摘要
加氫裂化技術(shù)是重油深度加工的主要工藝手段之一，也是唯一能在原料輕質(zhì)化的同時(shí)直接生產(chǎn)車用清潔燃料和優(yōu)質(zhì)化工原料的重要技術(shù)手段，是最有效利用原油資源的工藝。由于加氫裂化技術(shù)具有原料適應(yīng)性強(qiáng)、產(chǎn)品方案靈活、液體產(chǎn)品收率高、產(chǎn)品質(zhì)量好等諸多優(yōu)點(diǎn)，不但可以直接生產(chǎn)汽、煤、柴等清潔燃料，而且其生產(chǎn)的輕、重石腦油和加氫裂化尾油還是優(yōu)質(zhì)的化工原料，因此，近年來加氫裂化技術(shù)已逐步發(fā)展成為現(xiàn)代企業(yè)油、化有機(jī)結(jié)合的技術(shù)，多年來一直受到世界各國煉油企業(yè)及研究機(jī)構(gòu)的重視。加氫裂化催化劑作為加氫裂化技術(shù)的核心，它的一個(gè)重要開發(fā)方向就是開發(fā)高中油選擇性、高活性的加氫裂化催化劑，以最大限度的生產(chǎn)優(yōu)質(zhì)中間餾分油為目的。
中油型加氫裂化催化劑開發(fā)的技術(shù)難點(diǎn)主要是如何平衡中油選擇性和活性，在保持相同中油選擇性的前提下，進(jìn)一步提高催化劑活性，降低裝置能耗。通過分子篩改性、優(yōu)化催化劑制備工藝、提高加氫活性組分分散度、應(yīng)用新型催化材料等方法，國內(nèi)外研究機(jī)構(gòu)已經(jīng)實(shí)現(xiàn)了現(xiàn)有加氫裂化催化劑性能的進(jìn)一步提升。
本研究針對一段串聯(lián)加氫裂化工藝，進(jìn)行了NiO-WO3/USY中油型加氫裂化催化劑的研制工作。200ml固定床加氫裝置評價(jià)結(jié)果表明，研制的加氫裂化催化劑，在控制原料>350℃餾分油轉(zhuǎn)化率為75%的高轉(zhuǎn)化率條件下，加氫裂化生成油C5+液收98.2m%，加氫裂化生成油中138～370℃柴油餾分的收率67.84m%，中油選擇性80.2%，能滿足工業(yè)裝置最大量生產(chǎn)中間餾分油的需要，整體催化性能優(yōu)于參比劑。

關(guān)鍵詞：催化劑；加氫裂化；中間餾分油；中油選擇性

Research of NiO-WO3/USY Hydrocracking Catalyst
for Maximum Middle Distillate Production

ABSTRACT
The technology of the hydrocracking is one of the main way to process heavy oil to light oil.It is the only way of producing cleanness fuel for automobile and high quality chemical raw material while hydrocracking the feeds.It is the most efficient way to utilize crude oil.It has extensive adaptability to many feeds,it can produce many products with high quality,and the yield of liquid is high,so this technology is becoming of one link between the refinery and the chemical plant.The refineries and the research institutes pay more attention on it.Hydrocracking catalyst is the core of the technology,one of the most important way is to research out a kind of catalyst with high active and selectivity to Middle Distillate.
It is important to set up a balance between the selectivity of middle distillate and the activity.It is a good catalyst which has high selectivity to Middle Distillate,and has high
activity at the same time.Now Hydrocracking catalyst is developing quickly by treating the molecular sieve,optimizing the produsing technology of the catalyst,improving the disperse
of the hydrogenation and using many kinds of new catalysis materials.
Novel hydrocracking catalyst was developed for producing more middle distillate with two reactors in series process.Evaluation of catalytic performance of the
hydrocracking catalyst was carried on a 200mL fixed-bed hydrogenation unit,the results howed that under the 75%conversion of>350℃feedstock distillate,C5 +
liquid yield of the hydrocracking product can reach more than 98.2m%,138～370℃diesel oil yield of hydrocracking product was 67.84m%,selectivity of middle distillate was 80.2%,the
catalyst can meet the need of producing more middle distillate in the industrial unit, catalytic performance of the catalyst was better than reference catalyst.

Keywords:Catalyst,Hydrocracking,Middle Distillate,selectivity of middle
Distillate





目錄
前言......................................................................................................................................1
第一章概述........................................................................................................................3
1.1加氫裂化技術(shù)簡介.......................................................................................................3
1.2國內(nèi)外技術(shù)現(xiàn)狀及發(fā)展趨勢........................................................................................3
1.2.1加氫裂化工藝的技術(shù)現(xiàn)狀...................................................................................3
1.2.2加氫裂化催化劑的技術(shù)現(xiàn)狀...............................................................................4
1.2.3發(fā)展趨勢...............................................................................................................6
1.3加氫裂化機(jī)理及化學(xué)反應(yīng)............................................................................................6
1.3.1烷烴（烯烴）的加氫裂化反應(yīng)...........................................................................6
1.3.2環(huán)烷烴的加氫裂化反應(yīng).......................................................................................7
1.3.3芳烴的加氫裂化反應(yīng)...........................................................................................8
1.4本課題的主要研究內(nèi)容和技術(shù)關(guān)鍵............................................................................9
1.5預(yù)期達(dá)到的研究成果和具體學(xué)術(shù)價(jià)值........................................................................9
1.6本課題的研究思路......................................................................................................10
第二章試驗(yàn)過程..................................................................................................................12
2.1主要原材料與試劑......................................................................................................12
2.2催化劑制備..................................................................................................................12
2.3分析及表征..................................................................................................................12
2.3.1比表面分析（BET）.........................................................................................12
2.3.2物相分析（XRD）............................................................................................12
2.3.3酸性表征（Py-IR）...........................................................................................12
2.3.4組成分析（XRF）.............................................................................................12
2.3.5晶型晶貌表征（SEM-EDS）............................................................................13
2.3.6原料油及產(chǎn)品分析.............................................................................................13
2.4催化劑性能評價(jià)..........................................................................................................13
2.4.1評價(jià)原料.............................................................................................................13

2.4.2評價(jià)氫氣.............................................................................................................14
2.4.3評價(jià)裝置.............................................................................................................14
2.4.4評價(jià)方法............................................................................................................14
第三章催化劑的研發(fā)..........................................................................................................16
3.1載體組分確定..............................................................................................................16
3.1.1無定形硅鋁的篩選.............................................................................................16
3.1.2分子篩的篩選.....................................................................................................17
3.2活性金屬組分及負(fù)載方式研究..................................................................................18
3.3催化劑制備工藝的優(yōu)化及確定..................................................................................19
3.4催化劑的表征..............................................................................................................19
3.4.1物化性質(zhì)..........................................................................................................19
3.4.2 BET表征.........................................................................................................20
3.4.3 SEM電鏡.........................................................................................................20
3.4.4金屬分散性分析..............................................................................................21
3.4.5催化劑的酸性..................................................................................................21
3.5加氫裂化性能評價(jià).....................................................................................................22
3.5.1工藝條件考察..................................................................................................22
3.5.2 200ml評價(jià).......................................................................................................24
3.5.3同國內(nèi)外參比劑對比評價(jià)..............................................................................25
3.5.4轉(zhuǎn)化率與產(chǎn)品分布及性質(zhì)的關(guān)系..................................................................27
3.5.5催化劑耐氮性能試驗(yàn)......................................................................................28
3.5.6 2000小時(shí)活性穩(wěn)定性試驗(yàn).............................................................................28
3.6本章小結(jié).....................................................................................................................29
第四章催化劑中試放大......................................................................................................31
4.1催化劑表征..................................................................................................................31
4.2放大催化劑的性能評價(jià)..............................................................................................32
4.2.1 200ml加氫評價(jià)...............................................................................................32
4.2.2 3L加氫評價(jià)....................................................................................................32
4.2.3 1500hr活性穩(wěn)定性試驗(yàn)..................................................................................334.3本章小結(jié).....................................................................................................................33
結(jié)論......................................................................................................................................35
參考文獻(xiàn)..................................................................................................................................36
致謝....................................................................................................................................381