含MCM—41分子筛的FCC催化剂半工业应用试验

合成出了可用于催化裂化的MCM－41分子筛,并制成FCC催化剂。经半工业应用试验表明：使用系统藏量中含有50％MCM－41分子筛的FCC催化剂具有较好的裂化重油的能力,与原用催化剂相比柴油收率可增加1．85个百分点,轻质油收率增加3．47个百分点,焦炭产率下降了0．29个百分点。     

MCM—41分子筛的合成及其对煤油的脱色性能

采用水玻璃、氧化铝和十六烷基溴化胺为原料，在水热条件下合成孔径为3．5nm的MCM－41分子筛。以不合格变色煤油为研究对象，分别进行了Na－MCM－41、H－MCM－41、X、Y型分子筛、活性炭和白土的煤油脱色性能对比试验。结果表明H－MCM－41分子筛具有优异的煤油脱色性能。     

Ni2P/Ti-MCM-41的催化加氢脱硫性能

以MCM 41和Ti MCM 41介孔分子筛为载体,低温还原法(400℃)制备了磷化镍催化剂。采用XRD、BET、FT IR、Py FT IR、XPS、CO吸附等手段对催化剂进行了表征。采用固定床反应器,以二苯并噻吩为模型化合物,评价了磷化镍催化剂的加氢脱硫催化性能。结果表明,〖JP2〗金属Ti的引入可以增强载体和催化剂的B酸和L酸酸性;金属Ti因其电子助剂的作用,能够促进更细小尺寸的Ni2P活性相的形成。在反应温度340℃、反应压力30 MPa、质量空速(MHSV)35 h-1、V(H2)/V(Oil)=650的条件下,Ni2P/Ti MCM 41催化二苯并噻吩加氢脱硫反应的转化率高达9938%,与相同条件下制备的Ni2P/MCM 41相比,提高了约17百分点。Ni2P/Ti MCM 41催化剂具有更优的原料处理能力和更佳的催化活性的原因可归结为金属Ti的电子效应、活性相的尺寸和分散度以及催化剂适宜的酸性。     

以全硅MCM—41为载体制备W系深度加氢脱硫催化剂

用全硅MCM－41担载Ni-W和Co-W制备了深度加氢脱硫催化剂,并在中压固定床反应器上分别考察了对二苯并噻吩（DBT）和高硫直接馏柴油的加氢脱硫性能。结果表明,全硅MCM－41担载制成的W系催化剂表现出很高的加氢脱硫活性,其中Ni-W/MCM-41活性高于Co-W/MCM-41,但两类催化剂的最佳Ni(Co)/W原子比均为0．75。从加氢脱硫产物分布看,两类催化剂的脱硫反应路径不同,在Co-W/MCM-41上主要通过氢解脱硫,而在Ni-W/MCM-41上则是通过氢解以及先经芳环加氢后脱硫的两条路径来进行,对Ni-MCM-41来说,加氢活性随温度升高而升高。     

高温熔融法固化催化裂化废催化剂重金属研究

采用高温熔融处理技术对催化裂化（FCC）废催化剂进行固化处理,选取CaO,SiO₂,CaF₂作为助熔剂,考察助熔剂类型、助熔剂添加比例、反应温度和反应时间等条件对FCC废催化剂固化处理的影响。结果表明,3种助熔剂对FCC废催化剂上的重金属Ni、V都具有一定的固化作用,其中酸性助熔剂SiO2固化效果最好,表面微观结构显示添加SiO₂后的废催化剂表面更加光滑均匀、结构致密、表面无孔隙,其结构类似于玻璃体结构。当助熔剂SiO₂添加量（w）为20%、反应温度为1 000 ℃、反应时间为2 h时,重金属Ni和V的浸出质量浓度分别为1.0 mg/L和0.5 mg/L,提高反应温度和延长反应时间可以提高对重金属Ni、V固化程度。     

Al2O3改善FCC催化剂抗镍性的机理研究

研究了不同比表面积和孔径分布的Al2O3作为基质添加组分对FCC催化剂 性能的影响，结果表明，基质中添加活性Al2O3有利于改善FCC催化剂的重油转化能力、焦炭选择性以及抗Ni性能；借助XRD、TPR等手段研究了NiO在Al2O3表面上的分散度和还原性，结果表明：NiO在大孔径（4－60nm),低比表面积（46m^2/g)Al2O3上分散度较低，不易被还原，因而其脱氢活性低，致使FCC催化剂的抗镍性能较好。添加10％该Al2O3的催化剂与空白对比剂相比，重油转化率增加了3．6个百分点，焦炭选择性降低了0．36个百分点。     

MAXOFIN:大量生产轻烯烃的新型FCC工艺

MAXOFINI艺由M0bil和Kell。既两公司联合开发。其目的在于提高FCC装置的轻烯烃产率。主要内容包括：采用并列的双提升管催化裂化装置，一根提升管以蜡油为原料，提升管出口温度为538t，剂油比为8－9；另一根提升管以轻石脑循环油（催化裂化汽油）为原料，提升管出口温度为593℃，剂油比为25。该工艺可按多产轻烯烃或多产燃料油等几种模式操作，反映出该工艺的操作灵活性。为了多产轻烯烃，采用MAXOFIN习助催化剂，该剂的四＊－5分子筛含量在25W％以上，与常规该类型助催化剂相比，其丙烯产率可提高1．ZW啪，催化剂微反活性可提高4…     

超微粒介孔分子筛Ti-MCM-41的制备及苯乙烯的催化氧化

强酸性条件下，在40℃水浴中，以无水乙醇和异丙醉为混合剂，合成了n(Si)：n(Ti)为30的超微粒介孔分子筛Ti—MCM—41。研究了超微粒介孔分子筛Ti—MCM—41在苯乙烯与双氧水反应中的催化行为，并讨论了催化剂用量及反应条件对苯乙烯转化率的影响。     

MCM—41分子筛的模板剂脱除方式对其结构和酸性的影响

通过XRD、IR和N2吸附等多种手段研究了模板剂脱除方式对MCM－41分子筛结构和性能的影响。结果表明，采用在空气中直接焙烧的方法脱除模板剂在一定的程度上破坏了MCM－41分子筛的结构完整性，骨架脱铝现象最明显；在N2气氛中焙烧一段时间后继续在空气中焙烧对MCM－41分子筛的结构和酸性得到一定的保护；相比之下，经溶剂抽提再经空气短时间焙烧过的MCM－41分子筛显示出较高的结晶度和较好的酸性特征。     

催化裂化汽油改质研究

由过渡金属A和B活性组分与硅铝载体制备的催化剂，在固定床反应器中通过氢转移技术降低催化裂化汽油烯烃含量，达到改质目的。并对此催化剂作用下反应的工艺条件进行考察，在反应温度70～80℃，压力0．1～0．3MPa．体积空速为1．0h^-1的最佳条件下原料油的烯烃含量(PONA法)可降低20％以上．辛烷值基本保持不变，改质后的催化裂化(FCC)汽油品质基本上达到国家汽油新配方标准。     

hysicochemical Properties and Catalytic Performance of a Novel Aluminosilicate Composite Zeolite for Hydrocarbon Cracking Reaction

A novel micro-micro/mesoporous aluminosilicate ZSM-5-Y/MCM-41 composite molecular sieve with a MCM-41 type structure was synthesized through a novel process of the self-assembly of CTAB surfactant micellae with silica-alumina source originated from alkaline treatment of ZSM-5 zeolite. The physical properties of the ZSM-5-Y/MCM-41 composite molecular sieve were characterized by XRD, Py-FTIR and N2 adsorption-desorption techniques. Different kinds of molecular sieves including ZSM-5, Y zeolite, Al-MCM-41, ZSM-5/MCM-41 and ZSM-5-Y/MCM-41 as cracking catalysts were investigated, using 1,3,5-triisopropylbenzene (1,3,5-TIPB) as the probe molecule. Catalytic tests showed that the ZSM-5-Y/MCM-41 composite molecular sieve exhibited higher catalytic activity compared with the microporous ZSM-5 zeolite, Y zeolite, mesoporous Al-MCM-41 molecular sieve and ZSM-5/MCM-41 composite molecular sieve under the same conditions. The remarkable catalytic activity was mainly attributed to the presence of the hierarchical pore structure and proper acidity in the ZSM-5-Y/MCM-41 composite catalyst. Meanwhile, a carbenium ion mechanism was put forward for the cracking of 1,3,5-TIPB.     

Physicochemical Properties and Catalytic Performance of a Novel Aluminosilicate Composite Zeolite for Hydrocarbon Cracking Reaction

A novel micro-micro/mesoporous aluminosilicate ZSM-5-Y/MCM-41 composite molecular sieve with a MCM-41 type structure was synthesized through a novel process of the self-assembly of CTAB surfactant micellae with silica-alumina source originated from alkaline treatment of ZSM-5 zeolite.The physical properties of the ZSM-5- Y/MCM-41 composite molecular sieve were characterized by XRD,Py-FTIR and N_2 adsorption-desorption techniques. Different kinds of molecular sieves including ZSM-5,Y zeolite,Al-MCM-41,ZSM...     

Catalytic cracking of isopropylbenzene over hybrid HZSM-12/M41S (M41S = MCM-41 or MCM-48) micro-mesoporous materials

The catalytic cracking of isopropylbenzene was investigaded over hybrid ZSM-12/MCM-41 and HZSM-12/MCM-48 micro-mesoporous materials, in order to verify the effect of the acid site of the accessibility of mesoporous channels combined with the acid sites into the zeolite. The hybrid materials were synthesized by the hydrothermal method using the template mechanism. The obtained materials were characterized by X-ray diffraction and BET isotherms using nitrogen adsorption-desorption at 77 K. The X-ray diffraction patterns presented characteristic peaks of the microporous and mesoporous phases. These analysis revealed the formation of ordered hexagonal MCM-41 or cubic MCM-48 mesoporous phases, associated with the ZSM-12 structure. In order to generate acid sites, the materials were ion exchanged with ammonium chloride solution. The calcined hybrid materials were tested as catalyst for cracking of isopropyl-benzene, using a fixed bed reactor at 450 ^oC and nitrogen gas. The catalytic tests showed that the HZSM-12/AlMCM-41 and HZSM-12/MCM-48 hybrid materials have potential for use in cracking reactions, bening more active than the zeolite or the M41S alone. The catalytic activities of the hybrid materials can be associated with a synergistic effect between the acid sites present on the zeolitic phase and the mesoporous phase. In order to verify how the structure of the hybrid materials may affect and control their catalytic performances, the results were compared with HZSM-12 physically mixed with MCM-41 and MCM-48.     

含MCM-22分子筛催化剂的裂化反应性能研究

研究了ZSM-5，Beta，MCM-22分子筛分别作为FCC催化剂添加组分的性能。结果表明，催化剂中含MCM-22的汽油和柴油产率高于含ZSM-5，与含Beta相当；气体产物的产率低于ZSM-5，高于Beta而焦炭产率比二者都高。并且发现，含MCM-22的氢转移活性比含ZSM一5和含Beta高；裂化机理比率（CMR）低于ZSM-5．与Beta相当，说明在催化裂化反应中MCM-22晶体表面的12MR孔穴起重要作用。MCM-22的催化裂化反应性能介于ZSM-5和Beta之间，更接近于Beta．     

Conversion of n-heptane over different catalysts: Effect of catalyst-to-oil ratio and temperature

Catalytic cracking of n–heptane was investigated over various catalysts including ZSM-5, MCM-41, USY and mordenite. The influence of reaction temperature and catalyst-to-oil ratio was investigated in the case of ZSM-5 as more favorable catalyst in terms of conversion and light olefins yield. The highest n-heptane conversion of 97.3 wt.% was achieved over USY zeolite. Both conversion and olefin selectivity were increased by temperature over ZSM-5 zeolite. Increasing catalyst-to-oil ratio enhanced conversion with no significant changes in olefins selectivity. The highest olefin production was achieved over ZSM-5 zeolite in catalyst-to-oil ratios of 1.5 and 3.0 (g/g) at 550°C.     

Physical mixture of MCM-41/ZSM-5 as an active catalyst component for maximization of propylene in Catalytic cracking of VGO

The performance of a novel catalyst additive containing highly porous MCM-41 and ZSM-5 zeolite was investigated using a commercial equilibrium FCC catalyst in catalytic cracking of vacuum gas oil. The catalytic tests were assessed in a fixed-bed microactivity test unit at reaction temperatures 500–620 °C. The highest propylene yield of 23.8 wt% was achieved at 600 °C. The propylene yield increased from 14.49 wt% to 23.8 wt% when the temperature rose from 500 to 600 °C; however the gasoline yield fell from 22.47wt% to 16.49 wt% by increasing the temperature from 580 °C to 620 °C, respectively.     

无黏结剂沸石颗粒催化剂制备中硅铝胶基质的特性

 采用硅溶胶为硅源、偏铝酸钠为铝源制备无黏结剂 MCM-22沸石颗粒催化剂。通过对不同 pH 值硅溶胶进行 TEM、TG、比表面积的表征和 NaAlO₂溶液电位滴定实验可知,在 pH 值为9.9时最有利于硅溶胶和 NaAlO₂中硅原子与铝原子通过氧桥联结制备硅铝胶基质,为进一步制备无黏结剂沸石颗粒催化剂创造最有利的条件。不同 pH 值所得硅铝胶基质制备无黏结剂 MCM-22沸石颗粒催化剂实验结果表明,采用在 pH 值为9.6~12.0范围内得到的硅铝胶基质,均能得到无黏结剂 MCM 22沸石颗粒催化剂,pH 值为10.0时所得沸石颗粒催化剂最佳,样品相对结晶度达到100%,整个颗粒样品的表面和内部都完全晶化成 MCM-22沸石晶片;而 pH 值在8.5~9.3范围内,最终所得样品仍然为无定形的硅铝胶。     

Hydroconversion of rapeseed oil to hydrocarbons in the presence of MFI/MCM-41 micro–mesoporous materials synthesized by the hydrothermal microwave method

Catalysts containing an MFI zeolite and an MFI/MCM-41 composite synthesized by the hydrothermal microwave method have been first studied in rapeseed oil hydroconversion. Catalysts provide the production of valuable petrochemicals, namely, high-octane components of motor fuels and С₂–С₄ olefins. Synthesized MFI zeolite mostly catalyzed the formation of aromatic hydrocarbons (ArH); incorporation of this zeolite into the matrix of mesoporous silicate MCM-41 leads to a decrease in the ArH content in the liquid hydrocarbon products owing to an increase in the yield of liquid aliphatic hydrocarbons. Promotion of the MFI zeolite synthesized by the hydrothermal microwave method with zinc ions leads to the formation of a catalyst providing the formation of liquid products consisting of ArH.     

MCM-41-HY介-微孔复合分子筛的水热合成及应用

 以微孔HY浆液为母液,合成了一种介-微孔复合分子筛HY/MCM-41。通过XRD,BET,NH3-TPD等手段对复合材料进行了表征,并对复合分子筛的水热稳定性进行了考察。结果表明,复合材料同时具有中孔分子筛MCM-41和微孔HY型沸石的特点,并且和纯MCM-41分子筛相比,复合分子筛的酸性明显增强,并且水热稳定性提高。利用一段串联加氢裂化工艺,考察了复合分子筛的催化性能。200ml固定床加氢装置评价结果表明,在控制原料>350℃馏分油转化率为75%的条件下,加氢裂化生成油C5+液收为98.51%,最大量柴油馏分的收率为69.09%,中油选择性80.5%,能满足工业装置最大量生产柴油的需要。     

干气和苯催化蒸馏制乙苯

研究了MCM-22沸石催化剂对于干气和苯催化蒸馏制乙苯的反应性能,对β,Y,MCM-22沸石催化剂在催化蒸馏和固定床反应工艺中的催化性能进行了比较。实验结果表明,催化蒸馏制乙苯工艺具有操作压力较低、乙苯选择性高、副产物生成量少的优点,但催化剂用量大;以MCM-22沸石为催化剂,随催化蒸馏塔操作温度和压力的升高,液相中乙烯浓度呈升高趋势、乙烯转化率也明显提高,乙苯选择性可达96%以上。催化蒸馏制乙苯过程的速率控制步骤是液相催化反应。