艾迪奧特曼
石油學(xué)報(bào)(石油加工)ACTA PETROLEI SINICA(PETROLEUM PROCESSING SECTION)2004 Vol.20 No.1 P.12-21--------------------------------------------------------------------------------EFFECT OF STEAM TREATMENT AND PHOSPHOROUS ACID MODIFICATION OF HZSM-5 ON ITS PHYSICOCHEMICAL AND CATALYTIC PROPERTIESAbstract:Physicochemical and catalytic properties of phosphorous acid modified HZSM?5 ze olites treated with 100% steam at 673,873,and 1073*!K have been investigated.T he structure of the samples was characterized by XRD.The acidity and distributio n of the acidic sites were studied by IR using pyridine as probe molecule and te mperature programmed desorption (TPD) of ammonia.The state of phosph orus were studied by XPS,showing that P (Ⅲ) was oxidized to P (Ⅴ),a model for the surface structure of the modification is proposed.Th e textural properties of catalysts determined by nitrogen isothermal adsorption ?desorption measurements suggest the isothermal type of all samples is a combin ation of type Ⅰ and type Ⅳ,all hysteresis loops resemble the H4?type in the IUPAC classification.The state of aluminum was characterized by 27 Al MAS N MR spectroscopy.AM1 (Austin model) semi?empirical method and cluster model method have been employed to study the stability of two possible phosphor us modified zeolite geometries,the difference was the bridging oxygen of phosph orus coordination with aluminum or the terminal oxygen of phosphorus coordinatio n with aluminum.The result showed that the terminal oxygen coordination was more possible according to the heat of formation (HF).The ?n??heptane cracking reaction was selected as probe reaction to investigate the activity of studied samples.?Keywords:HZSM?5 zeolites;steam treatment;phosphorous acid modificati on;texture;cracking activity 亞磷酸和水蒸氣聯(lián)合改性的HZSM-5的物化性質(zhì)和催化性能研究呂仁慶 唐博 王震宇 王秋英 項(xiàng)壽鶴 摘 要:考察了由亞磷酸改性的HZSM-5在673、873和1073K溫度下100%水蒸氣處理樣品的物化和催化性質(zhì).采用XRD表征了樣品的結(jié)構(gòu).通過吸附吡啶紅外光譜和NH3-TPD進(jìn)行了酸性和酸分布研究.XPS的研究結(jié)果表明,P由+3價(jià)氧化成了+5價(jià),并提出了可能的改性的表面結(jié)構(gòu)模型.通過N2吸附-脫附等溫線研究了樣品的孔結(jié)構(gòu),樣品的吸附-脫附等溫線為Ⅰ型和Ⅳ型的復(fù)合型,滯后環(huán)為IUPAC分類的H4型.Al的狀態(tài)由27Al MAS NMS表征.采用AM1(Austin Model Ⅰ)半經(jīng)驗(yàn)量子化學(xué)方法和模型簇法篩選了磷改性可能的兩種結(jié)構(gòu)模型,其區(qū)別在于磷上的橋氧與鋁配位還是端氧與鋁配位,結(jié)果表明端氧與鋁配位的可能性更大.以正庚烷裂化反應(yīng)為探針反應(yīng)考察了樣品的活性.關(guān)鍵詞:HZSM-5沸石;水熱處理;亞磷酸改性;結(jié)構(gòu);裂化活性CLC Number:TE624.4 Document ID:AArticle ID:1001-8719(2004)01-0012-10 Foundation Item:國(guó)家自然科學(xué)基金(20233030)和石油大學(xué)中國(guó)石油天然氣集團(tuán)公司催化重點(diǎn)實(shí)驗(yàn)室資助項(xiàng)目Author Resume:呂仁慶(1969-),男,講師,博士研究生,從事沸石催化研究;唐博(1964-),男,高級(jí)工程師,博士研究生,從事工業(yè)催化研究;王震宇(1974-),男,工程師,碩士,從事催化劑生產(chǎn)工作;王秋英(1964-),女,高級(jí)工程師,碩士,從事沸石催化研究:項(xiàng)壽鶴(1939-),男,教授,從事沸石合成與催化研究. 通訊聯(lián)系人:呂仁慶 Author Unit:呂仁慶(南開大學(xué),化學(xué)系,天津,300071) 唐博(南開大學(xué),化學(xué)系,天津,300071) 王震宇(南開大學(xué),催化劑廠,天津,300071) 王秋英(南開大學(xué),催化劑廠,天津,300071) 項(xiàng)壽鶴(南開大學(xué),化學(xué)系,天津,300071) References:〔1〕Scherzer J.Octane-enhancing,zeolitic FCC catalysts,scientific and technical aspects[J].Catal Rev-Sci Eng,1989,31(3):215-354.〔2〕Lischke G,Eckelt R,Jerschkewitz H-G,et al.Spectroscopic and physicochemical characterization of P-modified H-ZSM-5[J].J Catal,1991,132(1):229-243.〔3〕Kaeding W W,Chu C,Young L B,et al.Shape selective reactions with zeolite catalysts[J].J Catal,1981,69:392-398.〔4〕Jentys A,Rumplmayr G,Lerche r J A.Hydroxyl groups in phosphorus-modified HZSM-5[J].Appl Catal,1989,53:299-312.〔5〕Chen N Y,Kaeding W W,Dwyer F G.Para-directed aromatic reactions over shape-selective molecular sieve zeolite catalysts[J].J Am Chem Soc,1979,101(20-22):6783-6784.〔6〕Vinek H,Rumplmayr G,Lercher J A.Catalytic properties of postsynthesis phosphorus modified H-ZSM-5 zeolite[J].J Catal,1989,115(2):291-300.〔7〕Lercher J A,Rumplmayr G.Controlled decrease of acid strength by orthophosphoric acid on ZSM-5[J].Appl Catal,1986,25:215-222.〔8〕Young L B,Butter S A,Kaeding W W.Shape selective reactions with zeolite catalysts[J].J Catal,1982,76:418-432.〔9〕Chandawar K H,Kulkarni S B,Ratnasamy P.Alkylation of benzene with ethanol over ZSM-5 zeolites[J].Appl Catal,1982,4:287-295.〔10〕Kaeding W W,Chu C,Young L B,et al.Selective alkylation of toluene with methanol to produce para-xylene[J].J Catal,1981,67:159-174.〔11〕Caro J,Bulow M,Derewinski M,et al.NMR and IR studies of zeolite HZSM-5 modified with orthophosphoric acid[J].J Catal,1990,124:367-375.〔12〕Romannikov V N,Tissler A J,Thome R.Alkylation of aromatics on P-containing ZSM-5 zeolites[J].React Kinet Catal Lett,1993,51(1):125-134.〔13〕Nunan J,Cronin J,Cunningham J.Combined catalytic and infrared study of the modification of H-ZSM-5 with selected poisons to give high p-xylene selectivity[J].J Catal,1984,87(1):77-85.〔14〕Kaeding W W,Butter S A.Production of chemicals from methanol I Low molecular weight olefins[J].J Catal,1980,61(1):155-164.〔15〕Vedrine J C,Auroux A,Dejaifve P,et al.Catalytic and physical properties of phosphorus modified ZSM-5 zeolite[J].J Catal,1982,73;147-160.〔16〕Tynjala P,Pakkanen T T.Modification of ZSM-5 zeolite with trimethyl phosphite Part I Structure and acidity[J].Microporous Mesoporous Materials,1998,20:363-369.〔17〕Rahman A,Lemay G,Adnot A,et al.Spectroscopic and catalytic study of P-modified ZSM-5[J].J Catal,1988,112(2):453-463.〔18〕Rahman A,Adnot A,Lemay G,et al.Chemical modification of H-ZSM-5 by adsorption of rhodium and phosphorus complexes[J].Appl Catal,1989,50:131-147.〔19〕Seo G,Ryoo R.31P,27Al and 129Xe NMR study of phosphorus-impregnated HZSM-5 zeolite catalysts[J].J Catal,1990,124:224-230.〔20〕Suzuki K,Kiyozumi Y,Matsuzaki K.Effect of modification of ZSM-5 type zeolite with calcium phosphate on its physico-chemical and catalytic properties[J].Appl Catal,1988,39:315-324.〔21〕Ikai S,Okamoto M,Nishioka H,et al.HZSM-5 pelletized and modified with α-Ca3(PO4)2 and HPO?42- as a catalyst for methanol conversion[J].Appl Catal,1989,49:143,163.〔22〕Shen Y F,Ko A N,Grange P.Study of phosphorus-modified aluminum pillared montmorillonite I Effect of the nature of phosphorus compounds[J].Appl Catal,1990,67:93-106.〔23〕Wu E L,Lawton S L,Olson D H,et al.ZSM-5-type material,factors affecting crystal symmetry[J].J Phys Chem,1979,83(21):2777-2781.〔24〕Mastikhin V M,Zamaraev K I.Studies of heterogeneous catalysis using high-resolution solid state NMR[J].Applied Magnetic Resonance,1990,1:295-350.〔25〕Lü R Q,Wang Q Y,Tang B,et al.Physicochemical characterization and catalytic study of steam combined with phosphorus modified HZSM-5[C].ZMPC2003 Symposium,August 3-6 in Sapporo,Japan,submitted.〔26〕Lischke G,Eckelt R,Jerschkewitz H-G,et al.Spectroscopic and physicochemical characterization of P-modified H-ZSM-5[J].J Catal,1991,132(1):229-243.〔27〕Wagner C D,Riggs W M,Davis L E,et al.Handbook of X-ray photoelectron spectroscopy,A reference book of standard data for use in X-ray photoelectron spectroscopy[M].Published by Perkin-Elmer Corporatio n physical electronics Division 6509 Flying Cloud drive Eden Prairie,Minnesota 55344.〔28〕Dewar M J S,Zoebisch E G,Healy E F S.AM1: A new general purpose quantum mechanical molecular model[J].J Am Chem Soc,1985,107:3902-3909.Manuscript Received:2003年1月13日Published:2004年2月25日

MIssinGLess
磷。
第15號(hào)化學(xué)元素,符號(hào)P。處于元素周期表的第三周期、第ⅤA族。磷存在于人體所有細(xì)胞中,是維持骨骼和牙齒的必要物質(zhì),幾乎參與所有生理上的化學(xué)反應(yīng)。
磷還是使心臟有規(guī)律地跳動(dòng)、維持腎臟正常機(jī)能和傳達(dá)神經(jīng)刺激的重要物質(zhì)。沒有磷時(shí),煙酸(又稱為維生素B3)不能被吸收;磷的正常機(jī)能需要維生素D(維生素食品)和鈣(鈣食品)來(lái)維持。
磷被首次發(fā)現(xiàn)存在于恒星爆炸后的宇宙殘余物里。對(duì)超新星殘余物仙后座A的最新觀測(cè)揭示了磷存在的最新證據(jù)。它是在深空發(fā)現(xiàn)的兩大元素之一,或可能給科學(xué)家提供有關(guān)生命在宇宙里的可能性的線索。
關(guān)于磷元素的發(fā)現(xiàn),還得從歐洲中世紀(jì)的煉金術(shù)說起。那時(shí)候,盛行著煉金術(shù),據(jù)說只要找到一種聰明人的石頭──哲人石,便可以點(diǎn)石成金,讓普通的鉛、鐵變成貴重的黃金。
煉金術(shù)家仿佛瘋子一般,采用稀奇古怪的器皿和物質(zhì),在幽暗的小屋里,口中念著咒語(yǔ),在爐火里煉,在大缸中攪,朝思暮想尋覓點(diǎn)石成金的哲人石。
1669年,德國(guó)漢堡一位叫布朗特(Brand H)的商人在強(qiáng)熱蒸發(fā)人尿的過程中,他沒有制得黃金,卻意外地得到一種像白蠟一樣的物質(zhì),在黑暗的小屋里閃閃發(fā)光。這從未見過的白蠟?zāi)拥臇|西,雖不是布朗特夢(mèng)寐以求的黃金,可那神奇的藍(lán)綠色的火光卻令他興奮得手舞足蹈。
他發(fā)現(xiàn)這種綠火不發(fā)熱,不引燃其它物質(zhì),是一種冷光。于是,他就以“冷光”的意思命名這種新發(fā)現(xiàn)的物質(zhì)為“磷”。磷的拉丁文名稱Phosphorum就是“冷光”之意,它的化學(xué)符號(hào)是P,它的英文名稱是Phosphorus。
參考資料:百度百科-磷
初記裝飾
磷 phosphorus (P)硫 sulphur (S)錳 manganese (Mn)硅 silicon (Si)碳 carbon (C)希望對(duì)你有幫助!
興業(yè)騰達(dá)裝飾
p是化學(xué)元素磷元素。
磷,原子序數(shù)15,原子量30.973762, 磷有白磷、紅磷、黑磷三種同素異構(gòu)體。白磷又叫黃磷為白色至黃色蠟性固體,熔點(diǎn)44.1°C,沸點(diǎn)280°C,密度1.82克/厘米3。
白磷活性很高,必須儲(chǔ)存在水里,人吸入0.1克白磷就會(huì)中毒死亡。白磷在沒有空氣的條件下,加熱到250°C或在光照下就會(huì)轉(zhuǎn)變成紅磷。
紅磷無(wú)毒,加熱到400°C以上才著火。在高壓下,白磷可轉(zhuǎn)變?yōu)楹诹祝哂袑訝罹W(wǎng)絡(luò)結(jié)構(gòu),能導(dǎo)電,是磷的同素異形體中最穩(wěn)定的。
擴(kuò)展資料:
一、元素描述
單質(zhì)磷有幾種同素異形體。其中,白磷或黃磷是無(wú)色或淡黃色的透明結(jié)晶固體。密度1.82克/厘米3。熔點(diǎn)44.1℃,沸點(diǎn)280℃,著火點(diǎn)是40℃。放于暗處有磷光發(fā)出。有惡臭。劇毒。
白磷幾乎不溶于水,易溶解與二硫化碳溶劑中.在高壓下加熱會(huì)變?yōu)楹诹?,其密?.70克/厘米3,略顯金屬性。電離能為10.486電子伏特。不溶于普通溶劑中。
白磷經(jīng)放置或在400℃密閉加熱數(shù)小時(shí)可轉(zhuǎn)化為紅磷。紅磷是紅棕色粉末,無(wú)毒,密度2.34克/厘米3,熔點(diǎn)59℃,沸點(diǎn)200℃,著火點(diǎn)240℃。不溶于水。
在自然界中,磷以磷酸鹽的形式存在,是生命體的重要元素。存在于細(xì)胞、蛋白質(zhì)、骨骼和牙齒中。在含磷化合物中,磷原子通過氧原子而和別的原子或基團(tuán)相聯(lián)結(jié)。
二、磷的發(fā)現(xiàn)
關(guān)于磷元素的發(fā)現(xiàn),還得從歐洲中世紀(jì)的煉金術(shù)說起。那時(shí)候,盛行著煉金術(shù),據(jù)說只要找到一種聰明人的石頭──哲人石,便可以點(diǎn)石成金,讓普通的鉛、鐵變成貴重的黃金。
煉金術(shù)家仿佛瘋子一般,采用稀奇古怪的器皿和物質(zhì),在幽暗的小屋里,口中念著咒語(yǔ),在爐火里煉,在大缸中攪,昭思慕想尋覓點(diǎn)石成金的哲人石。
1669年,德國(guó)漢堡一位叫布朗特(Brand H)的商人在強(qiáng)熱蒸發(fā)人尿的過程中,他沒有制得黃金,卻意外地得到一種像白蠟一樣的物質(zhì),在黑暗的小屋里閃閃發(fā)光。
這從未見過的白蠟?zāi)拥臇|西,雖不是布朗特夢(mèng)寐以求的黃金,可那神奇的藍(lán)綠色的火光卻令他興奮得手舞足蹈。他發(fā)現(xiàn)這種綠火不發(fā)熱,不引燃其它物質(zhì),是一種冷光。
于是,他就以“冷光”的意思命名這種新發(fā)現(xiàn)的物質(zhì)為“磷”。磷的拉丁文名稱Phosphorum就是“冷光”之意,它的化學(xué)符號(hào)是P,它的英文名稱是Phosphorus。
參考資料:
百度百科-磷元素
結(jié)婚201314
Hesper才是金星phosphor和phosphorus是 磷 的意思?!傲住保壕褪亲龌鸩竦哪欠N東西,磷火,星光?!敖鹦恰保河纸袉⒚餍恰⒃缟喜懦鰜?lái)的。所以在詩(shī)里Phosphor就成了金星了
優(yōu)質(zhì)英語(yǔ)培訓(xùn)問答知識(shí)庫(kù)