本文關(guān)鍵詞：催化裂化催化劑中分子篩與含鋁基質(zhì)材料的綠色合成和多功能化　出處：《華東師范大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 催化裂化 催化劑 FAU分子篩 硅鋁材料 氧化鋁 綠色合成 多級(jí)孔道 多功能化

【摘要】：流化催化裂化(FCC)是現(xiàn)代石油化工的基礎(chǔ)與核心。FCC催化劑的主要活性組分包括Y型分子篩和活性硅鋁基質(zhì)。隨著原油組成的日益重質(zhì)化,開發(fā)適用于大分子裂化的高選擇性和高活性FCC催化劑越來越迫切。本文圍繞FCC催化劑活性組分Y分子篩的脫鈉與脫鋁改性、多孔活性基質(zhì)的構(gòu)筑、及其對(duì)真實(shí)油品的催化裂化性能等開展研究,取得如下結(jié)果:論文第一部分首次將硫酸鋁用于NaY分子篩脫鋁,實(shí)現(xiàn)了一步脫鋁、脫鈉并成功引入介孔。硫酸鋁在酸性水熱條件下,與NaY分子篩的骨架鋁及Na+直接反應(yīng)生成明礬石。通過氫氧化鈉、碳酸鈉、氨水、氨水蒸汽等可將明礬石物種轉(zhuǎn)化為γ型氧化鋁,后者是FCC催化劑的基質(zhì)。最終脫鋁Y分子篩的比表面積為681m~2g~(-1),介孔表面積為142m~2g~(-1)。在800℃高溫水蒸氣處理17小時(shí)后,脫鋁Y分子篩依舊保持46%的相對(duì)結(jié)晶度,介孔表面積也保持127m~2g~(-1)。我們進(jìn)一步通過XRD表征手段揭示了硫酸鋁脫鋁過程的機(jī)理。結(jié)果表明,NaY分子篩的脫鋁程度與明礬石的生成量正相關(guān)。并且在酸性條件下,單獨(dú)利用Al_3~+或SO_42~-無法對(duì)NaY分子篩進(jìn)行脫鋁或與NaY分子篩反應(yīng)生成明礬石。我們推測(cè),硫酸鋁與NaY分子篩的骨架鋁及Na+反應(yīng)生成熱力學(xué)更穩(wěn)定的明礬石是脫鋁的重要原因。另外,硫酸鋁會(huì)選擇性的將NaY分子篩中四元環(huán)對(duì)位鋁脫除,所以該脫鋁Y分子篩比傳統(tǒng)水蒸氣脫鋁USY分子篩具有更多的強(qiáng)酸位點(diǎn),更強(qiáng)的烷烴裂化活性和裂化氫轉(zhuǎn)移指數(shù)。論文第二部分通過靜電吸附作用,將SBA-15與纖維薄水鋁石溶膠簡(jiǎn)單組裝,經(jīng)老化和焙燒等步驟制備了一種纖維氧化鋁包裹SBA-15的兩相SiO_2/Al_20_3復(fù)合基質(zhì)材料。所得SiO_2/Al_20_3復(fù)合材料具有開放的多級(jí)孔道結(jié)構(gòu),比表面積為425m~2g~(-1),孔體積為0.97m~3g~(-1)�；旌舷嘀械摩眯脱趸X可以穩(wěn)定其表面積。由于硅鋁物種在復(fù)合材料中的遷移,纖維氧化鋁的A1-OH在復(fù)合后消失,四配位硅羥基窩鋁在焙燒前后分別增加到2%和5%。由于硅鋁的遷移,SiO_2/Al_2O_3復(fù)合材料同時(shí)擁有Bronsted和Lewis酸位點(diǎn)。盡管高溫水蒸氣會(huì)導(dǎo)致復(fù)合材料的比表面積下降,但它會(huì)促進(jìn)硅鋁遷移,使其具有更強(qiáng)的酸性。由于其開放的多級(jí)孔道結(jié)構(gòu),SiO_2/Al_2O_3復(fù)合材料比傳統(tǒng)用浸漬法得到的硅鋁材料具有更高的1,3,5-三異丙基苯(TIPB)裂化活性,并且TIPB裂化轉(zhuǎn)化率在800℃高溫100%水蒸氣處理后保留較好。論文第三部分以拜爾石為前驅(qū)體,在無模板劑的情況下,合成了多級(jí)孔道薄水鋁石。所得花狀結(jié)構(gòu)薄水鋁石初級(jí)粒子厚度僅1～5 nm,并具有雙重孔道結(jié)構(gòu)。含乙醇/水/硫酸銨的反應(yīng)母液為反應(yīng)體系提供穩(wěn)定的pH,并可以重復(fù)用于花狀結(jié)構(gòu)薄水鋁石。通過XRD、SEM和27A1 MAS NMR等表征手段,我們發(fā)現(xiàn)花狀結(jié)構(gòu)薄水鋁石逐漸從拜耳石顆粒外向顆粒內(nèi)部生長(zhǎng)。轉(zhuǎn)化過程中,拜耳石相和薄水鋁石相的晶粒大小和鋁的配位狀態(tài)保持不變,但比表面積從28m~2g~(-1)上升到221m2 g~(-1)。經(jīng)過焙燒后,花狀結(jié)構(gòu)氧化鋁的表面積高達(dá)281m2 g~(-1)。由于其開放的孔道結(jié)構(gòu)和較大的孔徑,花狀結(jié)構(gòu)γ型氧化鋁對(duì)TIPB裂化的轉(zhuǎn)化率是工業(yè)γ型氧化鋁的近2倍。另外,花狀結(jié)構(gòu)γ型氧化鋁的形貌在800℃高溫100%水蒸氣處理后保留較好。論文還考察了上述材料在接近工業(yè)FCC條件下的催化裂化性能。將新型脫鋁Y分子篩和多功能化硅鋁基質(zhì)噴霧成小球形催化劑,在微型流化催化裂化反應(yīng)裝置上進(jìn)行催化性能評(píng)價(jià)。經(jīng)硫酸鋁脫鋁的Y分子篩比傳統(tǒng)的USY擁有更好的骨架鋁分布和更高的介孔表面積,前者噴霧成型的催化劑對(duì)渣油有更好的裂化轉(zhuǎn)化率和汽油收率。新型脫鋁Y分子篩和硅鋁基質(zhì)噴霧成型的催化劑,比工業(yè)FCC催化劑具有更高的渣油裂化轉(zhuǎn)化率,汽油收率和液化石油氣收率。
[Abstract]:Fluid catalytic cracking (FCC) is the main active component base and core of modern petrochemical.FCC catalyst consists of Y zeolite and activated silica alumina matrix. With the composition of crude oil is heavy, apply to the development of macromolecular cracking of high selectivity and high activity of FCC catalyst is more and more urgent. This paper focuses on the activity of FCC catalyst composition of Y molecular sieve and desodium dealumination, construct porous active matrix, and carry out research on real oil catalytic cracking performance. The results are as follows: the first part of the paper for the first time for aluminum sulfate NaY zeolite was achieved one-step dealumination, sodium removal and the successful introduction of mesoporous. Aluminum sulfate in acidic hydrothermal conditions, and the framework of NaY zeolite and Na+ direct reaction of aluminum alunite. By sodium hydroxide, sodium carbonate, ammonia, ammonia vapor can be transformed into species of alunite alumina, which is FCC The catalyst matrix. Finally dealuminated Y zeolite specific surface area of 681m~2g~ (-1), surface area of mesoporous 142m~2g~ (-1). In the 800 high temperature water vapor treatment after 17 hours, dealuminated Y zeolite crystallinity remained 46%, mesoporous surface area 127m~2g~ (-1). We reveal the mechanism of aluminum sulfate removal during aluminium further characterized by XRD method. The results show that the generation of dealumination degree and alunite NaY molecular sieve and positive correlation. In acidic conditions, the use of Al_3~+ or SO_42~- alone cannot sieve dealuminated NaY zeolite or reaction of alunite on NaY molecules. We speculate that the Na+ reaction thermodynamic framework aluminum and aluminum sulfate and NaY molecular sieve more stable alunite is an important cause of dealumination. In addition, aluminum sulfate selectively NaY molecular sieve element four ring para removal of aluminum, so the dealuminated Y zeolite than traditional water vapor Dealuminated USY zeolite has more stronger acid sites, the alkane cracking activity and hydrogen transfer cracking index. In the second part, through electrostatic adsorption, SBA-15 and fiber boehmite sol by simple assembly, aging and calcination. The preparation phase of SiO_2/Al_20_3 composite matrix material for fiber alumina coated SBA-15. The SiO_2/Al_20_3 composite materials with hierarchical pores open, specific surface area is 425m~2g~ (-1), pore volume of 0.97m~3g~ (-1). Gamma alumina mixed phase can stabilize its surface area. The silicon aluminum species in the composite fiber migration, alumina in composite A1-OH disappear after four coordination silicon hydroxyl aluminum in the nest before and after calcination were increased to 2% and 5%. due to the migration of silicon and aluminum, SiO_2/Al_2O_3 composite materials have both Bronsted and Lewis acid sites. Despite the high temperature water vapor will lead to composite material The specific surface area of the material decreased, but it will promote silicon aluminum migration, which has stronger acidity. The hierarchical structure of its open, aluminum silicon SiO_2/Al_2O_3 composites than the traditional impregnation method was obtained with higher 1,3,5- three isopropyl benzene (TIPB) cracking activity and TIPB conversion rate. Good retention at 800 degrees Celsius to 100% after water vapor treatment. The third part of bayerite as precursor, without template agent, mesoporous boehmite was synthesized. The structure of boehmite primary particle thickness of only 1 ~ 5 nm, and has a double pore structure. Ethanol / water / provide stable pH reaction solution of ammonium sulfate as reaction system, and can be used for flower like structure of boehmite. By XRD, SEM and 27A1 MAS NMR techniques, we found that the flower like boehmite particles gradually from bayerite particles inside extroversion Growth. In the process of transforming, bayerite phase and boehmite phase and particle size of aluminium coordination state remains unchanged, but the specific surface area from 28m~2g~ (-1) up to 221m2 g~ (-1). After calcination, the flower like structure of alumina surface area up to 281m2 g~ (-1) as. The open pore structure and large pore diameter, flower like structure of alumina on the transformation of TIPB cracking rate is nearly 2 times of industrial alumina. In addition, the morphology of flower structure alumina retained well in high temperature of 800 DEG C 100% after water vapor treatment. The paper also studied the catalytic performance of these materials in close to the industry under the condition of FCC. The new type of dealuminated Y zeolite and multi functional silicon aluminum matrix spray into small spherical catalyst, catalytic cracking reaction device in micro flow on the catalytic performance. Y molecular sieve by aluminum sulfate and aluminum is better than the traditional USY with the aluminum frame distribution And the higher surface area of mesoporous catalyst, the former spray molding has better conversion rate and yield of gasoline residue. The new catalyst dealuminated Y zeolite and silicon aluminum matrix spray molding, with residuum higher conversion rate than FCC industrial catalyst, gasoline yield and LPG yield.

【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TE624.91

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