Catalytic co-cracking of distilled bio-oil and ethanol over Ni-ZSM-5_MCM-41 in a fixed-bed

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简述双氧水装置生产工艺流程及其原理

简述双氧水装置生产工艺流程及其原理双氧水装置生产工艺流程包括原料配制、反应器制备、反应过程、产品分离等步骤。

The production process of hydrogen peroxide plantincludes raw material preparation, reactor preparation, reaction process and product separation.首先，将氢和氧混合后送入反应器中，生成过氧化氢。

First, the mixture of hydrogen and oxygen is sent intothe reactor to produce hydrogen peroxide.然后，通过分离技术将过氧化氢与水分离。

Then, the hydrogen peroxide is separated from water through separation technology.接着，进行产品的精馏和净化处理，得到高纯度的双氧水。

Next, the product is distilled and purified to obtainhigh-purity hydrogen peroxide.最后，对双氧水产品进行包装、储存和输送。

Finally, the hydrogen peroxide product is packaged, stored, and transported.双氧水装置生产工艺原理是利用氢和氧的催化反应来生成过氧化氢。

The principle of the hydrogen peroxide plant production process is to generate hydrogen peroxide through the catalytic reaction of hydrogen and oxygen.在反应过程中，需要控制温度、压力和反应时间等参数，以确保产品的质量和产量。

aliphatic脂肪族

HYDROCARBONSI. IntroductionHydrocarbons are covalent compounds containing hydroqen and carbon only. They can be aliphati c脂肪族, alicyclic脂環族or aromatic芳香族.(A) Aliphatic HydrocarbonsThe three most important groups of aliphatic hydrocarbons are alkanes烷烴, alkenes 烯烴and and alkynes 炔烴(B) Alicyclic HydrocarbonsExamples cyclobutane cyclohexene(C) Aromatic HydrocarbonsExamples methylbenzene NaphthaleneNote : Saturated hydrocarbons : ______________________________Unsaturated hydrocarbons: _____________________________30.1 ALKANESThe alkanes are a homologous series of saturated hydrocarbons containing only the C—C single and C—H single bonds.All carbon atoms are sp3 hybrize , and are consequently surrounded tetrahedrally by hydrogen or other carbon atom.The carbon atoms join into straight or branched chain : C n H2n+2The carbon atoms join into a ring (cycloalkane ) : C n H2nI. Natural Source of AlkanesThe natural source of alkanes is crude oil which is a mixture of various types of hydrocarbons.Different types of hydrocarbons can he obtained by two process and cracking.(A) Fractional distillation of crude oilCrude oil can be fractionally distilled into fraction of a mixture of hydrocarbons which have different boiling points. The fractions of Mid-east crude oil is listed belowRefinery gas 液化石油氣(C1 - C4 ) 5%Gasoline 汽油(C5 - C10 ) 10%Naphtha 石腦油(C5 - C7 ) 5%Kerosene. 煤油(C11 - C12) 20%Gas oil 氣油(C13 - C25) 15%Heavy oil 重油(C25 or above) 45%(B) CrackingThe composition of the products depends on the conditions under which the cracking takes pl ace.<1> Thermal Cracking熱裂解This type of cracking is also known as pyrolysis. The alkane is heated to a temperature between 450 and 700°C. At these temperature, carbon -carbon bonds in the alkane molecules undergo homolytic fission. The reactions proceed by chain mechanisms involving a varity of radi cals.Example Cracking of butane(1) Initiation: In this stage methyl, ethyl and propyl radicals are produced(2) Propagation : In this stage, the alkyl radicals react with butane molecules to form butylradicals.The C—C bonds in the butyl radicals then undergo homolytic fission produce alkene molecules and more radicals.A variety of other propagation steps are also possible.(3) Termination: This occurs when two radicals combine to form a molecule.e.g. CH 3∙ + ∙CH 3 → CH 3—CH 3 CH 3∙ + CH 3CH 2∙ → CH 3—CH 2CH 3In practice the thermal cracking of butane produces a mixture of methane, ethene, propene but-1-ene, but –2-ene and hydrogen<2> Catalytic CrackingIn this method of cracking the alkane is passed over a catalyst at a temperature between 400°C and 500°C. The catalyst used is normally aluminium oxide mixed with either silica or chromium (VI) oxide. Like thermal cracking, catalytic cracking produces a mixture of shorter chain alkanes and shorter chain alkenes. However, unlike thermal cracking. catalytic cracking has an ionic mechanism. The acidic oxides used as catalyst promote the formation of carbon ions.Note ：There is a high demand for the use of small hydrocarbons as fuel. Thus, cracking is important in economics.II. Reactions of alkanesSince an alkane molecule contains a saturated carbon skeleton with non-polar C —C and C —Hbond, it is unreactive towards polar or ionic reagents like acids, alkalis, dehydrating agents or aqueous oxidizing agents.The non-polar alkane molecules are reactive towards other non-polar reagents like oxygen and halogens as chlorine and bromine. Energy (heat or light) should be supplied before the reactions can occur. Also, since the bonding atoms of alkanes are of similar electro negativities, bond breaking is normally homolytic, producing reactive free radicals,(A)Combustion of alkanesThe most important reaction of the alkanes is combustion. They burn to form the harmless products, carbon dioxide and water in an exothermic reaction.CH 4 + O 2 → CO 2 + 2H 2OC 8H 18 + 2112O 2 → 8CO 2 + 9H 2ONote ：<1>CH 4 is the main component of natural gas and domestic gas. C 8H 18 is thecomponent of petrol used for internal combustion engines. The large amount of energy released during combust Ion of these alkanet products makes them excellent fuels.<2> In a limited supply of air, carbon monoxide can be produced.CH 4 + O 2 → CO + H 2OCarbon monoxide is toxic as it displaces oxygen from blood haemoglobin, thus making it ineffective in carrying oxygen to v ariou s tissu es of th e body .L.S.T. Leung Chik Wai Memorial SchoolChapt. 30: p.4F.6 ChemistryChapter 30: A lkane 烷烴(B) Photochemical Reactions with halogensAlkanes do not react with chlorine in the dark. However, in the presence of sunlight they undergo a series of substitution reactions.Example: Methane and chlorine react explosively in sunlight. producing a mixture of chloromethane, dichloromethane, trichloromethane and tetrachlorom eth an e.The reaction is a photochemical chain reaction. It takes place in 3 stages.Stage 1: InitiationThis is the homolytic fission of the Cl—Cl bond producing chlorin e radicals.(Bond energy term of Cl—Cl : 242 kJ mol-1, C—H ：435 kJ mol-1 )Stage 2 : PropagationThis involves a number of reactions resulting in the formation of the productsCH3Cl, CH2Cl2, CHC13 and CCl4Stage 3：TerminationThis occurs when two radicals combine.Note : <1> In stage 2, further chlorination can produ ce CH2Cl2 ,CHCl3 an d CCl4.<2> A mixture of products is often found from su ch f ree radi cal reaction s.。

Filamentous Catalytic Beds for the Design of a Membrane Microreactor

M. Matlosz et al. (eds.), Microreaction Technology © Springer-Verlag Berlin Heidelberg 2001
aluminium surface resulting in a thin porous layer of a-Ah03. The obtained oxide layer had a very regular pore structure oriented perpendicularly to the flow direction. This porous layer served as support for the catalytically active components. The use of aluminium is restricted to temperatures up to 450°C. Therefore, different methods of deposition of active catalytic layers on other materials are under development. Sol-gel methods are commonly proposed to obtain a porous support layer on the wan of the micro channels [8]. The catalytically active phase can be deposited on the porous layer by precipitation or impregnation. In the present paper a novel concept of a microreactor system is proposed for the catalytic non-oxidative dehydrogenation of propane. It consists of a two zone tubular reactor of few millimeters in diameter fined with catalytically active filaments placed in parallel to the tube walls. The two zones are separated by a Pdmembrane, allowing to eliminate hydrogen from the reaction mixture, thus shifting the reaction equilibrium to higher conversions.

分子生物学词汇(中英文对照表 )

Reaction performance of FCC slurry catalytic cracking

Reaction performance of FCC slurry catalytic crackingXingying Lan,Chunming Xu,Gang Wang,Jinsen Gao*State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing102249,PR China1.IntroductionTheﬂuidized catalytic cracking of hydrocarbons is the main stayprocess for the production of gasoline and light hydrocarbonproducts from heavy hydrocarbons such as vacuum gas oils.Theresource of the crude oil forces the reﬁners to process more andmore vacuum resid in FCC units[1].With the use of heavierfeedstocks,increasing amounts of coke are found insideﬂuidcatalytic cracking(FCC)disengager vessel[2].Coke is commonlyobserved on the surface of the cyclone barrels,disengager dome,and walls[3,4].Coke deposition in the disengager vessel reducesthe operating reliability of FCC unit,due to the constant risk ofproblems linked to hampered catalyst circulation caused by piecesof coke breaking loose[5,6].Coke formation has been observed where condensation ofhydrocarbon vapors occurs[3].Heavier boiling components in thecracked products may be very close to their dew point,and theywill easily condense and form coke nucleation sites on evenslightly cooler surfaces.There are more heavy hydrocarbons in theFCC feedstocks with the increase of the resid blending percentage.It is hard to atomize completely the feedstocks,and the heavycomponents cannot be fully vaporized and adhere to the surface ofthe catalyst.The unvaporized heavy hydrocarbons are stripped inthe stripping section,and enter the disengager.Passage of strippedhydrocarbons through the cooler area of the disengager vessel,along with their extended residence time inside the vessel,enhances the chance of condensation of the heaviest componentsof stripped hydrocarbons,which causes coke formation inside thedisengager vessel.In the commercial operation,there are the two basic methods tominimize coking:avoid dead spots and prevent heat losses.Anexample of theﬁrst method is using dome steam or purge steam tosweep out stagnant areas in the disengager[7,8].An example of thesecond method is using proper insulation in the disengager vessels[9].In fact,the essential method to solve coking problems is toprevent heavy hydrocarbons from entering the disengager.In otherwords,heavy hydrocarbons should be converted to lighterhydrocarbons as completely as possible before they enter thedisengager.Therefore,if regenerated catalyst is introduced into thestripping zone and mixed with spent catalyst,the mixture of spentand regenerated catalystsﬂow downward through the stripper,where the countercurrent stream strips the entrained hydrocarbonfrom the catalyst mixture.This admixing of spent and regeneratedcatalyst not only raises the spent catalyst temperature to effectdesorption of entrained hydrocarbon,but also improves thecatalyst activity to enhance catalytic cracking of the entrainedhydrocarbon,thus converting more entrained heavy hydrocarbonsto lighter hydrocarbon products.Consequently,the quantity of theheavy hydrocarbons prone to coke is decreased,which reducessubsequent coke formation in the disengager vessel.Slurry oil is the heaviest component of FCC hydrocarbonproducts,and it is most likely to be condensed to form coke.Therefore,it should be converted to lighter hydrocarbons ascompletely as possible.In general,FCC Slurry is mainly used asblending composite for heavy fuel oil[10].In some commercial FCCunit,the slurry oil can be recycled and cracked along with freshCatalysis Today140(2009)174–178A R T I C L E I N F OArticle history:Available online4December2008Keywords:FCC slurryCatalytic crackingCokeA B S T R A C TThe condensation of heavy hydrocarbon causes the coke formation inside the disengager vessel.Slurry oilis the heaviest component of FCC hydrocarbon products and most likely to be condensed to form coke.Converting slurry to lighter hydrocarbons can alleviate coke formation.The slurry cracking experimentswere carried out in a conﬁnedﬂuidized bed reactor.The results showed that the crackability of slurry waslower than that of FCC feedstock,due to the difference of their properties.About30wt.%heavy oilremained in the product after the slurry was cracked,but its end point declined and the heaviercomponent decreased.The comparison of slurry cracking results at different reaction temperatures andregenerated catalyst contents indicated that the appropriate operating conditions for slurry conversionwere the reaction temperature of5008C and the regenerated catalyst content within25–50wt.%.Crown Copyrightß2008Published by Elsevier B.V.All rights reserved.*Corresponding author.Tel.:+861089733993.E-mail address:jsgao@(J.Gao).Contents lists available at ScienceDirectCatalysis Todayj o u r n a l h o m e p a g e:w w w.e l s e v i e r.c o m/l o ca t e/ca t t o d0920-5861/$–see front matter.Crown Copyrightß2008Published by Elsevier B.V.All rights reserved.doi:10.1016/j.cattod.2008.10.013feed.There is,however,limited information in the open literature on the cracking behavior of FCC slurry.So,this study was designed to investigate the catalytic cracking behavior of FCC slurry,and then to determine the appropriate operating conditions to convert slurry in FCC stripping section.2.Experimental2.1.Feedstocks and catalystsThe slurry was sampled from the commercial FCC unit of Petrochina Huabei Petrochemical Corporation.The physical properties of slurry oil analyzed were density,molecular weight, carbon residue,and hydrocarbon type.These analyses were tabulated in Table1.The catalyst was equilibrium LBO-16sample from the same commercial FCC unit,and its major properties were presented in Table2.The catalysts used in our experiments included spent catalysts and regenerated catalysts.The coke on spent catalysts was 1.12wt.%,while the coke on regenerated catalysts was0.02wt.%.2.2.ApparatusCracking experiments were carried out in a conﬁnedﬂuidized bed reactor system,shownin Fig.1.It is comprised ofﬁve sections:oil and steaminputmechanisms,reactionzone,temperaturecontrolsystem, products separation and collection system.A variable amount of distilled water was pumped into a furnace to form steam,and then mixed with the feedstock pumped simultaneously by another pump attheoutletofaconstanttemperaturebox.Themixturewasheatedin a pre-heater,and then entered into the reactor,where catalytic cracking reactions took place.After reaction,the oil gas was cooled and separated into liquid sample and gas sample.2.3.Analytical methodsCatalytic cracking products include gas,liquid and coke.An Agilent6890gas chromatograph with Chem Station software was used to measure the volume percentage of components in the gas product.The equation of state for ideal gases converts the volume data to mass percentages.The liquid product was analyzed with a simulated distillation gas chromatogram to get the weight percentage of gasoline,diesel oil and heavy oil.Coke content on catalysts was measured with a coke analyzer.2.4.Operating conditionsThe cracking experiments of slurry oil were carried out over regenerated catalysts sampled from a commercial FCC unit.TheTable1Properties of FCC slurry.Item DataDensity(g/cm3,208C)0.9668 API14.3 Carbon residue(wt.%) 5.70 Molecular weight425H/C ratio 1.48Group analysis(wt.%)Saturates50.46 Aromatics34.85 Resins9.40 Asphaltenes 5.29Table2Properties of catalyst LBO-16.Item DataMicro-activity index67 Surface area(m2/g)102 Pore volume(cm3/g)0.28 Packing density(g/cm3)0.90Component(wt.%)Al2O344.30 Re2O3 4.01Metals contentNa(wt.%)0.24 Fe(wt.%)0.41 Cu(m g/g)24 Ni(m g/g)12465V(m g/g)431Particle size distribution(wt.%)0–20m m0 20–40m m5 40–80m m51>80m m44Fig.1.Schematic diagram of conﬁnedﬂuidized bed reactor unit.(1)Constant temperature box;(2)steam furnace;(3)feedstock;(4)electronic balance;(5)oil pump;(6)water tank;(7)water pump;(8)pre-heater;(9)reactor furnace;(10)thermocouple;(11)reactor;(12)inlet and outlet of catalyst;(13)ﬁlter;(14)condenser;(15)collecting bottle for liquid products;(16)gas collection vessel;(17)beaker;(18)gas sample bag.n et al./Catalysis Today140(2009)174–178175operating conditions were listed as follows:catalyst loading was 60g,reaction temperature was 5008C,catalyst-to-oil weight ratio was 6,and weight hourly space velocity was 20h À1.In order to convert slurry oil to lighter hydrocarbons and reduce coke formation in the disengager vessel,regenerated catalysts are introduced into the stripping section to raise reaction temperature and improve catalyst activity.The quantity of the introduced regenerated catalyst and the temperature are key parameters to determine the conversion of slurry.So,we focused on investigating the effect of the two parameters on catalytic cracking of slurry oil.Spent catalysts and regenerated catalysts were mixed in different weight ratios.The content of regenerated catalyst in catalyst mixture varied in the range of 0–100wt.%and the temperature was within 450–5508C.Other operating conditions were the same as those in the cracking experiments of slurry oil.3.Results and discussion3.1.Catalytic cracking behavior of FCC slurryFig.2compared the results of cracking FCC slurry and corresponding FCC feedstock with reaction temperature of 5008C.As expected,a portion of FCC slurry can be converted during catalytic cracking.However,the slurry showed lower conversion.Moreover,the product yields of cracking slurry and FCC feedstock were obviously different.The light oil yield of cracking slurry was only 56%of that of cracking FCC feedstock,and the coke yield was 2.5times higher than that of cracking FCC feedstock.It is obvious that FCC slurry is more difﬁcult to crack.The difference in crackability of slurry and feedstock are due to the difference in their properties.Table 3listed the majorproperties of corresponding FCC feedstock.The comparison between Tables 1and 3showed that slurry oil had much higher density and carbon residue than FCC feedstock,and the ratio of hydrogen to carbon (H/C)of slurry oil was much lower than that of FCC feedstock.Previous work showed that the coke formed in FCC unit was not pure carbon atom,but condensed aromatic,whose H/C ratio was between 0.7and 1.0[11].The H/C ratio of light oil products was approximately 2,and it was higher than 2for gas products.The H/C ratios of saturates,aromatics,resins and asphaltenes in straightrun heavy oil were about 2.0,1.5,1.3and 1.0,respectively [12].The H/C ratio of slurry in the present study was 1.48,and between that of aromatics and resins.It was obvious that the hydrogen content in slurry oil was much lower than that in FCC feedstock.The hydrogen added in light oil had to be transformed from coke precursors during slurry catalytic cracking.Hence,from the viewpoint of hydrogen equilibrium,it is impossible to produce a large amount of light oil products.Consequently,light oil yield of cracking slurry was much lower than that of cracking FCC feedstock.Tables 1and 3showed that the aromatic content in slurry oil was 1.4times higher that in FCC feedstock.The aromatics in slurry were characterized by lower molecular weight,more condensed rings with less and shorter chains in structure.Most of them were mainly trinuclear and tetranuclear aromatics,and therefore evidently different from those in FCC feedstock [13].Moreover,the slurry contained 10wt.%resins,which were polar compounds with polynuclear aromatics in structure [14].In general,the feedstock containing polynuclear aromatics and oleﬁns is more easily to form coke [15].The characteristic of aromatics and resins in slurry determined that the slurry was harder to be cracked,and converted into coke by hydrogen-transfer and condensation reaction during catalytic cracking.Furthermore,the slurry oil was the cracking product and must contain some oleﬁns.Never-theless,the group analysis in Table 1did not include oleﬁns.The oleﬁns also led to form more coke during slurry catalytic cracking.The content of heavy component in slurry above 5508C was 22.0wt.%,indicated that the slurry contains a large amount of heavier components with coking tendency.Whereas,the content of heavy component above 5508C in slurry cracking products was only 0.7wt.%,and its end point was 557.88C.It was observed that after the slurry was cracked,about 30wt.%heavy oil remained in the product,but its end point declined and the heavier component also decreased.It implied that the condensation of stripped heavy hydrocarbons in the disengager vessel would decrease,thus reducing subsequent coke formation.3.2.Effect of reaction temperature and regenerated catalyst content on slurry crackingThe above experiments showed FCC slurry had some crack-ability at appropriate operating conditions.The sampling in commercial RFCC strippers showed that heavy hydrocarbons carried by catalysts underwent thermal cracking,catalytic cracking and dehydrogenation condensation reactions during stripping [16].Due to the low temperature and the catalyst was rather inactive,only a little reaction occurred.So,in order to enhance the conversion of heavy hydrocarbons in stripping section,regener-ated catalysts should be introduced to raise reaction temperature and therefore improve catalyst activity.The following study was designed to determine the appropriate operating conditions to convert heavy hydrocarbons in FCC stripping section.The cracking results of slurry oil at different reaction temperatures and regenerated catalyst contents were summar-ized in Table 4.In this study,the slurry oil conversion was deﬁned as the sum of the yields of dry gas,liqueﬁed petroleum gas(LPG),Fig.2.Cracking results of slurry and corresponding FCC feedstock.Table 3Properties of FCC feedstock.ItemData Density (g/cm 3,208C)0.9004Carbon residue (wt.%) 4.35H/C ratio1.80Group analysis (wt.%)Saturates 60.3Aromatics 25.0Resins14.5Asphaltenes0.2n et al./Catalysis Today 140(2009)174–178176gasoline,diesel oil and coke.Fig.3showed the effect of reaction temperature and regenerated catalyst content on the slurry conversion.In experimental tests,the slurry conversion was below 75%,and went up with increasing reaction temperature.The inﬂuence of regenerated catalyst content on slurry oil conversion was not monotonic with respect to the quantity of regenerated catalyst.As the regenerated catalyst content was below 50wt.%,the conversion increased greatly with increasing the quantity of regenerated catalyst.As the regenerated catalyst content was above 50wt.%,the addition of regenerated catalyst could not evidently improve the conversion of the slurry oil and the conversion decrease a little at high temperature (above 5008C).The desirable products of slurry cracking are gasoline and diesel oil.Fig.4compared the light oil yield of slurry cracking at different reaction temperatures and regenerated catalyst contents.It was observed that the light oil yield increased evidently with the regenerated catalyst content varied from 0to 25wt.%,whereas the regenerated catalyst content had a little inﬂuence on light oil yield as the content was above 25wt.%.The high light oil yield was obtained at 5008C and the regenerated catalyst content ranging from 25to 50wt.%,and increasing further the reaction tempera-ture and regenerated catalyst content was unfavorable for getting more light oil.As mentioned above,a large amount of coke was formed during slurry cracking.The inﬂuence of the reaction temperature and theTable 4Cracking results of slurry oil at different reaction temperatures and regenerated catalyst contents.Reaction temperature (8C)Regenerated catalyst Content (wt.%)Product yield (wt.%)Dry gasLPG Gasoline Diesel oil Heavy Oil Coke 4500 3.37.818.311.346.213.125 3.710.821.811.736.215.850 3.48.822.412.139.413.975 2.210.821.412.033.420.2100 2.610.221.710.630.824.14750 3.48.119.211.045.113.225 4.09.920.212.037.416.550 3.79.920.812.035.917.775 3.510.522.010.432.421.2100 3.310.019.511.433.322.55000 4.510.817.112.038.916.725 4.513.223.511.429.418.050 4.011.523.712.031.717.175 3.911.921.511.831.619.3100 3.511.819.612.331.221.65250 5.612.020.111.432.318.625 4.812.920.211.131.619.450 6.214.824.110.723.820.475 4.412.423.111.127.921.1100 3.411.223.610.733.317.85500 5.110.517.610.037.819.025 6.713.222.510.926.620.150 6.714.122.810.424.121.975 6.614.721.110.125.522.01005.513.422.910.425.921.9Fig.3.Effect of reaction temperature and regenerated catalyst content on slurryconversion.Fig.4.Effect of reaction temperature and regenerated catalyst content on light oil yield.n et al./Catalysis Today 140(2009)174–178177quantity of regenerated catalyst on coke yield was shown in Fig.5.The coke yield went up with increasing reaction temperature and regenerated catalyst content.The higher the reaction temperature and the regenerated catalyst content was,the higher activity catalyst possessed.Consequently,the cracking reaction occurred more drastically and more coke was formed.3.3.Operating conditions to convert slurry in FCC stripping section The purpose of introducing regenerated catalysts into the stripping section is to convert the entrained heavy hydrocarbons to lighter hydrocarbons as completely as possible.As a high conversion is pursued during slurry cracking,the formation of more light oil and less coke is desirable.The experimental results indicated that higher temperature was favorable for the conver-sion of slurry oil,which however resulted in more coke deposit on the catalyst.The increase of the deposition of coke on the catalyst can lead to excessive heat generation during catalyst regeneration.The additional heat can create a number of problems,including upsetting the heat balance and damaging the equipment and the catalyst.To reduce the formation of coke,the temperature in stripping section should not be very high.Fig.4showed that the light oil yield was higher at the reaction temperature of 5008C.Taking conversion and the yield of light oil and coke into account,the appropriate operating temperature for slurry cracking was about 5008C.The results showed that at 5008C,both the conversion and light oil yield increased initially and then decreased slightly with the increase of the regenerated catalyst content.As the regenerated catalyst content was in the range of 25–50wt.%,both slurry conversion and light oil yield were satisﬁed.On the basis of the above research,it can be concluded that,the appropriate operating conditions for slurry conversion are as follows:the reaction temperature is about 5008C and thecontent of regenerated catalyst introduced to the stripping section is within 25–50wt.%.4.ConclusionsThe cracking experiments of slurry oil from a commercial FCC unit over regenerated catalysts from the same FCC unit were carried out in a conﬁned ﬂuidized bed reaction.The results showed that the slurry oil was harder to crack than corresponding FCC feedstock,due to higher density and carbon residue,lower H/C ratio,as well as more polynuclear aromatics and oleﬁns.Hence,more coke formed and light oil yield decreased obviously during slurry cracking.After the slurry was cracked,about 30wt.%heavy oil remained in the product,but its end point declined and the heavier component also decreased.The reaction temperature and regenerated catalyst content had a profound effect on the slurry conversion,light oil and coke yield.The slurry conversion and the coke yield went up with increasing reaction temperature.As the regenerated catalyst content was below 50wt.%,the conversion and light oil yield increased with the quantity of regenerated catalyst.As the regenerated catalyst content was above 50wt.%,the addition of regenerated catalyst could not pronouncedly improve the conversion and furthermore decrease the light oil yield.The appropriate operating conditions for slurry conversion were the reaction temperature of 5008C and the regenerated catalyst content within 25–50wt.%.AcknowledgementsThe authors acknowledge the ﬁnancial supports from National Natural Science Foundation of China (No.20406013),China Petroleum &Chemical Corporation (No.105045),and the Program for New Century Excellent Talents in University (No.NECT-04-01070).References[1]M.Y.He,Catalysis Today 73(2002)49.[2]J.S.Gao,C.M.Xu,D.W.Gao,Petroleum Science and Technology 22(5/6)(2004)625.[3]L.J.Mcpherson,Oil &Gas Journal 10(September)(1984)139.[4]X.D.Ye,W.Q.Xu,J.X.Liu,Petroleum Processing and Petrochemicals 34(2)(2003)21.[5]R.C.Barlow,Hydrocarbon Processing 65(7)(1986)37.[6]P.Li,Petroleum Processing and Petrochemicals 34(4)(2003)31.[7]K.R.Dwight,E.F.Daniel,U.S.Patent 5,330,970(1994).[8]W.Q.Wang,X.C.Wang,G.H.Liu,Petroleum Reﬁnery Engineering 33(3)(2003)39.[9]Y.R.Fan,W.Zhai,C.J.Zhang,Petroleum Processing and Petrochemicals 31(6)(2000)17.[10]L.Zhang,Z.M.Xu,Y.X.Hu,Petrochemical Technology 28(5)(1998)337.[11]T.C.Ho,Industrial &Engineering Chemistry Research 31(1992)2281.[12]S.X.Lin (Ed.),Petroleum Reﬁning,Petroleum Industry Press,Beijing,2000.[13]Q.Shi,Z.M.Xu,Y.M.Lian,Acta Petrolei Sinica (Petroleum Processing Section)16(2)(2000)90.[14]C.D.Yang,J.L.Chen,Acta Petrolei Sinica (Petroleum Processing Section)3(4)(1987)75.[15]W.S.Letzsch,A.G.Ashton,in:J.S.Magee,M.M.Mitchell,Jr.(Eds.),Fluid CatalyticCracking:Science and Technology,Elsevier,Amsterdam,1993.[16]n,C.M.Xu,G.Q.Yu,J.S.Gao,Petroleum Reﬁnery Engineering 37(4)(2007)1.Fig.5.Effect of reaction temperature and regenerated catalyst content on coke yield.n et al./Catalysis Today 140(2009)174–178178。

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J Appl Electrochem (2009) 39:577-582DOI 10.1007/s10800-008-9695-zORIGINAL PAPERElectrochemical treatment of pharmaceutical azo dye amaranthfrom waste waterRajeev Jain . Nidhi Sharma . Keisham RadhapyariReceived: 25 February 2008/Accepted: 13 0ctober 2008/Published online: I November 2008@ Springer Science+Business Media B.V. 2008Abstract The electrochemical behavior of pharmaceuti-cal azo dye amaranth has been investigated in distilledwater and Britton-Robinson buffer. One well-definedirreversible cathodic peak is observed. This may beattributed to the reduction of the -N=N- group. Calculationof the number of electrons transferred in the reductionprocess has been performed and a reduction mechanismproposed. Results indicate that the electrode process isdiffusion controlled. The cathodic peak in the case of controlled potential electrolysis is found to reduce substantially with a decrease in color and absorbance. The reaction has first order kinetics with k value 5.75 x10-2 abs min-l. The effciency of different electrode materials (platinum and steel) for decolorisation is compared. Chemical oxygen demand (COD) decreases substan-tially from 2,680 t0 96 ppm at platinum and t0 142 ppm atsteel. This translates t0 97% COD removal at platinum and95% at steel.Keywords Electrochemical treatment . AmaranthAzo dye . Industrial effluents . CV, CODI IntroductionAzo dyes continue to be a source of pollution fromindustrial processes which employ dyes to color paper,R. Jain . N. Sharma . K. RadhapyariSchool of Studies in Chemistry, Jiwaji UniversityGwalior 474011, Indiae-mail: raj eevj ain54 @ yahoo.co.inplastics, foodstuffs, pharmaceutical products, and naturaland artificial fibers [1, 2]. It is reported that approximately5 tonnes of dye discharge from dye and coloration industriesevery year [3]. The release of such compounds into theenvironment is of great concern due to their toxicity,mutagenicity, carcinogenicity, and bio-transformationproducts [4-6]. Hence. much research has focused onmethods of azo dye destruction. Many treatment processeshave been investigated extensively to treat wastewaters suchas chemical precipitation [7], adsorption [8], biologicaltreatment [9], photocatalytic degradation [10, 11], electro-catalytic oxidation [12], ozonation [13], Fentons' reaction[14], and electrochemical methods [15-19]. Electrochemi-cal techniques are an attractive methodology for thetreatment of dye wastewaters. This technique has significantadvantages viz., wide application, simple equipment, easyoperation, lower temperature requirements. and no sludgeformation [20-24].Amaranth (Fig.1) [trisodium salt of l-(4-sulpho-l-naphthylazo)-2-naphthol-3, 6-disulphonic acid] is an acidicmonoazo dye used as food and pharmaceutical colorant.Only a few analytical methods, such as square waveadsorptive stripping voltammetry (SWAdSV) and spec-trophotometry are available for determination of amaranthin soft drink samples [25]. Degradation of amaranth fromenvironmental samples has been studied on activated car-bon fiber (ACF) electrodes [26,27]. The amaranth azo dyehas electroactive groups. However. its electrochemicalbehavior and treatment have not been investigated.Therefore, cyclic voltammetric and differential pulsepolarographic studies have been undertaken in the presentwork for understanding the electrochemical behavior ofamaranth. Results have been analyzed employing the cri-terion of complete decolorisation of the dye-containingsolutions.Springer578J Appl Electrochem (2009) 39:577-582Na07SOH S03NaFig. 1 Structure of amaranth2 Experimental2.1 InstrumentationO,NaCyclic voltammetric (CV) studies were carried out on an EGand G potentiostat (Princeton Applied Research) integratedwith applied electrochemistry software. The working elec-trode potential was cycled between -1.2 and +1.2 V atdifferent sweep rates (50-2.000 mV s-1). The electrochemical cell consisted of three electrodes (in close proximity) immersed in the solution to be electrolyzed. The voltammetric behavior was studied using platinum as working electrode, SCE as reference, and platinum wire as counter electrode. Controlled potential electrolysis was carried out using a cyclic voltammograph coupled to a digital electronic 2000 0mnigraph x-y/t recorder. The working electrodes used for controlled potential electrolysis (CPE) were platinum foil (3 x 3 cm2)and steel foil (4.5 x 3.5 cm2), Ag/AgCI as reference elec-trode and platinum wire as counter electrode.Differential pulse polarographic (DPP) measurementswere carried out on an Elico pulse polarograph model CL 90 connected with Polarocord recorder model LR-108.Triple distilled mercury was used for the DME. The capillary had a flow rate of 3.02 mg s-l together with a drop time of 3 s. The pH measurements were made on a Hach digital EC-40 Benchtop pH/ISE meter. The absorption spectra of samples were recorded using an Elico SL 159 UV-Visible spectrophotometer. The chemical oxygen demand (COD) was determined using the open reflux method using COD digester apparatus (Spectralab 2015-S).The synthetic azo dye amaranth was obtained from Aldrich USA. All chemicals used were AR grade. Readymade silica gel G plate for TLC, having fine coating on alumina sheet. was obtained from E-Merck.2.2 Reagents and materialsStock solution of amaranth (2 x l0-3 M) was prepared in doubly distilled water. In order to evaluate the effect of varying pH, BR buffers in the pH range 2.5-12.0 were prepared as per a literature method[,. ]. The supportingSpringerelectrolyte was l.0 M KCI.For the COD experiments reagents were prepared in accordance with standard methods (APHA. 1995) [29].2.3 ProcedureThe CV and DPP studies were carried out by mixing l.0 mL of potassium chloride, 1.0 mL stock solution, and 8.0 mL of appropriate BR buffer/distilled water. Solutions of different concentrations were prepared. Dissolved oxygen was removed from the solution by passing nitrogen gas for about 15 min. The polarograms and cyclic voltammograms were then recorded. The redox behavior was studied at varying pH (2.5-12.0), concentrations and sweep rates (100-2,000mV s-l). Controlled potential electrolysis of the dye solution was performed at slightly more negative potential than the peak potential of the respective peak. Absorbance of the olution was measured at different time intervals at 520 nm.The value of the rate constant k was calculated from the l091(absorbance) vs time plots. The number of electrons transferred was calculated from the decrease in current with time during electrolysis. Controlled potential coulometry was also carried out at different pH values. The progress of electrolysis was monitored by recording cyclic voltammograms at regular intervals of time. The end products of electrolysis were identified by TLC. For COD studies. The experiments were carried out as per standard methods.2.4 CoulometryFor the coulometric determination of number of electrons "n" consumed in the reduction. a solution of depolarizer,potassium chloride, and buffer/distilled water was mixed in the same ratio as that for CV and DPP studies. The solution was de-aerated by passing nitrogen gas for 15 min and cyclic voltammograms were recorded at slightly more negative potential than the peak potential. With the progress of electrolysis the color of the solution gradually faded and finally a colorless solution was obtained. The number of electrons "n" transferred at the platinum electrodewas determined from the formula Q = nFN.3 Results and discussion3.1 Cyclic voltammetric (CV) studiesThe cyclic voltammogram of amaranth in distilled water (2 x 10-4 M) exhibits reduction peak at -0.872 V and corresponding oxidation peak at -0.779 V at scan rate of 100 mV s-l. The cathodic peak can be safely assigned to the reduction of the azo (-N=N-) group. The separation between cathodic and anodic peak potentials is more than 60 mV. indicating the irreversible nature of the electrode process [30]. As the scan rate (v) is increased. the reduction peak potential shows negative shift and the oxidation peakpotential shows positive shift. At higher scan rate of1,000 mV s-1 the reduction peak appears at -1.0 V andthe oxidation peak at -0.697 V. The peak potential separation (AEp) increases gradually from 0.093 t0 0.306 V asthe scan rate is increased from 100 to 1,000 mV s-l suggesting the irreversible nature of the electrode process.The plot of ip,c vs 1/2 in the 6.5 pH solution is a straight line passing through the origin indicating the diffusion controlled nature of the electrode process (Fig. 2 (I)) This proportionality may be attributed to the fact that a steeper concentration gradient is established thereby increasing the rate of diffusion at faster scan rates. Reduced species will diffuse away from the electrode faster as the scan rate is increased [31,32]. A similar plot for the dye solution in neutral aqueous medium and at pH 8.8 is,once again, a linear behavior, however, not passing through the origin. This indicates adsorption effects contributing to diffusion current. In such a case an adsorbed species may undergo electron transfer.3.2 Effect of pHWell-defined cathodic peaks in the acidic pH range are obtained with both platinum and glassy carbon electrodes.With increase in pH the cathodic peak shifts negatively and the anodic peak positively with increasing pH, which indicates that proton transfer occurs as a step consecutive to an irreversible electrode process [33]. The plot of Ep.c vs pH is linear up to pH 6.5 as also above 6.5.However. the two linear segments have different slopes.The value of pH 6.5, is in accord with the pKa value.Above pH 6.5, the Ep,c becomes practically independent of pH. This indicates the reduction of unprotonated species34]. These results are presented in Table .3.3 Differential pulse polarographic studiesA single four-electron irreversible reduction peak is observed in the pH range 2.5 t0 12.0 at the mercury electrode. This may be attributed to reduction of the azo group(-N=N-). A shift in Ep,c towards more cathodic potentialwith pH, along with a break at pH 6.5, is observed. Beyondthis there is near constancy in Ep,c (Fig.3). This suggestsparticipation of protons in the rate determinatiAnalysisofthepeakEd.e.vs log刍）- O;,at4m, lo[rt]Xtand shifting of the peak potential towards more negativevalue with concentration suggests the irreversible nature ofthe electrode process [35,36]. The results of DPP studies arethus in close agreement with those of the CV studies.3.4 Controlled potential coulometric studiesBy using controlled potential coulometry, the number ofelectrons transferred "n" at platinum electrode werecalculated and this lies in the range 2土0.2 (Table ..). Thevalue of "n" lies in the range 4 + 0.2 at the steel electrode.Controlled potential electrolysis of amaranth (2 x 10-4 M)at platinum and steel electrodes was carried out at -1.20 V.Bench scale electrochemical treatment was carried out.Electrolysis results in complete disappearance of colorwhich is fairly faster in case of platinum where the solutionis decolorized within 10 min of electrolysis leading to thecomplete disappearance of the cathodic peak current. Withsteel. the colored solution took 80 min for complete colorremoval. The data are summarized in Table '_ . A compara-tive overlay of the dye solution of pH 8.8 before and afterelectrochemical treatment is presented as Fig. i.3.5 Spectral studiesUV-visible spectra of amaranth (2 x 10-4 M) in distilledwater were recorded at Amax = 532.5 nm. The progress of 有错controlled potential electrolysis was monitored by record-ing spectral changes at different time intervals. AtAnax = 532.5 nm, absorbance decreases systematically 有错with the progress of electrolysis. The kinetic measurementswere conducted at steel electrodes. The observed rateconstant, k= 5.75 x 10-2 a s min-l was determinedfrom the first-order kinetics plot of log absorbance vs time3.6 COD removalThe electrolyzed solution shows a substantial decrease inCOD from an initial value of 2,680 ppm to a final value of96 ppm at platinum and t0 142 ppm at steel.3.7 Proposed mechanismOn the basis of the coulometry, controlled potential elec-trolysis, chromatographic and spectral analysis, tworeduction mechanisms are proposed. One is the two elec-tron reduction to hydrazo compound at platinum (Fig. ).A four electron reduction at steel (Fig. ) may be favoredby the presence of the strong electron releasing substituent,the -OH group [37].In Fig.6, amaranth undergoes 2e- reduction in acidic aswell as alkaline medium. The reduction process proceedsby the protonation of the polarized molecule resulting in the formation of (B). In the second step, which is slow and rate determining, (B) accepts 2e- and a proton and results in the formation of stable hydrazo (-NH-NH-) form (C).In Fig.7, 4e- reduction takes place at the steel foil electrode. The I and II steps of reduction proceed in the same way as described in Fig. . In step III. (c) the hydrazo moiety undergoes a further two electron reduction resulting into two products (D) and (E).4 ConclusionThe newly developed electrochemical method gives satis- factory and promising results. The electrochemical reduction of amaranth under the experimental conditions described in this work is an irreversible process controlled by diffusion. Both platinum and steel electrodes exhibit great stability and resistance to redox and acidic/basic environments showing no deactivation. During the elec- trochemical degradation process, the COD decreases by approximately 97u/o at the platinum electrode and by 95% at the steel foil electrode with complete color removal. The electrochemical treatment developed achieves higher de- coloration and COD removal than that reported previously through the ACF electrode treatment method [26] which gives only 60% COD removal. Hence, the present elec- trochemical procedure is a better alternative approach for wastewater treatment resulting in significant lowering of toxicity.。

RECOVERY OF CATALYTIC METAL

专利名称：RECOVERY OF CATALYTIC METAL发明人：SUZUKI TAKASHI,KITAHARAKOUICHI,FURUTA TOMIYOSHI,NOZAKISADAO申请号：JP8234281申请日：19810529公开号：JPS57197039A公开日：19821203专利内容由知识产权出版社提供摘要：PURPOSE:To recover a catalytic metal, by a method wherein a distillation residue in a reaction using a Co and/or Mn catlyst is hydrated and then washed with an org. solvent having a specific dielectic constant. CONSTITUTION:A distillation residue obtained in a process wherein an aliphatic substituted aromatic hydrocarbon or an oxidized derivative thereof is oxidized in a liquid phase in the presence of a cobalt and/or a manganese catalyst and the formed aromatic carboxylic acid is distilled off from the obtained reaction product is hydrated and then washed with an org. solvent having a specific dielectic constant D of 3.0-3.5 such as acetone or ethyl acetate. By this method, an org. substance such as a tar-like byproduct is removed and cobalt and/or manganese can be recovered. Thus the catalytic metal is recovered simply.申请人：MITSUBISHI GAS KAGAKU KK更多信息请下载全文后查看。

一锅法制备铋基催化剂在乙炔氢氯化反应中催化性能的研究

一锅法制备铋基催化剂在乙炔氢氯化反应中催化性能的研究漆维霞;王璐;王丰;王吉德【摘要】本文采用一锅法(PM)和等体积浸渍法(IM)制备了铋基催化剂并考察了PM的制备条件对催化剂的影响.使用固定床反应器对催化剂进行评价.结果显示,PM催化剂具有较好的催化活性,此时的制备条件如下:反应温度为160℃,反应时间为2h.对催化剂进行XRD,BET,EDS和SEM等表征,结果表明,PM催化剂具有微球形貌,提供丰富的孔道结构,较大的比表面积和更多的活性位点,改善了催化剂的催化性能.除此之外,反应中积碳可能是导致铋基催化剂失活的一个原因.%In this work,Bi-based catalysts were prepared by one pot method (PM) and incipient wetness impregnation method (IM) and preparation conditions of the PM were researched.Catalytic activity of catalysts was evaluated using a fixed-bed reactor for acetylene hydrochlorination.The results displayed that the PM catalyst was prepared at 160℃ for 2 h possessed a superior catalytic performance compared to the IM catalyst.The characterizations of XRD,BET,EDS and SEM demonstrated that the PM catalyst was microspheres structure,which could provide richer channelstructures,larger specific surface areas and more active centres,thus improving the catalytic performances of catalysts.In addition,carbon deposition in the reaction was a possible reason for Bi-based catalysts deactivation.【期刊名称】《新疆大学学报（自然科学版）》【年(卷),期】2017(034)002【总页数】6页(P127-132)【关键词】一锅法;铋基催化剂;乙炔氢氯化【作者】漆维霞;王璐;王丰;王吉德【作者单位】新疆大学石油天然气精细化工教育部和自治区重点实验室,化学化工学院,新疆乌鲁木齐830046;新疆大学石油天然气精细化工教育部和自治区重点实验室,化学化工学院,新疆乌鲁木齐830046;新疆大学石油天然气精细化工教育部和自治区重点实验室,化学化工学院,新疆乌鲁木齐830046;新疆大学石油天然气精细化工教育部和自治区重点实验室,化学化工学院,新疆乌鲁木齐830046【正文语种】中文【中图分类】O643.320 IntroductionsVinyl chloride monomer(VCM)is an irreplaceable raw material for the production of polyvinyl chloride(PVC),which is one of important plastics and widely used in real life[1].Acetylene hydrochlorination,which was catalyzed by mercuric chloride supported on activated carboncatalyst(HgCl2/AC),is the main process for VCM production[2-4].However,HgCl2/AC catalyst is highly toxic and faces seriously challenge of resource shortage[5].Therefore,the development of mercury-free catalyst is an inevitable trend for the acetylene hydrochlorination.Noble metal(Au,Pd,Pt,Ru)and non-noble metal(Sn,Cu,Bi,etc.)catalysts[6-12]were studied for acetylene hydrochlorination in current years.Noblemetal catalysts displayed an excellent catalytic performance,but they were difficult to realize VCM industrial applications due to their high cost and the poor stability.Hence,non-noble metal catalysts have been attracted much attention for acetylene hydrochlorination recently.For example,Zhou et.al studied the Cu/Bi bimetallic catalyst and the results verified that its activity and stability presented more advantages in industrialization compared to others non-noble metal catalysts[13].For Bi-based catalysts,BiOCl was main active species and possessed a certain crystal and morphology[14].In our previous work,we found that the BiOCl crystal plane and morphology were exposed sufficiently after Bi-based catalysts were treated by high-temperature steaming[15]and catalytic activity was improved.Accordingly,a speculation that the catalytic activity of catalysts was related to the crystalline structure of active components BiOCl for acetylene hydrochlorination reaction was made.In order to explore the structure-activity relationship,a large number of methods such as chemical vapor transport approach,wet-chemical and one-pot solvothermal method[16-18]were used to prepare BiOCl with different morphology as photocatalysts and experimental results proved that the catalytic activity of photocatalysts was affected by the morphology ofBiOCl.Subsequently,Zhang et al.reported 2D BiOCl nanodisks[19]and proposed that the growth of nanodisks followed Ostwald ripening mechanism[17,20].Meanwhile,hierarchical nanostructures BiOCl were formed by one pot method with ethylene glycol as solvent[21]and results showed that the BiOCl of nanosheets exhibited high photodegradationefficiency.So far,there were only few literatures which reported systematically the relationship between the morphology of active components and catalytic performance in acetylene hydrochlorination reaction.In this paper,we reported a simple,efficient and environment-friendly method(one pot method)to prepare Bibased catalysts,which could be adequately applied for acetylene hydrochlorination.The results indicated that the PM catalyst prepared for 2 h at 160oC exhibited higher catalytic activity.The catalysts were characterized by X-ray diffraction(XRD),Scanning electron microscopy(SEM),Brunauer-Emmett-Teller(BET),and reason about high catalytic activity of the PM catalyst were discussed.1 Experimental1.1 Catalyst preparationThe Bi-based catalyst was prepared by using one pot method.About0.0256 mol Bi(NO3)3·5H2O and 0.0256 mol KCl(molar ratio of Bi/Cl=1)was added into 30 mL ethylene glycol(EG).After stirring for 1 h at room temperature in air,the mixture was transferred into a 100 mL Te flon-lined stainless steel autoclave with 5 g activated carbon.The autoclave was maintained at 160˚C for a period time,and cooled to ambient temperature.The sample was filtered and washed with distilled water for three times,then dried at 120˚C for 12 h.The obtained sample was designated as the PM catalyst.For comparison,a conventional catalyst(the IM catalyst)was prepared by ultrasonic-assisted incipient-wetness impregnation method using BiCl3aqueous solutions,as described in ourprevious work[14].1.2 Catalyst characterizationX-ray diffraction(XRD)data were collected using M18XHF22-SRA diffraction instrument operating at 50 kV,and 100 mA selecting the Cu-Kα i rradiation in the scan range of 2θ between 10˚and 80˚.The specific surface area and pore structure of catalysts were analyzed with JW-BK Brunauer-Emmett-Teller(BET)equipment at 77 K under liquid nitrogen environment for the samples outgassed at 150˚C for 2 h.Scanning electronmicroscopy(SEM)and energy dispersive X-ray(EDX)analyses were performed using a LEO1450VP detector.1.3 Catalytic performance testThe catalytic performance test of Bi-based catalysts was investigated in a fixed bed with a 10-mm-diameter quartz tube micro reactor operating just at normal pressure.N2 flow(25 mL·min−1)via calibrated mass flow controllers(SevenstarHuachuang electronics Co.ltd,Beijing,China)in a heated glass reactor and then hydrochloride ata flow rate of 20 mL·min−1passed t hrough the reactor to activate the catalyst.After the reactor was heated to 160˚C,hydrochloride(6.3 mL·min−1)and acetylene(8.8 mL·min−1)were fed through a mixing vessel containing catalyst(5.0g),giving a total gas hourly space velocity(GHSV)of 120 h−1.The exhaust gas mixture from the glass reactor was passed through an absorption bottle containing sodium hydroxide solution and the composition of gas mixture was determined immediately using a gas chromatograph(GC 2010,Shimadzu).Catalytic activity of the catalyst was evaluated byconversion of acetylene(XA)and the selectivity of VCM(SVCM).2 Results and discussion2.1 The effect of different preparation methods on catalytic performance The catalytic performance of Bi-based catalysts was shown in Fig1.Although the IM catalyst had a higher initial activity slightly than the PM catalyst,the acetylene conversion of the PM catalyst was remarkably higher than that of the IM catalyst during 12 h operation(with about76.12%acetylene conversion),it demonstrated that the catalyst prepared by one pot method could positively improve the catalytic performance for acetylene hydrochlorination.Fig 1 Evaluation of catalysts prepared by different methodsReaction condition:temperature=160˚C,feed volume ratioVHCl:VC2H2=1.25,GHS V=120 h−1.XRD characterization was used to exhibit the crystal structure of fresh and used PM and IM catalysts.The results were shown in Fig 2.It could be seen that the tetragonal structure of BiOCl(JCPDS No.06-0249)was easily detected in the fresh PM and IM catalysts.For the fresh PM catalyst,more intense and sharper peaks were tested,which proved that one pot method was bene ficial to acquire better crystallization and higher content of BiOCl on the surface of the activated carbon support.For the used PM catalyst,the all characteristic peaks of BiOCl disappeared,which indicated that the crystallographic structure or content of BiOCl were changed in the catalysts during the reaction.Pore structure parameters of the above catalysts are summarized in Tablepared with the AC support,the specific surface and total pore volume of the fresh PM and IM catalysts are decreased,but their average pore size was increased.The change of texture properties of Bi-based catalysts could be due to the active component was loaded on the support and covered some pores on the surface of the AC support[22].It is clearly that both the specific surface area and total pore volume of the fresh PM catalyst were higher than those of the fresh IM catalyst,but its average pore size was lower.Fig 3(a)and(b)illustrated the morphology of the PM and the IM catalysts,respectively.The PM catalyst exhibited homogeneous microsphere about 3.0-3.4µm,which could provide more active sites.But the IM catalyst presented irregular surface accumulation state without clear pore structure.Therefore,combining with BET,SEM and evaluation results,larger specific surface area,better BiOCl morphology and more active centres were provided on the surface of the PM catalyst,which would enhance the catalytic performance of the Bi-based catalyst.Table 1 Porous structure parameters of Bi-based catalystsAC 820 0.54 1.31 Fresh PM 413 0.28 1.37 Used PM 13 0.02 3.42 Fresh IM 144 0.15 2.01 Used IM 79 0.10 2.45Table 2 listed EDX spectra data of the PM and IM catalysts.For the fresh catalysts,the relative content of Bi in the PM catalyst 21.10 wt%was much more than that of the IM catalyst 15.32 wt%,but the relative content of C in the PM 49.36 wt%was less than that in the IM 62.61 wt%.More active component in the PM catalyst might attribute to its larger specific surface,which provided more active sites[23].This information indicatedthat the PM catalyst might have a better catalytic performance,which was in good agreement with the evaluation results.For the used catalysts,the relative content of Bi was lower than those of the corresponding fresh catalysts.The loss ratio of Bi in the PM catalyst is 19.62%less than that of the IM catalyst 48.56%.It was also demonstrated that the Bi-based catalyst prepared by one pot method had a better catalytic activity attributing to decreasing the loss of Bi active component.In addition,it is noted that the relative content of C increased in the all used catalysts.Therefore,it implied that the carbon deposition produced during the reaction could plug porous channels and cover active centers,leading to the reduction of catalytic activity[24],which was in accordance with the XRD characterization and evaluation results.Moreover,the decrease of relative content of Cl,O and K to some degree may be a considerable reason for the deactivation of the PM catalyst[25].Fig 2 XRD spectra of catalysts from different preparation methods:incipient wetness impregnation method(IM);one pot method(PM)Fig 3 Representative SEM images of the catalysts prepared by(a)PMand(b)IMTable 2 Elements content of the sample record by EDXFresh PM 49.38 14.26 14.73 0.53 21.10 Used PM 58.25 11.90 12.65 0.26 16.94 Fresh IM 62.61 11.72 10.35 0.00 15.32 Used IM 72.56 10.21 9.35 0.00 7.882.2 Effect of preparation conditions of one pot method on catalytic performanceIt was found that,in this work,the structure,morphology and catalyticperformance of the catalysts were affected by temperature and reaction time in the one pot method to prepare catalysts.The effects of temperature and reaction time on the catalytic performance of catalysts were shown in Fig 4 and Fig 5,respectively.As can be seen in Fig 4,the catalytic activity of catalysts was enhanced with the temperature of preparation increasing from 60oC to 160oC and the catalyst performed the best activity at160˚C:the conversion of acetylene was almost at 77%.While the catalytic activity declined rapidly as the temperature exceeded 160oC.Hence,160˚C was selected as the optimal temperature to prepare catalyst.For the reaction time,the catalytic activity of the catalyst prepared at 160oC for 2 h was higher than those at the 1 h,12 h and 36 h,as shown in Fig 5.Fig 4 Evaluation of catalysts prepared for 2 h at different reaction temperatureReaction condition:temperature=160oC,feed volume ratio VHCl:VC2H2=1.25,GHSV=120 h−1.Fig 5 Evaluation of the fresh catalysts prepared at 160˚C for different reaction timeReaction condition:temperature=160oC,feed volume ratio VHCl:VC2H2=1.25,GHSV=120 h−1.Fig 6 shows XRD patterns of the fresh catalysts prepared at 160oC for different reaction time.The tetragonal structures of BiOCl are exhibited on the all catalysts.The stronger and sharper diffraction peaks,especiallythe(101)diffraction peak,were observed in the catalyst prepared for 2h,suggesting better crystal was formed and more active centres were exposed on the surface of activated carbon carrier,resulting in higher catalytic activity of the catalyst.Fig 7 displayed the morphology of the freshcatalysts prepared at 160oC for different time.It was clearly that the spherical structure with 4µm diameters was formed on the surface of the catalyst when the reaction time was 2 h.No spherical morphology was found at the other reaction time:aggregated nanosheets at 1 h and 12 h, flower-like structure at 36 h,respectively.Therefore,according to above data showed that the spherical structure and fine crystallization of active component BiOCl of the catalyst,which prepared at 160oC for 2 h by one pot method,was bene ficial to the acetylene hydrochlorination.Fig 6 XRD spectra of catalysts prepared at 160oC for different reaction time:(A)1 h;(B)2 h;(C)12 h;(D)36 hFig 7 SEM images of catalysts prepared at 160oC for different reaction time:(a)1 h;(b)2 h;(c)12 h;(d)36 h3 ConclusionsThe paper compared catalytic performance for acetylene hydrochlorination of Bi-based catalysts prepared by different methods:one potmethod(PM)and incipient-wetness impregnationmethod(IM).Meanwhile,effect of temperature and reaction time on the performance of catalysts was investigated.The PM catalyst prepared at 160oC for 2 h displayed a better catalytic performance compared with IM catalyst.The characterization results demonstrated that the morphology of the PM catalyst was microspheres structure,which would provide larger specific surface areas,richer channel structures and more active centres,leading to improve catalytic performance ofcatalysts.Moreover,carbon deposition in the reaction was a possible reasonfor Bi-based catalysts deactivation.References：[1]Yoshioka T,Kameda T,Imai S,et al.Dechlorination of poly(vinyl chloride)using NaOH in ethylene glycol under atmosphericpressure[J].Polym Degrad Stab,2008,93(6):1138-1141.[2]Wei X,Shi H,Qian W,et al.Gas-phase catalytic hydrochlorination of acetylene in a two-stage fluidized-bed reactor[J].Ind Eng ChemRes,2008,48(1):128-133.[3]Conte M,Davies C J,Morgan D J,et 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中石油2016通用英语选读课文53Oil Refining石油炼制

53. Oil Refining石油炼制1.Primary Refining1.粗炼2.Petroleum refining is the process of separating the many compounds<混合物> present<目前的> in crude petroleum.This process is called fractional distillation<分馏>where the crude oil is heated;the various compounds boil at different temperatures and change to gases;and are later recondensed<v再浓缩，再凝结> back into liquids.The primary refining processes are the distillation<n.（蒸馏（过程）;蒸馏物;蒸流;升华>of the feedstock<n给料，进料>into its basic fractions<馏分>,and then the re-distillation of these,in separate towers,into highly concentrated<浓缩的，浓度的>intermediates<n媒介，半成品adj中间的>.2.石油炼制是将原油中的多种混合物进行分离的过程。

原油经过加热后，其中的不同组分将在不同的温度下沸腾并气化，随后又经冷凝浓缩转化为液体，这个过程称为分馏。

粗炼工序是将进料蒸馏成为其基本组分，然后再将这些组分在单独的炼塔中再蒸馏成为高浓度的半成品。

3.Distillation is the start of the refining process where the crude oil is split<分开，分裂>into a number of parts or cuts.The separation is made on the basis of boiling-point and groups of hydrocarbons boiling within a certain range are produced. The theory of distillation is very easy.The longer the carbon chain,the higher the temperature at which the compounds will boil.When crude oil boils,it sends out vapor<蒸汽> and condenses<冷凝>.All the different hydrocarbons in crude oil are at different temperatures.And their vapors all make separate liquids (fractions).The split are usually grouped into three categories:light distillates(LPG<液化石油气>,gasoline<汽油>,naphtha<n石脑油>),middle distillates(kerosene<煤油>,diesel<柴油>),heavy distillates and residuum<n剩余，残渣>(heavy fuel oil,lubricating oils<润滑油>,wax<蜡>,asphalt<n沥青>).3.蒸馏是炼油工艺流程的开始。

化工专业英语Unit8

通过改变工艺或者精炼模式它可以用于许多燃料的生产，而通过化学改变可以用于许多纯的化学物质——石油化工产perate continuously. First a tubular
heater（管式加热器） supplies hot oil to an efficient
异构烷烃系列，CnH2n+2 。这些带有支链的烷烃在内燃机中表现的比正构烷烃好因而是（人们）更加渴望得到的。他们也可以通过重整、烷基化、聚合反应或者异构化反应来制备。在原油中只有一小部分是以异构烷烃的形式存在。
• Olefin(石蜡), or Alkene（烯烃） Series, CnH2n.
paraffins and hence are considered more
desirable. They may be formed by catalytic
reforming, alkylation, and polymerization. Only
small amounts exist in crudes.
因为它是一种几千种有机物质的混合物，所以已经证明它可以适应我们（不断）改变的需要。
It has been adapted, through changing patterns of processing or refining, to the manufacture of a variety of fuels and through chemical changes to the manufacture of a host of pure chemical substances, the petrochemicals（石化产品） .
（期间）所采用的处理工艺包括各种个样的裂化单元（使大分子转化为小分子的操作），如聚合、重整、氢化裂解、氢化处理、异构化和更深度的处理——炼焦，（还有）许多其他的设计的工艺用来改变沸点和分子的几何（形状）。

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32
W. Ma et al. / Biomass and Bioenergy 102 (2017) 31e36
pressure distillation is one of the most commonly used separation methods in petrochemical and ﬁne chemical processing. It is also reported that the distillation process improved the corrosivity, storage stability and heating value of fast pyrolysis bio-oil [6]. Catalyst plays an important role in catalytic cracking process [7]. The ZSM-5 zeolite has been proved to be an effective catalyst for cracking, because it has high speciﬁc surface area, high adsorption ability and unique porous structure [8,9]. However, micro-porous structures limit mass transfer and increase diffusion resistance. Most of intermediate compounds in the pore cannot fast enough to escape, which can result in catalyst deactivation [9]. The mesoporous materials (such as MCM-41) have poor hydrothermal stability and weak acidity, which has been attributed to amorphous of hole wall [10]. The composite molecular sieves with microporous and mesoporous structures can possibly combine the advantages of variously-sized porous structures. Di et al. [11] reported that the ZSM-5/MCM-48 composite catalyst synthesised has high activity and stability for methanol to gasoline conversion. The interconnected microporous and mesoporous channel systems, has shown to greatly inﬂuence the distribution of the hydrocarbon products comparing to these on pure ZSM-5 zeolite. Sang et al. [12] found that micro-mesoporous H-ZSM-5/MCM-41 have a micropore and mesopore dual pore size distribution. This catalyst combined the channel advantage of mesoporous molecular sieve with the acidity of microporous zeolite, which greatly improved the reaction and diffusion of reactants in the pores. In order to further relieve catalyst deactivation caused by coke deposition on the surface of zeolites, incorporation of transition metal into the framework is necessary to reduce the generation of polycyclic aromatic hydrocarbons that is a key reason for coke formation [13]. Ni is a very active metal used for the zeolite catalyst modiﬁcation, which can enhance the oleﬁn oligomerization and deoxygenation activity, increase aromatics formation and limit coke formation [14,15]. There are few studies focusing on feedstock pretreatment by improving H/Ceff and using metal loading on micro-mesoporous ZSM-5/MCM-41 composite molecular sieves for catalytic cracking of bio-oil. In this study, in order to improve the H/Ceff value of feedstock, raw bio-oil from rice hull fast pyrolysis was ﬁrstly distilled under reduced pressure, then mixed with ethanol (H/Ceff of 2.00) by 2:3 weight. The mixtures were subjected to catalytic cocracking over ZSM-5/MCM-41 and Ni-ZSM-5/MCM-41 molecular sieves in a ﬁxed-bed reactor. The effect of metal loading (2%, 4%, 6%, 8% Ni) on cracking product yield and its characteristics was investigated. The catalysts were characterized by NH3-TPD, BET and N2 adsorption and desorption. The gaseous products were analyzed by gas chromatograph (GC). The distilled bio-oil and the upgraded biooil were quantiﬁed by gas chromatograph-mass spectrometry (GCMS). 2. Material and method 2.1. Material The raw bio-oil used in this study was obtained by Tianjin University, China [16] from the fast pyrolysis of rice-hull in a ﬂuidized bed reactor with a temperature of 550 C and normal pressure. 2.2. Catalyst preparation and characterization 2.2.1. Catalyst preparation ZSM-5/MCM-41 zeolite (Si/Al ¼ 50, 0.2e0.45 mm, Tianjin Nan Hua catalyst co., LTD. China) were calcinated from 20 C to 550 C with a heating rate of 2 C/min in air and kept 550 C for 5 h. All of the catalysts were prepared using the wet-impregnation
H=Ceff ¼ ðH À 2 Â O À 3 Â N À 2 Â SÞ=C
(1)
* Corresponding author. School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China. E-mail address: chen@ (G. Chen). /10.1016/j.biombioe.2017.04.006 0961-9534/© 2017 Published by Elsevier Ltd.
b
a r t i c l e i n f o
Article history: Received 23 December 2016 Received in revised form 12 April 2017 Accepted 19 April 2017
a b s t r a c t
The bio-oil from rice hull fast pyrolysis was distillated under reduced pressure at 0.005 Mpa, then mixed with ethanol (2:3 by weight). The mixture was subjected to catalytic co-cracking over Ni-ZSM-5/MCM-41 molecular sieves in a ﬁxed-bed at 500 C and 3.75 hÀ1 of the WHSV. The distillation results showed the distilled bio-oil, compared with raw bio-oil, contained lower oxygen content (decreased from 45.91 wt.% in raw bio-oil to 33.74 wt.%), higher (H/C)eff ratio (0.35) and HHV value (22.81 MJ/kg). The ethanol was involved in the ketonization, esteriﬁcation, aromatization and dehydration during the catalytic cocracking of distilled bio-oil and ethanol. The Ni loaded on ZSM-5/MCM-41 molecular sieves reduced char formation compared with ZSM-5/MCM-41. The ZSM-5/MCM-41 catalyst exhibited higher activity in the esteriﬁcation and aromatization, which converted acids in upgraded bio-oil to esters, aromatics or phenols. The Ni-ZSM-5/MCM-41 catalysts showed excellent activity that transformed acids to ketones by ketonization process. The 6% Ni-ZSM-5/MCM-41 catalyst performed the good activity with the minimum char formation (7.3 wt.%) and higher upgraded bio-oil (40.8 wt.%). Moreover, the acid content in the upgraded bio-oil dropped to 0.1 wt.% and the total concentration of CO2 and CO in the gas products was 36.8 vol.%. © 2017 Published by Elsevier Ltd.