cleaned and purified to remove impurities such as carbon dioxide, water, and sulfur compounds.The purified syngas is then reacted with carbon monoxide in a catalytic conversion process to produce dimethyl ether.This reaction is typically carried out in a fixed-bed or fluidized-bed reactor using catalysts such as zeolites or metal complexes.The choice of catalyst and reaction conditions can significantly affect the yield and quality of the DME product.After the conversion step, the DME is separated from the reactor effluent and further purified.This involves removing any remainingsyngas components, water, and impurities.The purified DME is then dried and compressed for storage or transportation as a liquid or gas.Finally, the process includes waste heat recovery and environmental controls to minimize energy consumption and ensure compliance with emission standards.The overall efficiency and economics of the synthesis gas to DME process depend on the scale of the facility, the cost of feedstocks, and the market value of the DME product.中文文档：合成气制二甲醚工艺流程合成气制二甲醚（DME）工艺是将合成气（一氧化碳和氢气的混合物）转化为清洁燃烧替代燃料的关键工业方法。
天然气合成氨流程图的简介
天然气合成氨流程图的简介The process of synthesizing ammonia from natural gas involves several key steps that are essential for ensuring a high level of efficiency and productivity. 天然气合成氨的过程涉及几个关键步骤，这些步骤对于确保高效率和生产力至关重要。
First and foremost, the raw material, natural gas, is subjected to a process known as steam reforming. Natural gas contains methane, and during steam reforming, it is reacted with steam at high temperatures to produce a mixture of hydrogen and carbon monoxide. 首先，原材料天然气经过一种称为蒸汽重整的过程。
天然气含有甲烷，在蒸汽重整过程中，它会在高温下与蒸汽反应，产生氢和一氧化碳的混合物。
Following steam reforming, the resulting mixture of hydrogen and carbon monoxide is then subjected to a process called the shift reaction. During this stage, the mixture is reacted with steam to convert the carbon monoxide into carbon dioxide and to increase the concentration of hydrogen. 在蒸汽重整后，产生的氢和一氧化碳的混合物随后要经过一种称为转移反应的过程。
gaussview练习题
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磷酸酯的水解反应（碱性条件下，未加催化剂）的反应路径 RC 表示反应物，TS 表示过渡态，PC 表示产物，IM 为反应中间体，括号内为能量值（单位： 卡） ，1 和 2 表示该反应的两种反应路径。 催化剂催化
NH 2
HO
NH 2 NH 2
01 SiH2+H2的分子结构说明部分 Blank line 12、运用过渡态理论研究下列反应的机理：
HCN HNC
13、烯烃的环丙烷化反应机理研究
LiCH2F +
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Li CH2
H2 C
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H2C
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14、磷酸酯水解机理研究，通过寻找过渡态，对可能的反应路径进行 比较，并做一些合理的解释；运用 GaussView 构造催化剂分子。
11、 预测下面反应的过渡态结构， 比较过渡态与反应物的 Si-H 和 H-H 的键长。
SiH4 SiH2 + H2
Step1：优化SiH4 的结构 Step2：优化SiH2+H2 的结构 Step3：找寻过渡态 # hf/6-31g* opt(qst2，addredundant) Blank line SiH4 reactant Blank line 01 SiH4的分子结构说明部分 Blank line SiH2+H2 Blank line products
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合成氨主要工艺流程的三个基本步骤
合成氨主要工艺流程的三个基本步骤英文回答：The three basic steps in the main process of ammonia synthesis are as follows:Step 1: Synthesis gas production.The first step involves the production of synthesis gas, which is a mixture of hydrogen and nitrogen. The most common method for producing synthesis gas is the steam reforming of natural gas. In this process, natural gas is reacted with steam in the presence of a catalyst to produce hydrogen and carbon monoxide. The carbon monoxide is then further reacted with steam in a water-gas shift reaction to produce additional hydrogen and carbon dioxide. Finally,the carbon dioxide is removed through a purification process, leaving behind a mixture of hydrogen and nitrogen.Step 2: Ammonia synthesis.In the second step, the synthesis gas is fed into a reactor where it undergoes the ammonia synthesis reaction. This reaction is typically carried out at high pressure (100-250 bar) and moderate temperature (300-500°C). The synthesis gas reacts with a catalyst, usually based on iron or ruthenium, to produce ammonia. The reaction is exothermic, meaning that it releases heat, and is reversible. As a result, the reaction is typically operated at high pressure to favor the formation of ammonia. The ammonia synthesis reaction can be represented by the following equation:N2 + 3H2 ⇌ 2NH3。
Fischer-Tropsch process
1.1Fischer-Tropsch(FT)ProcessCoal and natural gas can be utilized as feedstock of the chemical industry and the transportation fuels market.The conversion of natural gas to hydrocarbons(Gas-To-Liquids route)is currently one of the most promising topics in the energy industry due to economic utilization of remote natural gas to environmentally clean fuels,specialty chemicals and waxes.Alternatively,coal or heavy residues can be used on sites where these are available at low costs.The resources of coal and natural gas are very large, see Table1.1.Coal and natural gas can be converted into synthesis gas,a mixture of predominantly CO and H2,by either partial oxidation or steam reforming processes. Possible reactions of synthesis gas are shown in Figure1.1.Natural gasCoalFigure1.1Possible reactions from synthesis gas.Table1.1World fossil fuel reserves and consumption(EJ,1018J)[1].Coal(1991)271856991Crude oil(1992)605414367Natural gas(1992)451279442C HAPTER1Table1.2Major overall reactions in the Fischer-Tropsch synthesis.Side reactions4.Alcohols2n H2+n CO C n H2n2O+n1H2O5.Boudouard reaction2CO C+CO2The conversion of the synthesis gas to aliphatic hydrocarbons over metal catalysts was discovered by Franz Fischer and Hans Tropsch at the Kaiser Wilhelm Institute for Coal Research in M¨u llheim in1923[2,3].They proved that CO hydrogenation over iron,cobalt or nickel catalysts at180-250˚C and atmospheric pressure results in a product mixture of linear hydrocarbons.The Fischer-Tropsch product spectrum con-sists of a complex multicomponent mixture of linear and branched hydrocarbons and oxygenated products.Main products are linear paraffins and-olefins.The overall reactions of the Fischer-Tropsch synthesis are summarized in Table1.2.The hydro-carbon synthesis is catalyzed by metals such as cobalt,iron,and ruthenium.Both iron and cobalt are used commercially these days at a temperature of200to300˚C and at 10to60bar pressure[4,5].The reactions of the FT synthesis on iron catalysts can be simplified as a combi-nation of the FT reaction and the water gas shift(WGS)reaction:CO1m2n H21n C n H m H2O F T-H FT=165kJ/mol(1.1) CO H2O CO2H2W GS-H W GS=41.3kJ/mol(1.2)where n is the average carbon number and m is the average number of hydrogen atoms of the hydrocarbon products.Water is a primary product of the FT reaction,and CO2 can be produced by the WGS reaction.The WGS activity can be high over potassium-promoted iron catalysts and is negligible over cobalt or ruthenium catalysts.I NTRODUCTION3Figure1.2shows a block diagram of the overall Fischer-Tropsch process config-uration.The commercial process involves three main sections,namely:synthesis gas production and purification,Fischer-Tropsch synthesis,and product grade-up.These subjects are described in more detail below.Choi et al.[6]gives a capital cost break-down of these three individual process sections for a45,000bbl/day FT plant.The synthesis gas preparation(that is air separation plant,partial oxidation,steam reform-ing of natural gas,and syngas cooling)is about66%of the total on-site capital costs. The FT synthesis section consisting of FT slurry reactors,CO2removal,synthesis gas compression and recycle,and recovery of hydrogen and hydrocarbons is22%of the total costs.Finally,the upgrading and refining section of hydrocarbons is about12 %.Consequently,cost reduction of synthesis gas production is the most beneficial. Note,however,that at afixed production rate the selectivity of the FT process directly affects the size of the syngas generation section.A high selectivity of the FT process to desired products is of utmost importance to the overall economics.1.1.1Synthesis Gas ProductionSynthesis gas can be obtained by steam reforming or(catalytic)partial oxidation of fossil fuels:coal,natural gas,refinery residues,biomass or industrial off-gases.The composition of syngas from the various feedstocks and processes is given in Table1.3 [7,8].Synthesis gas can be obtained from reforming of natural gas with either steam or carbon dioxide,or by partial oxidation.The most important reactions are:Steam reforming CH4+H2O CO+3H2CO2reforming CH4+CO22CO+2H2Partial oxidation CH4+14C HAPTER1Figure1.2Overall process scheme Fischer-Tropsch.I NTRODUCTION5 Table1.3Synthesis gas compositions.Natural gas,steam SR173.815.56641 Natural gas,steam,CO2CO2-SR252.326.185131 Natural gas,O2,ATR260.230.27520 steam,CO2Coal/heavy oil,steam Gasification167.828.72906 Coal,steam,oxygen Texaco gasifier135.151.810625 Coal,steam,oxygen Shell/Koppers gasifier130.166.12513 Coal,steam,oxygen Lurgi gasifier339.118.92971236C HAPTER 10.4NaturalFigure 1.3Feedstocks and catalysts [10].for development of commercial Fischer-Tropsch reactors are the high reaction heats and the large number of products with varying vapor pressures (gas,liquid,and solid hydrocarbons).The main reactor types which have been proposed and developed after 1950are [5,15,16]:1.Three-phase fluidized (ebulliating)bed reactors or slurry bubble column reac-tors with internal cooling tubes (SSPD:Sasol;GasCat:Energy International,AGC-21:Exxon,see Figure 1.4a)2.Multitubular fixed bed reactor with internal cooling (Arge:Sasol;SMDS:Shell,see Figure 1.4b)3.Circulating fluidized bed reactor with circulating solids,gas recycle and cooling in the gas/solid recirculation loop (Synthol:Sasol)(Figure 1.4c)4.Fluidized bed reactors with internal cooling (SAS:Sasol)(Figure 1.4d)Sie [5]compared the advantages and disadvantages of the two most favorite reactor systems for the Fischer-Tropsch synthesis of high molecular weight products:that is the multitubular trickle bed reactor and the slurry bubble column reactor.Major drawbacks of the bubble column are requirements for continuous separation betweenI NTRODUCTION7 coolant8C HAPTER11.1.3Product Upgrading and SeparationConventional refinery processes can be used for upgrading of Fischer-Tropsch liquid and wax products.A number of possible processes for FT products are:wax hydro-cracking,distillate hydrotreating,catalytic reforming,naphta hydrotreating,alkylation and isomerization[6,20].Fuels produced with the FT synthesis are of a high quality due to a very low aromaticity and zero sulfur content.The product stream consists of various fuel types:LPG,gasoline,diesel fuel,jet fuel.The definitions and conventions for the composition and names of the different fuel types are obtained from crude oil refinery processes and are given in Table1.4.Table1.4Conventions of fuel names and composition[1].Fuel gas C1-C2LPG C3-C4Gasoline C5-C12Naphtha C8-C12Kerosene Jet fuel C11-C13Diesel Fuel oil C13-C17Middle distillates Light gas oil C10-C20Soft wax C19-C23Medium wax C24-C35Hard wax C35I NTRODUCTION9 Table1.5Product quality,adapted from Sie[5]and Gregor[22].Diesel Cetane number7074min.40Cloud point,˚C-10-7-20to+201.2Industrial Fischer-Tropsch ProcessesBelow,the major industrial Fischer-Tropsch processes are discussed briefly.The em-phasis is on processes developed after1980.Table1.6gives an overview of the major companies and their patents divided in the following sections:1.FT catalyst devel-opment;2.process design and development;3.upgrading of specific FT products.A comparison of the several industrial Fischer-Tropsch companies is presented in Ta-ble1.7.Table1.6Estimate of patents of the major companies active in Fischer-Tropsch(April 1998).BP1340Exxon71155Rentech180Sasol233Shell452713Statoil531Syntroleum01010C HAPTER1Table1.7Comparison of the major companies active in Fischer-Tropsch(October1998).Energy Int.PO with O2slurry-CoExxon CPO(O2)slurry200Co Rentech PO with O2,SR,ATR slurry235FeSasol PO with O2,SR,slurry2,500Fe,Cocoal gasificationfluidized110,000Shell2PO with O2fixed12,500Co Syntroleum ATR with airfixed2Cowas dismantled and transported to Arunachal,India were it is expected to produce 350bbl/day of waxes in1999in cooperation with the Indian company Donyi Polo Petrochemicals Ltd.SasolSasol has operated commercial Fischer-Tropsch plants since1955.A detailed review of Sasol’s commercial plants from1950to1979is given by Dry[32].A commercial plant in Sasolburg(South Africa)(Sasol1)use multitubular(2050tubes,50mm ID)fixed bed and entrained bed Kellogg reactors.Synthesis gas is predominantly pro-duced with Lurgi coal gasifiers.Sasol2and Sasol3plants in Secunda went on stream in the beginning of the eighties.These plants use circulatingfluidized bed reactors (Synthol,Figure1.4c)for the production of fuels and low molecular weight olefins. Currently,Sasol has two new processes for the Fischer-Tropsch synthesis.A process at high temperatures(HTFT:330-350˚C)for the production of gasoline and light olefins and a process for wax production at lower temperatures(LTFT:220-250˚C). The HTFT is performed in Synthol circulatingfluidized bed(CFB)reactors,but a more efficient Sasol Advanced Synthol(SAS)reactor with gas-solidfluidization was devel-oped recently[16].The Synthol reactors will be replaced by the new SAS reactors. Conventionally,ARGE tubularfixed bed reactors were used for the LTFT process. In1990,a slurry bubble column reactor(Sasol Slurry Phase Distillate;SSPD)with a diameter of1m was commissioned[15].A commercial-scale slurry reactor is in operation since1993and has a diameter of5m and a height of22m with a capacity of about2,500bbl/day.Table1.8shows an overview of different Sasol reactors[15,19]. Further scale up of the SSPD reactor is planned to20,000bbl/day per reactor.Table1.8Sasol Fischer-Tropsch commercial reactors(bbl/day),adapted from Jager[19].Total installed capacity1100001100032002500 Capacity per reactor650011000500-7002500Potential per reactor750020000300020000technology in Nigeria.The estimated cost price of this complex is$500-600million (Remote Gas Strategies,May1998).Most patents of Sasol(see Table1.6)concern the development of a slurry reactor with continuous in-situ wax-solid separation[33]and grade-up of olefins by hydroformulation[34].ShellIn1993,Shell started up a$850million FT synthesis plant in Bintulu,Malaysia.The Shell Middle Distillate Synthesis(SMDS)process[5,35]produces heavy paraffins on a cobalt catalyst in multitubular trickle bed reactors.Part of these products are sold as wax specialties;another part is hydro-cracked over a noble metal catalyst into clean transportation fuels(see Table1.5).The plant converts100million cubic feet/day of natural gas from off-shorefields by non-catalytic partial oxidation into12,500bbl/day hydrocarbons.The air separation plant of the SMDS plant in Bintulu exploded in December1997.Shell Oil wants to reopen the SMDS plant in1999(Remote Gas Strategies,April1998).Most Shell patents focus on either catalyst development or on the way the SMDS process is preferably carried out,for example,see patents[36,37]. Some patents for improving a slurry process have beenfiled as well[38–40].StatoilPatents of Statoil involve slurry reactor design and continuous catalyst-wax separations with the use offiltration[41].Recent patents with respect to Fischer-Tropsch catalysis concern the development of cobalt catalysts promoted with Rh,Pt,Ir,or Re on alumina (for example,[42]).Statoil formed an alliance with Sasol for the development of floating Fischer-Tropsch plants on ships orfloating production systems.Thesefloating off-shore plants can be used to utilize natural gas associated with oil production[43].SyntroleumSyntroleum is a small researchfirm in Tulsa,Oklahoma,USA,which has signed li-censing agreements with Texaco,ARCO,Kerr-McGee,and Enron.A laboratory pilot plant(2bbl/day)is used to demonstrate their FT process.They claim that their pro-cess eliminates a costly air separation unit,since their Autothermal Reformer(ATR) produces nitrogen-diluted synthesis gas from natural gas[44].Nitrogen can be used to remove some of the generated heat during the FT reaction.The Syntroleum process is the basis of an agreement between Texaco,Brown&Root and Syntroleum to developa2,500bbl/day GTL plant,starting end1999(Remote Gas Strategies,January1998). Recently,Syntroleum and Enron announcedfinal agreement to build a8,000bbl/day GTL plant in Wyoming,USA.The plant is expected to operate in2001[45].1.3Research on the Fischer-Tropsch SynthesisAn optimal design with respect to product yield and selectivity of a large scale reactor requires a deep understanding of hydrodynamics,reaction kinetics,catalytic system and FT chemistry(see Figure1.5).Research on the various aspects of the FT process will be discussed briefly.A detailed review on kinetics and selectivity of the Fischer-Tropsch process is given in Chapter2.Figure1.5Modeling of a large scale Fischer-Tropsch reactor.Reaction KineticsThe complexity of the FT reaction mechanism and the large number of species in-volved is the major problem for development of reliable kinetic expressions.Most catalyst studies aim at catalyst improvement and postulate empirical power law kinet-ics for both the carbon monoxide conversions and the carbon dioxide formation rate [46,47].Langmuir-Hinshelwood-Hougen-Watson(LHHW)type of rate equations have been applied in literature(see Chapter2.8).The water gas shift reaction can play a dominant role on iron catalysts.Only a few studies report on WGS kinetics oniron catalysts under FT conditions.A thorough comparison of the available literature models is presented in Chapter2.Product SelectivityThe products from the Fischer-Tropsch synthesis form a complex multicomponent mixture with substantial variation in carbon number and product type.Main products are linear paraffins and-olefins.According to Anderson[48],the product distribu-tion of hydrocarbons can be described by the Anderson-Schulz-Flory(ASF)equation: m n1n1with m n the mole fraction of a hydrocarbon with chain length n and the growth probability factor independent of n.determines the total carbon number distribution of the FT products.The range of depends on reaction condi-tions and catalyst type.Dry[49]reported typical ranges of on Ru,Co,and Fe of: 0.85-0.95,0.70-0.80,and0.50-0.70,respectively.More recent references report Co catalysts with chain growth factors between0.85-0.95[5].Significant deviations from the ASF distribution are reported in literature:i)Relatively high yield of methane.ii) Relatively low yield of ethene.iii)Change in chain growth parameter and expo-nential decrease of the olefin to paraffin ratio with increasing carbon number.These deviations are predominantly caused by secondary reactions of-olefins,which may readsorb on growth sites of the catalyst surface and continue to grow via propagation with monomer or terminate as hydrocarbon product.Details on the characteristics of the product selectivity and on modeling of the selectivity are discussed in Chapter2. Reactor Engineering ModelMathematical modeling of FT slurry bubble columns was reviewed by Saxena et al.[17]and more recently by Saxena[50].He showed that none of the available mod-els is accurate enough for a reliable reactor design.The bottleneck appears to be the lack of reliable kinetic equations for all products and reactants based on realistic re-action mechanisms.Until now,none of the available literature models obtain enough details to describe the complete product distribution of the Fischer-Tropsch synthesis at industrial conditions(high temperature and pressure)as a function of overall con-sumption of synthesis gas components and operating conditions.Either the product distribution model(ASF behavior)or the kinetic scheme(no WGS and rates equa-tions withfirst order in hydrogen)is oversimplified,or the hydrodynamic situation is unrealistic under industrial(churn-turbulent or heterogeneousflow regime)operating conditions.The features of the models available will be compared in Chapter7.1.4Aims and Outline of this ThesisThe problem to be dealt with in this thesis is the lack of accurate models for prod-uct distributions and reaction kinetics,necessary for reliable design and scale up of industrial Fischer-Tropsch processes.Therefore,the major aim of this thesis is the development of a product distribution model and a kinetic model both in gas-slurry as well as in gas-solid reactors over a commercial precipitated iron catalyst based on own experimental work.The product distribution model should be able to explain the deviations from the ASF distribution observed experimentally.It should include a mechanistic model of olefin readsorption and kinetics of chain growth and termination on the same catalytic sites.Accurate intrinsic rate expressions for the CO conversion to Fischer-Tropsch products and for the water gas shift(WGS)reaction over a precipitated iron catalyst on the basis of reliable mechanisms are another aim.A detailed multicomponent mathematical model for a large scale slurry bubble column reactor with use of our detailed models is the final aim of this thesis.Chapter2presents a literature review on the kinetics and selectivity of the Fischer-Tropsch synthesis.The focus is on the reaction mechanisms and kinetic models of the water gas shift and Fischer-Tropsch reactions.Literature product selectivity models are reviewed as well.Here the areas which require further research will be defined.Chapter3describes the experimental setup of the kinetic experiments both in a gas-solid and gas-slurry laboratory kinetic reactor and the catalyst applied.The ana-lytical section and the experimental procedures are described as well.The development of a new-Olefin Readsorption Product Distribution Model (ORPDM)based on own experiments for the gas-solid FT synthesis,over a precip-itated iron catalyst is presented in Chapter4.The effect of variation of process condi-tions on the selectivity is described as well.Chapter5presents the kinetic experiments and kinetic modeling of the CO hydro-genation and the water gas shift reaction of gas-solid Fischer-Tropsch synthesis over the precipitated iron catalyst.The influence of the slurry liquid on the product selectivity and the reaction ki-netics is presented in Chapter6.The product selectivity model developed for the gas-solid system will be applied for the description of the product selectivity at in-dustrially relevant conditions over a precipitated iron catalyst suspended in the slurry phase.Furthermore,Chapter6describes kinetic modeling of the gas-slurry Fischer-Tropsch synthesis based on a methodology derived in Chapter5.The models obtained in Chapters4-6and literature data on hydrodynamics and mass transfer in the heterogeneousflow regime are incorporated in a multicomponent reaction engineering model for a large scale Fischer-Tropsch slurry bubble column reactor in Chapter7.The main novel aspect of this model is that,for thefirst time, multicomponent vapor-liquid equilibria with detailed kinetic expressions for all reac-tants and products(based on original experimental work)are combined to predict the compositions of the gaseous and liquid streams and the performance of a slurry bubble column reactor.References[1]Kroschwitz,I.;Howe-Grant,M.,Kirk-Othmer encyclopedia of chemical tech-nology,Wiley&Sons,New York,fourth edn.1996.[2]Fischer,F.;Tropsch,H.,Uber die Herstellung synthetischer¨o lgemische(Syn-thol)durch Aufbau aus Kohlenoxyd und Wasserstoff,Brennst.Chem.1923,4, 276–285.[3]Fischer,F.;Tropsch,H.,German Patent4843371925.[4]Jager,B.;Espinoza,R.,Advances in low-temperature Fischer-Tropsch synthesis,Catal.Today1995,23,17–28.[5]Sie,S.T.,Process development and scale up:IV Case history of the developmentof a Fischer-Tropsch synthesis process,Rev.Chem.Eng.1998,14,109–157. [6]Choi,G.N.;Kramer,S.J.;Tam,S.T.;Fox,J.M.,Design/economics of a naturalgas based Fischer-Tropsch plant,in Spring National Meeting,American Institute of Chemical Engineers,Houston,1996.[7]Cybulski, A.;Edvinsson,R.;Irandoust,S.;Andersson, B.,Liquid-phasemethanol synthesis:modelling of a monolithic reactor,Chem.Eng.Sci.1993, 48,3463–3478.[8]Perry,R.H.;Green,D.,Perry’s chemical engineers‘handbook,McGraw-Hill,New York,6th edn.1984.[9]Basini,L.;Piovesan,L.,Reduction on synthesis gas costs by decrease ofsteam/carbon and oxygen/carbon ratios in the feedstock,Ind.Eng.Chem.Res.1998,37,258–266.[10]Rentech,Gas to liquids home page,/tech2.htm(ac-cessed December1998).[11]Rao,V.U.S.;Stiegel,G.J.;Cinquegrane,G.J.;Srivastave,R.D.,Iron-based cat-alysts for slurry-phase Fischer-Tropsch process:Technology review,Fuel Pro-cess.Technol.1992,30,83–107.[12]Xu,L.;Bao,S.;R.J.,O’Brien;Raje,A.;Davis,B.H.,Don’t rule out iron catalystsfor Fischer-Tropsch synthesis,CHEMTECH1998,8,47–53.[13]Raje,A.P.;Davis,B.H.,Fischer-Tropsch synthesis:process considerations basedon performance of iron-based catalysts,Fuel1997,76,273–280.[14]Udovich,C.A.,Ceramic membrane reactors for the conversion of natural gas tosyngas,Stud.Surf.Sci.Catal.1998,119,417–422.[15]Jager,B.,Developments in Fischer-Tropsch technology,Stud.Surf.Sci.Catal.1997,107,219–224.[16]Jager,B.;Dry,M.E.;Shingles,T.;Steynberg,A.P.,Experience with a new typeof reactor for Fischer-Tropsch synthesis,Catal.Lett.1990,7,293–302. [17]Saxena,S.C.;Rosen,M.;Smith,D.N.;Ruether,J.A.,Mathematical modeling ofFischer-Tropsch slurry bubble column reactors,mun.1986,40, 97–151.[18]De Swart,J.W.A.,Scale-up of a Fischer-Tropsch reactor,Ph.D.thesis,Univer-sity of Amsterdam,Amsterdam,The Netherlands1996.[19]Jager,B.,Developments in Fischer-Tropsch technology,Stud.Surf.Sci.Catal.1998,119,25–34.[20]Choi,G.N.;Kramer,S.J.;Tam,S.T.;Fox,J.M.;Carr,N.L.;Wilson,G.R.,De-sign/economics of a once-through natural gas based Fischer-Tropsch plant with power co-production,in Coal liquefaction and solid fuels,Pittsburgh,1997. [21]Fox,III,J.M.,The different catalytic routes for methane valorization:an assess-ment of processes for liquid fuels,Catal.Rev.-Sci.Eng.1993,35,169–212. [22]Gregor,J.H.,Fischer-Tropsch products as liquid fuels or chemicals.An econom-ical evaluation,Catal.Lett.1990,7,317–332.[23]Singleton,A.H.,Advances make gas-to-liquids process competitive for remotelocations,Oil Gas J.1997,68–72.[24]Eisenberg,B.;Fiato,R.A.;Mauldin,C.H.;Say,G.R.;Soled,S.L.,Exxon’s ad-vanced gas-to-liquids technology,Stud.Surf.Sci.Catal.1998,119,943–948. [25]Davis,B.H.,Fischer-Tropsch conversion of gas to liquid,Appl.Catal.A1997,155,N4–N7.[26]Behrmann,W.C.;Mauldin,C.H.;Pedrick,L.E.,Patent WO94147351994,Exxon.[27]Koros,R.B.,US Patent53843361995,Exxon.[28]Benham,C.B.;Bohn,M.S.;Yakobson,D.L.,US Patent55041181996,Rentech.[29]Benham,C.B.;Bohn,M.S.;Yakobson,D.L.,US Patent56206701997,Rentech.[30]Benham,C.B.;Bohn,M.S.;Yakobson,D.L.,US patent56211551997,Rentech.[31]Benham,C.B.;Bohn,M.S.;Yakobson,D.L.,US Patent55344371996,Rentech.[32]Dry,M.E.,The Fischer-Tropsch synthesis,in J.R.Anderson;M.Boudart,eds.,Catalysis-Science and technology,vol.1,Springer-Verlag,New York,1981pp.160–255.[33]Inga,J.R.;Jager,B.;Kelfkens,R.C.;Malherbe,F.E.J.;Smith,M.A.;Steynberg,A.P.,Eur.Patent609079,US patent55998491994,Sasol.[34]Betts,M.J.Dry,M.E.;Geertsema,A.;Rall,G.J.H.,Patent WO97015211997,Sasol.[35]Sie,S.T.;Senden,M.M.G.;Van Wechum,H.M.H.,Conversion of natural gas totransportation fuels via the Shell Middle Destillate Synthesis process(SMDS), Catal.Today1991,8,371–394.[36]Bode,D.;Sie,S.T.,Eur.Patent1883041986,Shell.[37]Post,M.F.M.;Sie,S.T.,Eur.Patent1672151984,Shell.[38]Engel,D.C.;Van der Honing,G.,Patent WO97316931997,Shell.[39]Wijn,E.F.;Danckaarts,A.M.,Eur.Patent6943251996,Shell.[40]McEwan,M.W.;Teekens,M.B.,US Patent6943251978,Shell.[41]Lorentzen,G.B.;Myrstad,T.;Westvik,A.,US Patent55208901995,Statoil.[42]Eri,S.;Goodwin,J.G.;Marcelin,G.;Riis,T.,US Patent48015731989,Statoil.[43]Statoil,Press release April14,1997.[44]Agee,K.L.;Willingham,F.Y.,WO Patent97338471997,Syntroleum.[45]Syntroleum,Press release February24,1998.[46]Bub,G.;Baerns,M.,Prediction of the performance of catalyticfixed bed reactorsfor Fischer-Tropsch synthesis,Chem.Eng.Sci.1980,35,348–355.[47]Newsome,D.S.,The water-gas shift reaction,Catal.Rev.-Sci.Eng.1980,21,275–318.[48]Anderson,R.B.,Catalysts for the Fischer-Tropsch synthesis,vol.4,Van Nos-trand Reinhold,New York1956.[49]Dry,M.E.,Catalytic aspects of industrial Fischer-Tropsch synthesis,J.Mol.Catal.1982,17,133–144.[50]Saxena,S.C.,Bubble column reactors and Fischer-Tropsch synthesis,Catal.Rev.-Sci.Eng.1995,37,227–309.。
甲烷转化工程流程图,并叙述
甲烷转化工程流程图,并叙述英文回答：Methane conversion is a complex process that involves several steps to convert methane gas into useful products. The process typically includes the following steps:1. Methane extraction: Methane is extracted from natural gas reserves or produced as a byproduct of various industrial processes, such as coal mining or oil refining.2. Purification: The extracted methane gas is purified to remove impurities such as sulfur compounds, water, and other hydrocarbons. This is typically done through processes like cryogenic distillation or adsorption.3. Reforming: Methane is then subjected to reforming reactions to convert it into more reactive intermediates. One common method is steam methane reforming (SMR), where methane reacts with steam in the presence of a catalyst toproduce hydrogen gas and carbon monoxide. Another method is partial oxidation, where methane is reacted with oxygen to produce hydrogen gas and carbon dioxide.4. Synthesis gas production: The hydrogen gas and carbon monoxide produced in the reforming step are combined to form synthesis gas, also known as syngas. This is usually done through the water-gas shift reaction, where carbon monoxide reacts with steam to produce carbon dioxide and more hydrogen gas.5. Catalytic conversion: The syngas is then subjected to catalytic reactions to convert it into desired products. For example, Fischer-Tropsch synthesis can be used to convert syngas into liquid hydrocarbons, such as gasoline or diesel. Alternatively, methanol synthesis can be used to produce methanol, which can serve as a building block for various chemicals and fuels.6. Product separation: The resulting mixture of products is then separated through various separation techniques, such as distillation or adsorption, to obtainthe desired products in pure form.7. Product refinement: The separated products may undergo further refinement processes, such as hydrocracking or hydrotreating, to improve their quality or adjust their properties.8. Product utilization: The final products obtainedfrom methane conversion can be used in various applications, such as transportation fuels, chemical feedstocks, or as energy sources.Overall, the methane conversion process involves aseries of steps that require careful control of reaction conditions, catalyst selection, and separation techniquesto achieve desired product yields and quality.中文回答：甲烷转化是一个复杂的过程，涉及多个步骤将甲烷气体转化为有用的产品。
Process for synthesis gas production
专利名称：Process for synthesis gas production发明人：Filippi, Ermanno,Skinner, Geoffrey Frederick申请号：EP05004894.1申请日：20050306公开号：EP1700823A1公开日：20060913专利内容由知识产权出版社提供专利附图：摘要：A process for obtaining a synthesis gas (GS) at a predetermined high pressure corresponding to the ammonia synthesis pressure, in which there are hydrogen andnitrogen in a 3/1 molar ratio, comprising the steps of feeding a continuous flow of natural gas to a primary reforming step (RP) with steam and to a subsequent secondaryreforming step (RS) with excess air obtaining a gaseous flow (GF) comprises hydrogen, excess nitrogen with respect to said molar ratio, undesired substances such as impurities and inerts and subjects said gaseous flow to a purification step comprising cryogenic rectification in a separator unit (S) obtaining a continuous flow of synthesis gas (GS) comprising hydrogen and nitrogen in a 3/1 molar ratio, and to a subsequent compression step up to a pressure value required for ammonia synthesis.申请人：Ammonia Casale S.A.地址：Via Giulio Pocobelli, 6 6900 Lugano-Besso CH国籍：CH代理机构：Zardi, Marco更多信息请下载全文后查看。
SYNTHESIS GAS PRODUCTION
专利名称：SYNTHESIS GAS PRODUCTION 发明人：KENNETH M. BARCLAY,JAMES R.BIRK,WILLIAM E. PARKINS申请号：AU1409176申请日：19760519公开号：AU498375B2公开日：19790308专利内容由知识产权出版社提供摘要：A process for the production of a synthesis gas, capable of being upgraded to a high BTU pipeline gas, by the partial oxidation and substantially complete gasification of a carbonaceous material under CO-promoting conditions wherein the carbonaceous material, oxygen, and recycled carbon dioxide from the process are introduced into a molten salt containing an alkali metal carbonate and a minor portion of an alkali metal sulfide, the system being operated at a selected temperature and pressure between 1400 DEG and 2000 DEG F and between 1 and 100 atmospheres. The molar ratio of carbon dioxide to oxygen employed is controlled at from about 0.6:1 to about 1.2:1 to control the CO production and also to maintain the molten salt at a desired operating temperature. Sulfur and ash introduced with the fuel are retained in the molten salt. The gaseous effluent, containing a molar ratio of carbon monoxide to carbon dioxide substantially greater than one, is reacted in a water gas shift reaction, followed by removal of the carbon dioxide present in the gaseous effluent from the shift reaction to produce the synthesis gas, capable of being reacted further under appropriate conditions to produce pipeline gas, methanol, ammonia, or gasoline. At least a portion of the removed carbon dioxide is recycled for admixture with the oxygen to form the feedgas to the molten salt containing the carbonaceous material.申请人：ROCKWELL INTERNATIONAL CORP.更多信息请下载全文后查看。
合成氨工艺流程 英文
合成氨工艺流程英文Ammonia Synthesis ProcessAmmonia, a colorless gas with a pungent odor, is one of the most widely produced and utilized industrial chemicals in the world. It serves as a crucial feedstock for the production of fertilizers, which are essential for sustaining global food production. The synthesis of ammonia is a complex process that involves several steps and the use of specialized equipment and technologies. In this essay, we will delve into the details of the ammonia synthesis process, exploring its key stages and the underlying principles that govern this important chemical reaction.The primary raw materials required for the ammonia synthesis process are hydrogen and nitrogen. Hydrogen is typically obtained through the steam reforming of natural gas or the electrolysis of water, while nitrogen is extracted from the air using an air separation unit. The first step in the ammonia synthesis process is the purification and preparation of these raw materials.The hydrogen stream is first subjected to a desulfurization process to remove any trace amounts of sulfur compounds, which can act ascatalytic poisons in the subsequent steps. The desulfurized hydrogen is then combined with the purified nitrogen stream, and the mixture is compressed to a high pressure, typically in the range of 150 to 300 atmospheres.The compressed gas mixture is then fed into the ammonia synthesis reactor, where the key chemical reaction takes place. This reaction is known as the Haber-Bosch process, named after the German chemists Fritz Haber and Carl Bosch, who developed the process in the early 20th century. The Haber-Bosch process involves the direct combination of hydrogen and nitrogen to form ammonia, according to the following chemical equation:N2 + 3H2 ⇌ 2NH3The reaction is carried out at high temperatures, typically between 400 and 500 degrees Celsius, and in the presence of a suitable catalyst, such as iron oxide or ruthenium. The catalyst helps to lower the activation energy required for the reaction, thereby increasing the rate of ammonia formation.The ammonia synthesis reactor is a critical component of the overall process, as it is responsible for the conversion of the raw materials into the desired product. The reactor design and operating conditions, such as temperature, pressure, and catalyst composition,must be carefully optimized to achieve high conversion rates and efficient utilization of the raw materials.As the gas mixture flows through the reactor, the ammonia is continuously formed and removed from the reaction zone. This is typically accomplished through the use of a cooling system, which lowers the temperature of the gas stream and causes the ammonia to condense and separate from the unreacted hydrogen and nitrogen.The ammonia-rich stream is then further purified and compressed to the desired storage or transportation pressure. This may involve additional separation and purification steps, such as distillation or adsorption, to remove any remaining impurities and ensure the purity of the final ammonia product.The unreacted hydrogen and nitrogen gases are typically recycled back to the beginning of the process, where they are recompressed and reintroduced into the ammonia synthesis reactor. This recycling of the unreacted gases helps to improve the overall efficiency of the process and minimize the consumption of raw materials.The ammonia produced through this process is then transported and stored for various industrial and agricultural applications. It is a versatile chemical that can be used as a feedstock for the productionof fertilizers, explosives, and a wide range of other chemical products.The ammonia synthesis process is a complex and highly integrated system that requires the careful coordination of multiple unit operations and the optimization of various process parameters. Advances in catalyst technology, reactor design, and process control have led to significant improvements in the efficiency and sustainability of ammonia production over the years.In conclusion, the ammonia synthesis process is a critical component of the global chemical industry, enabling the production of essential fertilizers and other important chemicals. By understanding the key stages and underlying principles of this process, we can better appreciate the technological and scientific advancements that have made the large-scale production of ammonia a reality.。
荒煤气制氨水工艺流程
荒煤气制氨水工艺流程Ammonia water is a key chemical in various industries, including agriculture, manufacturing, and pharmaceuticals. 它是一种重要的化学品, 在农业、制造业和制药业等各行各业都起到了关键作用。
The production process of ammonia water involves a complex series of steps, and one common method to produce it is the coal gasification process. 制备氨水的生产过程涉及一系列复杂的步骤，其中一种常见的方法是煤气化工艺。
The coal gasification process begins with the gasification of coal to produce syngas, which contains a mixture of carbon monoxide and hydrogen. 这个过程以煤的气化开始，生产合成气，其中含有一种碳氧化合物和氢气的混合物。
This syngas is then purified and undergoes a series of chemical reactions to produce ammonia. 接着这种合成气被纯化并经历一系列的化学反应来生产氨。
The purification process involves the removal of impurities such as sulfur compounds, which can be harmful to the catalyst used in the subsequent chemical reactions. 纯化过程包括去除硫化物等杂质，这些杂质对随后的化学反应中所使用的催化剂造成危害。
以煤为原料生产合成氨种流程方程式
以煤为原料生产合成氨种流程方程式英文回答:To produce ammonia from coal, a process called coal gasification is used. In this process, coal is first heated in the absence of air to produce a mixture of gases known as synthesis gas or syngas. Syngas consists mainly of carbon monoxide (CO) and hydrogen (H2). The reaction can be represented by the following equation:C + H2O → CO + H2。
The coal gasification process can be carried out using various methods, such as partial oxidation or steam reforming. Once syngas is obtained, it undergoes a series of steps to produce ammonia. One of the key steps is the water-gas shift reaction, which converts carbon monoxide and water into carbon dioxide and hydrogen. The reaction is represented by the following equation:CO + H2O → CO2 + H2。
After the water-gas shift reaction, the syngas is further purified to remove impurities such as sulfur compounds and carbon dioxide. This is important because these impurities can deactivate the catalyst used in the next step. The purified syngas is then fed into a catalytic reactor known as a Haber-Bosch reactor.In the Haber-Bosch process, the syngas is reacted with nitrogen gas (N2) under high pressure and temperature in the presence of a catalyst, typically iron. The reaction results in the formation of ammonia (NH3) according to the following equation:N2 + 3H2 → 2NH3。
天然气气化操作流程
天然气气化操作流程英文回答：The process of natural gas gasification involves converting natural gas into a gaseous state for various applications. This process is commonly used in industries such as power generation, chemical production, and heating systems.The first step in the gasification process is the removal of impurities from the natural gas. This is done through a series of purification steps, including the removal of sulfur compounds, water vapor, and other contaminants. The purified natural gas is then ready for the gasification process.The next step is the actual gasification of the natural gas. This is typically done through a process called steam methane reforming. In this process, natural gas is mixed with steam and passed over a catalyst at high temperatures.This reaction produces a mixture of hydrogen and carbon monoxide, known as synthesis gas or syngas.The syngas produced in the gasification process can be further processed and used for various applications. One common application is power generation. The syngas can be burned in a gas turbine or a combined cycle power plant to generate electricity. Another application is the production of chemicals, such as methanol or ammonia, which can beused in various industries.In addition to power generation and chemical production, the syngas can also be used for heating systems. For example, in some areas where natural gas pipelines are not available, syngas can be used as a substitute for natural gas in residential and commercial heating systems.Overall, the process of natural gas gasificationinvolves the purification of natural gas, followed by the gasification of the purified gas to produce syngas. This syngas can then be used for power generation, chemical production, and heating systems.中文回答：天然气气化的操作流程涉及将天然气转化为气体状态以供各种应用。
甲醇的化工生产技术
(Chemical Technologies of Methanol)
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应用知识
1．合成气和甲醇的生产方法及特点； 2．天然气蒸汽转化的原理及设备特点； 3．甲醇合成、精制原理及工艺流程； 4．天然气蒸汽转化制合成气及甲醇合成的工艺条件和影响因 素。
技能目标
1．能熟练运用工具书、期刊及网络资源等查阅有关合成气和 甲醇的资料，并能进行资料的归纳总结；
2．能对甲醇合成工艺条件的选择进行分析； 3．能对照流程图描述甲醇的合成及精制的工艺流程，并分析 主要设备的作用；
4．能根据生产情况和要求选择适宜的甲醇原料路线。
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一、合成气的生产 Synthesis Gas Production
二、甲醇的合成过程
Synthetic process of Methanol
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(6)脱碳 工业生产中脱除二氧化碳的方法很多，一般采用溶液吸收法：
➢ 化学吸收法常用的方法有氨水法、改良热钾碱法等； ➢ 物理吸收法一般用水和有机溶剂为吸收剂，常用的方法有加压 水洗法、碳酸丙烯酯法、低温甲醇法、聚乙二醇二甲醚法等；
➢物理化学吸收法兼有物理吸收和化学吸收的特点，方法有环丁砜 法、甲基二乙醇胺(MDEA)法等。
常用的干法脱硫有钴钼加氢转化法、氧化锌法、活性碳法、分子筛法等。
湿法脱硫 ①物理吸收法：低温甲醇法、 聚乙醇二甲醚法、碳酸丙烯酯法等 ②化学吸收法：烷基醇胺法、碱性盐溶液法 ③湿式氧化法：改良ADA法、栲胶法、PDS法 及络合铁法等 ④物理化学吸收法：环丁砜法
湿法脱硫具有吸收速率快、生产强度大、脱硫过程连续、溶液再生等特点，适 用于硫化氢含量较高、净化度要求不太高的场合。
无声放电和电晕放电转化温室气体比较研究
无声放电和电晕放电转化温室气体比较研究姜涛;Baldur;Eliasson;等【摘要】在无声放电和电晕放电条件下,研究了温室气体甲烷和二氧化碳的转化特性.实验结果表明,甲烷和二氧化碳在不同放电形式下反应得到不同的产物.甲烷、二氧化碳电晕放电反应的主要产物是合成气,无声放电反应的产物包括合成气、烃、含氧化物和高聚物等,类似于Fischer-Tropsch合成的产物,但分布不符合Schulz-Flory方程.在实验条件下,电晕放电反应体系的能量产率是2.26mol/(kW·h),无声放电反应体系的为0.34mol/(kW·h).输入功率对等离子体反应影响较显著,甲烷和二氧化碳转化率随体系输入功率的提高而很快增加.将13X分子筛催化剂引入无声放电反应,提高了烃类产物选择性,抑制了炭黑和高聚物的生成,但甲烷和二氧化碳转化率分别由64.3%和55.4%降低至51.6%和41.7%,合成气的H2/CO比由1.7降至1.4.【期刊名称】《天津大学学报》【年(卷),期】2002(035)001【总页数】4页(P19-22)【关键词】等离子体;无声放电;电晕放电;甲烷;二氧化碳【作者】姜涛;Baldur;Eliasson;等【作者单位】天津大学化工学院,天津,300072;天津大学化工学院,天津,300072;天津大学化工学院,天津,300072;天津大学化工学院,天津,300072;天津大学化工学院,天津,300072;Energy and Global Change,ABB Corporate Research Ltd,BadenCH5405,Switzerland;Energy and Global Change,ABB Corporate Research Ltd,Baden CH5405,Switzerland【正文语种】中文【中图分类】O646.9甲烷是天然气、煤层气、油田伴生气及一些化工厂副产气的主要成分，有望成为合成液体燃料的主要原料.与从原油生产的燃料相比，从甲烷合成的燃料不含或含极少量的硫、氮和金属等.此类清洁燃料的使用有助于降低硫化物、氮氧化物和金属氧化物等的排放，保护大气环境.从甲烷直接合成液体燃料在热力学上不可行.一般先将甲烷转化为合成气，再由合成气合成液体燃料.从甲烷生产合成气主要有两种过程：一种是甲烷部分氧化；另一种是甲烷水蒸汽或二氧化碳重整.甲烷和二氧化碳的过量排放是引起地球温室效应的主要因素，甲烷、二氧化碳重整制合成气因此而引起人们的兴趣.但该工艺过程在能耗和催化剂寿命等方面还存在一些问题，有必要在改进催化剂的同时开发新的工艺过程.等离子体技术在甲烷和二氧化碳转化利用方面得到了广泛应用[1～4]，国外学者已经进行了用热等离子体生产合成气的中间试验[5].在热等离子体中，气体分子、离子和电子的能量分布接近热平衡，在放电区域，所有粒子的放电温度都很高.通过热等离子体进行的能量传输过程是在高温条件下进行的，为了获得高的目的产物选择性，常常需要对等离子体进行快速“淬灭”，由此导致整个过程的复杂化并浪费能量.因此，很多研究改用冷等离子体进行.冷等离子体具有显著的非平衡性，主要表现在气体温度可低至室温，电子温度高达上万度.冷等离子体主要包括电晕放电、无声放电、辉光放电等.研究发现[6，7]，冷等离子体能在常压低温下有效实现甲烷和二氧化碳的转化.本文研究在电晕和无声放电两种形式下甲烷和二氧化碳转化的规律性，比较甲烷和二氧化碳不同类型等离子体反应的产物，考察两种放电反应的能耗及向放电区域引入催化剂对甲烷、二氧化碳等离体转化的影响. 无声放电和电晕放电均采用管式反应器，如图1所示.无声放电反应器由外管电极、内管电极和绝缘介质组成，外管电极为接地电极，内管电极为高压电极.电晕放电反应器由石英管制成，电极采用针-板结构.实验在室温常压下进行，等离子体反应装置见图2.反应原料气经质量流量计控制进入反应器.利用高压电源产生放电使气体发生反应.反应后的气体经冷凝、计量后，在线分析组成.无声放电所用电源为天津大学制造的高压交流电源，电晕放电所用电源为北京静电设备厂生产的高压直流电源.原料气和尾气分析采用的色谱仪为美国惠谱公司生产的HP 4890型气相色谱和上海分析仪器厂生产的102G型气相色谱.能量产率计算公式为能量产率(m ol/(kW·h））=被转化的甲烷的摩尔数/输入的能量2.1不同放电形式下反应的产物分布由产物气相色谱分析结果可知，在两种放电形式下，甲烷-二氧化碳反应都有合成气产生，此外还有不同的烃类产物生成.表1为在两种放电下等离子体反应产物的比较.由表可见无声放电反应的产物比电晕放电复杂，除合成气和低碳烃外，还产生了一些高碳烃、含氧化物和高聚物.表2为无声放电条件下反应的产物分布，产物包括了CO烃和少量甲醇，及以上烃和高聚物.气态产物选择性占总产物的59%，其它为高碳烃和高聚物.分析表明，高碳烃的90%以上是支链烃，支链烃有很好的燃烧学特性，适于作燃料.上述结果表明，无声放电转化甲烷和二氧化碳得到的产物类似于F-T合成的产物，包含了烃类和含氧化物，但无声放电转化得到的产物分布不满足Schu lz-Flory分布方程.分析表明，无声放电产生的含氧化物有甲醇、乙醇、二甲醚、酸、酮和酯类等，这些组分的含量较低.表3为甲烷和二氧化碳电晕放电反应得到产物的选择性，未包括低碳烃.在有些条件下，低碳烃含量极少.较难分析出.2.2输入功率对等离子体转化的影响输入功率是影响等离子体反应的重要参数之一，在一定气体流量下，输入功率的高低决定了甲烷、二氧化碳的转化率.图3和图4分别为无声放电和电晕放电条件下甲烷、二氧化碳转化率随输入功率的变化情况.可见，在两种放电形式下，甲烷和二氧化碳转化率均随输入功率的提高而增加，这说明等离子体反应参数在甲烷、二氧化碳转化过程中起着重要作用.表4从能量利用角度分析了两种放电反应的效率.能量产率定义为单位输入功率所转化的反应物的量.从表4结果可见，在本研究的条件下，无声放电和电晕放电反应气体的停留时间分别为20.6 s和0.7 s，尽管电晕放电反应的停留时间比无声放电的短很多，电晕放电反应的甲烷转化率(95%）却比无声放电(64%）高得多.表中能量产率的计算结果与此相吻合.电晕放电的能量产率为2.26 m ol/(kW·h），远高于无声放电的能量产率0.34 m ol/(kW·h）.其它研究也得到了类似的结果.李明伟等[8]用甲烷和二氧化碳电晕放电制备合成气，在输入功率50 W、原料气流量60 m L/m in、原料气为1/2的条件下，体系的能量效率达5.9%.Gesser等[9]利用两个串联的无声放电反应器在输入电压13 kV、电流25 m A，为1/1时，体系的能量效率低于1%.2.3 催化剂对两种放电形式转化甲烷和二氧化碳的影响在无声放电反应中，有一定数量碳黑和等离子体聚合物生成，当介质被这些产物完全覆盖后，将影响反应正常进行.在放电间隙加入13X分子筛，考察加入催化剂后的反应情况.加入催化剂前，甲烷和二氧化碳的转化率分别为64.3%和55.4%，加入催化剂后，分别降为51.6%和41.7%，合成气比由1.7降为1.4.加入催化剂后，无声放电反应的产物选择性也有明显变化.如表5所示.与表2未加催化剂的结果相比，CO选择性略有下降，各烃组分的选择性有不同程度的提高.催化剂的引入抑制了碳黑和等离子体聚合物的生成，在反应后的催化剂表面发现了一些含碳物种. 在甲烷、二氧化碳电晕放电制合成气[8]反应中引入NaY、HZSM-5和NaZSM-5等催化剂，结果使甲烷转化率略有降低，但明显提高了产物中的比值.1）用无声放电和电晕放电转化甲烷和二氧化碳，得到不同的产物.电晕放电反应的产物主要是合成气，而无声放电的产物除合成气外，还有烃类和含氧化物.2）输入功率对甲烷和二氧化碳等离子体转化有显著影响，在无声放电和电晕放电下，甲烷和二氧化碳的转化率均随输入功率的提高而增加.3）在所研究的范围内，电晕放电的能量产率比无声放电的高.在无声放电反应间隙加入13X分子筛，能够抑制碳黑和高聚物的生成，同时提高烃的选择性.4）加入催化剂使甲烷和二氧化碳转化率分别由64.3%和55.4%降低至51.6%和41.7%，合成气的比由1.7降至1.4.[1]Kogelschatz U，Zhou L-M，Xue B，et al.Production of synthesis gas through p lasm a-assisted reform ing of greenhouse gases[A].Proc of the 4thInt Con f On Greenhouse Gas Control Tech[C].Sw itzerland.1998：385-390.[2]Liu C J，Xu G H，W ang T.Non-therm al p lasm a approaches inCO2utilization[J].Fuel Processing Tech，1999，58：119-134.[3]M alik M A，Jiang X Z.The CO2reform ing of natural gas in a pulsed corona discharge reactor[J].Plasm a Chem OPlasm a Processing，1999，19(4）：505-512.[4]Liu C J，M allinson R G，Lobban L L.Nonoxidative m ethane conversion to acetylene over zeolite in a low tem perature p lasm a[J].J of Catalysis，1998，179：326-334.[5]Blutke A S，Bohn E M，V avruska J S.Plasm a technology for syngas p roduction for offshore GTL p lants[A].Presentation of M anaging A ssociated O ffshore Natural Gas [C].Houston：1999，123-128.[6]Eliasson B，Liu C J，Kogelschatz U.Direct conversion of m ethane and carbon dioxide to higher hydrocarbons using catalytic DBD w ithzeolite[J].Ind Eng Chem Res，2000，39(5）：1221-1227.[7]Zhou L M，Xue B，Kogelschatz U，et al.Non equilibrium p lasm a reform ing of greenhouse gases to synthesis gas [J].Energy and Fuels，1998，12(6）：1191-1199.[8] 李明伟.温室气体冷等离子体反应制合成气基础研究[D].天津：天津大学，1999.[9]Gesser H D，Hunter N R and Probaw ono D.The CO2reform ing of natural gas in a silent discharge reactor[J]. Plasm a Chem Plasm a Processing，1998，18(2）：241-245.·h），respectively，under the present reactive conditons.The conversions of m ethane and carbon dioxide increase rapid ly w ith increasing input pow er.The presence of 13X zeolite w ithin the gap of DBD discharge im proves the selectivity of hydrocarbons and inhibits the form ation of carbon b lack and the p lasm a polym er.Conversions of methane and carbon dioxide decrease from 64.3%and 55.4%to 51.6%and 41.7%，respectively，and m olar ratio of H2/CO of syngas from 1.7 to 1.4 w hen 13X w as used.。
甲烷辅助高温电解制氢气和合成气
阳极侧甲烷反应类型将甲烷辅助 SOEC 分成 2 大类： 甲烷部分氧化(POM)辅助 SOEC 和甲烷深度氧化辅 助 SOEC(图 1)，两者阳极侧产物分别为高附加值产 物——合成气和 CO2+H2O，因此 POM 辅助 SOEC 模式更加具有商业应用潜力。
甲烷辅助高温电解制氢气和合成气
王 瑶，刘 通
(武汉大学动力与机械学院，水力机械过渡过程教育部重点实验室，武汉 430072)
摘 要：基于固体氧化物电解池(SOEC)的高温电解技术具有能量转换效率高、模块化易组装、应用灵活等优点，是一种极具 应用前景的能量转化和存储技术。新型甲烷辅助高温电解模式将 SOEC 系统与甲烷部分氧化(POM)反应耦合，在有效降低电 解能耗的同时制备高品位合成气。这种新型 SOEC 模式打通了电、热、气等不同能源网络，能够高效、灵活地实现不同能量 之间的转化，实现能量和资源的最优利用。本文简述了甲烷辅助 SOEC 模式的研究进展，详细分析和阐述了该种新型 SOEC 模式下电解池的热力学参数、Nernst 电势、电化学性能、产物组成和能量结构及效率，同时，总结了适用于甲烷辅助 SOEC 模式的电极体系的研究现状，最后对甲烷辅助 SOEC 模式的应用前景进行了展望。
整反应(reverse water gas shift，RWGS)转化为 CO，
O2–在外电压的驱动下穿过致密的电解质从阴极到
达阳极，并且在阳极释放电子生成 O2。电极反应为：
阴极反应：H2O+2e–=H2+O2–
(4)
CO2+2e–=CO+O2–
(5)
或 RWGS: CO2+H2=CO+H2O
(6)
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AR TIC LE D ATA
Article history: Received 4 June 2008 Received in revised form 15 September 2008 Accepted 27 September 2008 Keywords: Steam reforming CO2 reforming Synthesis gas H2/CO ratio Aspen Plus Steam hydrogasification
See discussions, stats, and author profiles for this publication at: https:///publication/244238834
Synthesis gas production using steam hydrogasification and steam reforming
⁎ Corresponding author. Bourns College of Engineering, Center for Environmental Research and Technology, University of California, Riverside, 1084 Columbia Ave, Riverside, CA — 92507, United States. Tel.: +1 951 781 5771; fax: +1 951 781 5790. E-mail address: cspark@ (C.S. Park). 0378-3820/$ – see front matter © 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2008.09.011
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Synthesis gas production using steam hydrogasification and steam reforming
Article in Fuel Processing Technology · February 2009
Impact Factor: 3.35 · DOI: 10.1016/j.fuproc.2008.09.011
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3 authors, including: Arun SK Raju University of California, Riverside
technologies available for syngas production depending on the input gas composition; each usually resulting in a specific fixed H2/CO syngas ratio [3]. Steam methane reforming produces a H2/ CO syngas ratio of four or higher whereas partial oxidation gasification produces a syngas ratio of 1; and autothermal reforming produces a ratio of 2. The composition of the syngas from either gasification processes or syngas production technologies are generally not suited for direct use in the downstream fuel process. In several cases, H2/CO syngas ratio adjustment techniques such as downstream shift reactors, membrane separators or pressure swing adsorption are employed to meet the ratio requirement [3,6]. This adds cost and complexity to the overall process. Steam methane reforming is a well known commercial technology and is often a preferred choice for hydrogen production from methane. It has been well established that the presence of
Arun S.K. Raju, Chan S. Park⁎, Joseph M. Norbeck
Bourns College of Engineering, Center for Environmental Research and Technology (CE-CERT), Department of Chemical and Environmental Engineering, University of California, Riverside, California 92521-0425, United States
1.
Introduction
The efficient commercial production of synthesis gas (a mixture of hydrogen and carbon monoxide) is gaining significant attention as the worldwide interest in synthetic fuels and chemicals is increasing. Synthesis gas (syngas) is a versatile feedstock that can be used in the production of a number of hydrocarbons, including synthetic Fischer–Tropsch (FT) diesel. The required molar ratio of hydrogen to carbon monoxide (referred to as the syngas ratio) varies depending on the desired product and fuel processing technology [1,2]. For example, the production of Fischer–Tropsch diesel fuel may require a H2/CO syngas ratio from less than one to over two depending on the catalyst and specific technology used [1]. Oxosynthesis and other processes such as dimethyl ether synthesis generally require a H2/CO ratio of 1 [2]. There are several commercial
ABSTR ACT
Experimental work has been carried out on the mixed reforming reaction, i.e., simultaneous steam and CO2 reforming of methane under a wide range of feed compositions and four different reaction temperatures from 700 °C to 850 °C using a commercial steam reforming catalyst. The experiments were conducted for a CO2/CH4 ratio from 0 to 2 and a steam to methane ratio from 3 to 5. The effect of CO2/CH4 ratio on the exit H2/CO ratio and the conversions of the reactants indicate that the dry reforming reaction is dominant under increased carbon dioxide in the feed. Steam reforming of typical steam hydrogasification product gas consisting of CO, H2 and CO2 in addition to steam and methane has also been investigated. The H2/CO ratio of the product synthesis gas varies from 4.3 to 3.7 and from 4.8 to 4.1 depending on the feed composition and reaction temperature. The CO/CO2 ratios of the synthesis gas varied from 1.9 to 2.9 and 2.0 to 3.3. The results are compared with simulation results obtained through the Aspen Plus process simulation tool. The results demonstrate that a coupled steam hydrogasification and reforming process can generate a synthesis gas with a flexible H2/CO ratio from carbon-containing feedstocks. © 2008 Elsevier B.V. All rights reserved.