Process conditions for preparing methanol from cornstalk gas

The low-heat-value cornstalk gas produced in the down-flow fixed bed gasifier was tentatively used for methanol synthesis. The cornstalk gas was purified and the technical procedures such as deoxygenation, desulfurization, catalytic cracking of tar, purification and hydrogenation were studied. The catalytic experiments of methanol synthesis with cornstalk syngas were carried out in a tubular-flow integral and isothermal reactor. The effect of reaction temperature, pressure, catalyst types, catalyst particle size, syngas flow at entering end and composition of syngas was investigated. The optimum process conditions and yield of methanol from cornstalk syngas were obtained. The experimental results indicated that the proper catalyst for the synthetic reaction was C301 and the optimum catalyst size was 0.833 mm x 0.351 mm. The optimum operating temperature and pressure were found to be 235癈 and 5 MPa, respectively. The suitable syngas flow 0.9-1.10 mol/h at entering end was selected and the best composition of syngas were CO 10.49%, CO2 8.8%, N2 37.32%, CnHm 0.95% and H2 40.49%. The best methanol yield was 0.418 g/g cornstalk. This study provided the technical support for the industrial test of methanol production from biomass (cornstalk) gas.     

POC的结构参数对DMCC发动机排放影响的试验研究

在一台直列4缸增压中冷电控单体泵柴油机的进气道上增加甲醇喷射装置,实现柴油甲醇二元燃料燃烧(DMDF)模式.利用废气分析仪对其主要气体排放进行测量,研究在排气管上加装的柴油颗粒氧化催化转化器结构参数对尾气催化效率的影响,试验结果表明:POC长度越长,对碳烟、THC、和未燃甲醇的转化效果越好,甲醇替代率为30%、POC长度为100 mm时,对碳烟、CO、THC和未燃甲醇的平均净化效率分别为15.00%、91.61%、75.56%、66.96%,长度增加至200 mm后,上述效率明显提高,分别提高到30.37%、99.29%、67.55%、95.44%;POC孔密度增加,POC对碳烟、CO及未燃甲醇的转化效率有小幅增加,甲醇替代率为30%时,孔密度从200目增加到300目,对碳烟、CO和未燃甲醇的催化效率分别从19.61%、94.66%、86.07%提高到23.06%、97.44%和88.56%;POC结构参数的改变对NO_x的转化效率影响不大.     

城市污泥两段式催化热解制合成气研究

为了把城市污泥中温热解产生的挥发性产物转化为可直接利用的洁净可燃性气体或重要的化工原料合成气,采用两段式热解装置对城市污泥进行了催化热解实验研究,讨论了不同催化剂对城市污泥热解挥发性产物的催化裂解能力,结果表明:城市污泥在热解终温500℃,热解液产率最大,超过500℃,热解液产率减少,热解气增多,固相产率基本不变;城市污泥热解液的裂解温度需在900℃以上,产生的气体组分主要为H2、CO、CH4等小分子非冷凝性气体;Ni/分子筛复合催化剂对热解液转化为合成气的作用效果较好,合成气体(H2+CO)体积含量占气体总量的85%以上.     

甲醇燃料汽车排气净化

在燃用纯甲醇(M100)的BJ492Q型四冲程发动机的台架试验中,用堇青石蜂窝金属钯催化剂进行了排气净化试验。在发动机的混合比调整和负荷特性试验条件下观察了排气中甲醇、甲醛和一氧化碳的净化效果,观察了发动机的怠速起动和暖机过程中催化剂的净化性能。结果表明,发动机排气经催化净化后,排气中甲醇、甲醛和一氧化碳的浓度分别降低到3—17ppm,1—13ppm和0.01—0.30%;净化率分别达到93—99%,92—98%和80—99%。在发动机怠速起动和暖机过程中催化剂可点燃发挥净化作用。制作了催化箱,在武汉213型越野客货车上初步考察了其实用性能。     

城市生活垃圾催化气化制取富氢气体的研究

采用下吸式固定床气化炉,以煅烧白云石为催化剂水蒸气气化城市生活垃圾(MSW)有机组分,在气化温度为750~950℃,S/M(水蒸气和垃圾物料进料质量比)为0.57~1.28时,探讨了催化剂种类、气化温度和S/M等因素对富氢气体成分、产氢率、潜在产氢率、低位热值和碳转化率等的影响。较高气化温度有利于富氢气体的生成,增加碳转化率和产气率,但会降低富氢气体的热值;在实验条件下,富氢气体中H2体积分数最高达53.29%,产氢率达到7.13~46.52mol/kg,潜在产氢率为55.48~90.11mol/kg;镍基催化剂催化效果优于煅烧白云石,能大幅增加H2含量,使焦油在850℃以上完全分解。     

掺甲醇汽油对国III汽油机排放性能影响

在一台整车试验满足国III排放法规要求的多点电喷汽油机上,采用甲醇掺入汽油的混合燃料（甲醇的体积分数分别为0%、15%和50%）进行台架试验,使用傅里叶变换红外光谱分析仪（FTIR）在线检测了常规车用三效催化转化器前后的常规和非常规排放.研究结果表明：怠速工况下,掺醇燃料对NOx排放基本没有影响,但CO和HC随掺醇比增加而普遍降低,非常规排放中乙醛排放有所降低,甲醇和甲醛则随掺醇比的增加有较大幅度升高,热怠速时经催化后掺醇燃料对各种排放均无影响,可被控制在极低的水平;其它工况下,随掺醇比增加,CO和HC减少,NOx在高掺醇比下低速低负荷和高速高负荷时有较为明显的改善,非常规排放甲醛和甲醇排放随掺醇比增大而急剧增加,乙醛排放则随之减少.经三效催化转化器作用,无论常规排放NOx、CO和HC,还是非常规排放甲醛、甲醇和乙醛基本上能够实现零排放.     

不同掺混比例甲醇汽油车的排放特性

采用《轻型汽车污染物排放限值及测量方法》(GB 18352.3─2005)规定的Ⅰ型试验方法,对汽油车和不同掺混比例的甲醇燃料车在原催化器和新催化器条件下的瞬态常规污染物排放特性进行了研究. 结果表明:甲醇燃料汽车CO和HC排放较汽油车低,其NO_x的排放通常高于汽油车,且随甲醇比例的提高而增加,使用针对甲醇燃料开发的新催化器后,3种常规污染物排放均明显降低;甲醇燃料汽车CO的排放多数出现在第1个195工况,HC的瞬态排放规律与CO相近,NO_x几乎在每个急加速阶段和城郊运行工况(EUDC)循环中均出现峰值.      

城市生活垃圾水蒸气催化热解的实验研究

采用自行设计的外热式催化热解实验装置,以城市生活垃圾为原料,对温度(600℃～900℃)、物料的组分、加热方式、水蒸气以及白云石催化剂等影响垃圾热解的因素进行了分析。结果表明,气化温度、水蒸气、催化剂对垃圾热解性能影相显著。随热解温度的升高,产气量不断上升,H2和CO的含量增加,当温度为900℃时,产气量达到0.96m3/kg,H2和CO含量分别达35.1%和31.8%;催化剂使用、水蒸汽通入显著改善产品气质量,特别是H2含量,可达45%左右;挥发分含量较高的物料热解性相对较好;快加热方式有利于提高产品气质量。     

Cost comparison of syngas production from natural gas conversion and underground coal gasification

Underground coal gasification (UCG) is a promising technology to reduce the cost of producing syngas from coal. Coal is gasified in place, which may make it safer, cleaner and less expensive than using a surface gasifier. UCG provides an efficient approach to mitigate the tension between supplying energy and ensuring sustainable development. However, the coal gasification industry presently is facing competition from the low price of natural gas. The technology needs to be reviewed to assess its competiveness. In this paper, the production cost of syngas from an imaginary commercial-scale UCG plant was broken down and calculated. The produced syngas was assumed to be used as feedstock in liquid fuel production through the Fischer-Tropsch process or methanol synthesis. The syngas had a hydrogen (H₂) to carbon monoxide (CO) ratio of 2. On this basis, its cost was compared with the cost of syngas produced from natural gas. The results indicated that the production cost of syngas from natural gas is mainly determined by the price of natural gas, and varied from $24.46 per thousand cubic meters (TCM) to $90.09/TCM, depending on the assumed price range of natural gas. The cost of producing UCG syngas is affected by the coal seam depth and thickness. Using the Harmon lignite bed in North Dakota, USA, as an example, the cost of producing syngas through UCG was between $37.27/TCM and $39.80/TCM. Therefore, the cost of UCG syngas was within the cost range of syngas produced by natural gas conversion. A sensitivity analysis was conducted to investigate how the cost varies with coal depth and thickness. It was found that by utilizing thicker coal seams, syngas production per cavity can be increased, and the number of new wells drilled per year can be reduced, therefore improving the economics of UCG. Results of this study indicate the competitiveness of UCG regarding to natural gas conversion technologies, and can be used to guide UCG site selection and to optimize the operation strategy.     

重载柴油机采用非SCR和DPF实现国Ⅳ排放研究

在1台电控高压共轨重载柴油机上采用柴油/甲醇二元燃料(DMDF)燃烧方式,后处理采用氧化催化转化器(DOC)紧耦合微粒氧化催化器(POC),对其排放特性开展了试验研究.结果表明:DMDF模式可以同时减少NOx和炭烟排放,且随着甲醇掺烧比例的增加降低效果更加显著;在80%负荷时当甲醇掺烧比例为50%时,NOx和炭烟排放分别减少了25.3%和69.3%;DOC+POC对HC、CO和甲醛排放的催化效率均超过了98%,优于原机水平;经ETC、ESC和ELR检测,柴油机采用DMDF模式结合后处理器DOC+POC可满足国Ⅳ排放要求.     

温度对干化污泥水蒸气气化产气特性的影响

采用固定床气化装置,在水蒸气流量为0.32 kg/h条件下进行了污泥水蒸气气化实验。研究了温度对污泥气化气体产率、氢气产率、气体成分与低位热值、气体能源转化率的影响。结果表明:随着反应温度从700℃上升到1 000℃;气体产率从0.39 m3/kg升至0.61 m3/kg;氢气产率从0.18 m3/kg升至0.34 m3/kg;气体能源转化率从54%升至88%;产气的低位热值从10 688.1 kJ/m3提高至11 168.9 kJ/m3。同时产气中H2和CO含量随着温度的升高而增加,CH4、CO2和CnHm含量随温度的升高而减少。因此,为了获得更多的可燃气体,建议在污泥水蒸气气化工艺中,气化温度必须大于800℃。     

不同含水率污泥和小麦秸秆混合热解制备富氢合成气

为拓展活性污泥资源化利用方向,在固定床反应器中研究了不同含水率污泥与小麦秸秆的共热解。将不同含水率的污泥和秸秆在600~900 ℃范围内混合热解,研究了热解温度、污泥含水率和秸秆添加量对气体组成的影响。当污泥含水率一定时,随着反应器温度的升高,H₂和CO的含量逐渐增加。在相同温度下,随着污泥含水率的增加,H₂的含量呈现先增加后减少的趋势,而CO含量呈逐渐下降趋势。当污泥含水率为60%时,H₂的含量达到最大值。当热解温度为800 ℃时,制备富氢合成气的最佳比例为40%的秸秆与含水率为60%的污泥混合热解。     

铜锰基整体式催化剂对烧结烟气CO净化特性

基于改性铜锰氧化物作为CO催化活性组分,分别制备了催化剂原粉、以泡沫金属、堇青石为载体的两种整体式催化剂,在实验室配气条件下对比了3种样品的CO催化效率及稳定性,优选了堇青石整体式催化剂,并在某钢厂实际烧结烟气条件下测试了其在不同催化剂负载量、空速、温度下的CO催化效率、稳定性以及衰减后样品催化特性;最后批量制备了2m³优选整体式催化剂并开展了6000m³/h烧结烟气CO净化中试实验.结果表明,烟气高浓水蒸气显著抑制CO催化反应,经240h催化后T₉₀最大提升38℃;催化剂负载量越高,T₉₀越低,催化效率衰减时间越短,稳定后的效率越高,但随着空速增加,该优势减小;1440h(2个月)中试实验中,进气温度185~195℃下,CO催化效率大于85%(平均90%),出口CO浓度低于1000×10^-6,出口平均烟温达220℃,具有节能减排双重效益.     

Ni/钙铝石催化剂对焦油模拟物甲苯的催化研究

以高温烧结法制备的钙铝石为载体,利用溶液浸渍法制备出Ni/钙铝石催化剂。以甲苯为生物质焦油模拟物,在N2气氛下研究Ni/钙铝石催化剂对甲苯催化裂解的性能。采用XRD、SEM、BET等分析手段对催化剂进行表征,然后在实验室自制固定床反应装置中考察了反应温度、镍负载量对催化产气成分、产氢量及甲苯转化率的影响。结果表明:随着反应温度的增加,甲苯转化率升高,产气量增加;较高温度下,增加镍负载量有利于提高产氢量。     

制氨厂尾气中CO的变压吸附提纯

制氨厂尾气含有大量CO,若采用有效的分离、纯化工艺,可获得碳一化工(C1)所需的高纯度CO.本文研究了用PU1型吸附剂变压吸附提纯制氨厂尾气,同时比较了PU1型吸附剂和ZMS-5A型沸石的性能.试验采用一段法变压吸附工艺研究了不同操作条件下CO的纯化和回收,气体流速为0.2～0.8 m³/h,并对工艺条件进行了优化.结果表明PU1吸附性能较好,在吸附压力0.3 MPa、原料气CO浓度30%时,CO回收率为75%,CO产品气的纯度可大于98%.     

铂、钯蜂窝催化剂高温老化对甲醇深度氧化的影响

本研究对铂、钯蜂窝催化剂及分别添加助化剂CeO_2或WO_3,并于500℃、700℃、900℃或1100℃下经受热老化4h后,考察催化剂比表面、晶相结构及其对甲醇深度氧化活性、产物分布及反应动力学网络变化的情况。实验证明,添加CeO_2后,降低了铂催化剂的耐高温性能,但对钯催化剂无明显影响。添加WO_3,降低了钯催化剂对甲醇的氧化活性。经X-线衍射分析证明,在1100℃高温下,WO_3与堇青石载体中的氧化镁和氧化钙发生强相互作用,生成了相应的钨酸盐。甲醇氧化反应动力学研究表明,甲醇在新鲜和高温热老化的铂催化剂上,反应动力学网络表示式是有区别的。     

Photocatalytic performance of TiO2 catalysts modified by H3PW12O40, ZrO2 and CeO2

The binary composite photo-catalysts CeO2/TiO2, ZrO2/TiO2 and the ternary composite photo-catalysts H3PW12O40-CeO2/TiO2,H2PW12O40-ZrO2/TiO2 were prepared by sol-gel method. The catalysts were characterized by thermogravimetric-differential thermal analysis (TG-DTA), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photocatalyfic elimination of methanol was used as model reaction to evaluate the photocatalytic activity of the composite catalysts under ultraviolet light irradiation. The effects of doped content, activation temperature, time, initial concentration of methanol and gas flow rate on the catalytic activity were investigated. The results showed that after doping a certain amount of CeO2 and ZrO2, crystaniTation process of TiO2 was restrained, particles of catalysts are smaller and more uniform. Doping ZrO2 not only significantly improved the catalytic activity, but also increased thermal stability. Doping H3PW12O40 also enhanced the catalytic activity. The catalytic activities of binary and ternary composite photocatalysts were significantly higher than tin-doped TiO2. The dynamics law of photocatalytic reaction over the binary CeO2/TiO2 and ZrO2/TiO2 catalysts has been studied. The activation energy 15.627 and 15.631 kJ/mol and pre-exponential factors 0.5176 and 0.9899 s-1 over each corresponding catalyst were obtained. This reaction accords to the first order dynamics law.     

陕北气田含醇污水综合治理室内实验研究

陕北气田生产中大多采用甲醇抑制水合物的形成,一部分甲醇溶于水相形成了含醇污水。含醇污水中的甲醇需回收循环使用,以降低天然气的生产成本。该含醇污水水质特点是矿化度非常高,油分和机械杂质含量也较高,pH值较低,同时溶解有一定量的CO2及O2,因此在甲醇回收装置运行中经常出现管线、设备腐蚀穿孔、精馏塔结垢堵塞等现象,严重影响装置的安全运行。针对以上问题在此提出用絮凝/缓蚀阻垢技术综合治理陕北气田含醇污水,含醇污水经处理后,总铁、H2S、机杂、油分含量大为降低;含醇污水对碳钢腐蚀速率可控制在0.15 mm/a以下,阻垢率达到100%,可以完全解决陕北气田含醇污水甲醇回收处理过程中存在的结垢、腐蚀、堵塞等问题。     

提高柴油/甲醇组合燃烧尾气排放质量的研究

对原机、柴油/甲醇组合燃烧,以及带氧化催化转化器的柴油/甲醇组合燃烧3种情况下的尾气排放进行了比较和研究.针对柴油/甲醇组合燃烧可以使NOx、烟度大幅度下降,但同时PM、CO和HC的排放浓度与原机相比反而增加的现状,通过加装氧化催化转化器,对废气进行处理后,发现HC、CO和PM排放明显减少.与原机相比,不仅可以实现大幅度降低NOx,而且PM排放也有较大幅度下降.采用透射电子显微镜观察发现,与原机相比,柴油/甲醇组合燃烧的PM排放中干炭烟(DS)减少,但是可溶有机物(SOF)增加.经过氧化催化转化器处理后,尾气的PM中大量SOF和HC化合物被消除,致使PM的质量明显减少.     

废轮胎流化床气化特性试验研究

为了掌握废轮胎在流化床内的气化特性,利用自行设计的小型流化床试验装置系统,对废轮胎在不同的过量空气系数下在400～700℃温度范围内进行了空气气化实验.分析了废轮胎气化效率、固定碳转化率、气化气热值、产气量以及气化气成分随气化温度、过量空气系数的变化规律.结果表明,废轮胎气化的最佳运行条件为气化初始温度700℃,过量空气系数α=0.4.在此条件下得到的气化气成分主要包括CH₄、CO、H₂、C₂H₆和高分子有机化合物,此时的气化效率为47.96%,气化气低位热值为4 804kJ/m³.