Technical Advantage
——創(chuàng)新的DYC催化劑技術(shù)平臺
——Innovative DYC Catalyst Technology Platform
重油催化裂化反應(yīng)中的主反應(yīng)是大分子烴類在固體酸中心上所發(fā)生的正碳離子裂化反應(yīng)過程。對于FCC催化劑而言，其結(jié)構(gòu)與酸性具有同等的重要性。我們認(rèn)為，當(dāng)前的FCC催化劑設(shè)計應(yīng)從上世紀(jì)80 年代提出的“配方設(shè)計理念”轉(zhuǎn)變?yōu)椤敖Y(jié)構(gòu)導(dǎo)向設(shè)計理念”，讓催化劑的結(jié)構(gòu)與酸性充分協(xié)同，以適應(yīng)FCC 工藝及原料的變化要求。 催化劑結(jié)構(gòu)包括：孔結(jié)構(gòu)（開放式還是封閉式）及其分布（階梯狀還是同梯度）、活性中心（包括酸中心和其他功能中心）及其結(jié)構(gòu)（均勻分布還是殼核分布）等；催化劑的酸性匹配包括：B酸與L酸的匹配、強(qiáng)酸與弱酸的匹配、酸量大小的匹配等。
The main reaction of RFCC is cracking reaction of high-molecular-weight hydrocarbons through carbenium ion intermediate on solid acid site. For FCC catalyst, pore architecture is as important as acidity. We believe that FCC catalyst design of today should transform from “Formula Design” to “Structure-Oriented Design”, achieving effective synergy between pore architecture and acidity to meet requirements from FCC processing and feedstock. The pore architecture of FCC catalysts includes pore distributions and pore structure (open type, close type), active sites species (acid sites and other functional centers) and its structure (uniform distribution, core-shell structure); The acidity matching of catalyst includes B acidity and L acidity matching, strong acidity and weak acidity matching, acid site number matching)
公司研發(fā)人員開發(fā)了具有豐富二次孔結(jié)構(gòu)的低生焦Y分子篩催化材料制備技術(shù)和纖維狀特種高活性氧化鋁材料制備技術(shù)，這兩種材料的制備工藝技術(shù)都已申請國家發(fā)明專利。下面是低生焦Y分子篩掃描射電鏡（SEM）照片、纖維狀特種高活性氧化鋁透射電鏡（TEM）照片和XRD圖。
The Researcher of Duo You Technology developed rich mesoporous Y molecular sieve with low coke selectivity and fibrous high activity alumina preparative technique, and both technologies have applied for the national invention patents. The SEM photos of low coke Y molecular sieve, TEM photos and XRD patterns of the fibrous high activity alumina are shown below.
圖 1 低生焦Y分子篩掃描電鏡（SEM）照片
Figure 1 SEM Photo of Low Coke Y Molecular Sieve
圖 2 纖維狀特種高活性氧化鋁透射電鏡（TEM）照片
Figure 2 TEM Photo of Fibrous High Activity Alumina
同時，公司技術(shù)人員從催化裂化反應(yīng)機(jī)理出發(fā)，按照“結(jié)構(gòu)導(dǎo)向”的思路，以低生焦Y分子篩催化材料和纖維狀特種高活性氧化鋁材料為基礎(chǔ)，采用了高固含量催化劑制備技術(shù)，開發(fā)了創(chuàng)新的多友催化劑——“DYC系列FCC催化劑”技術(shù)平臺。采用該技術(shù)平臺制備的催化劑不僅提高了活性中心可接近性，并且從反應(yīng)的角度解決了催化裂化過程中生焦率高的技術(shù)難題，同時還使該催化劑具有了優(yōu)異的抗重金屬污染能力。下面是DYC催化劑的掃描電鏡(SEM)照片和孔徑分布圖。
At the same time, starting from catalytic cracking mechanism, following the "structure - oriented" idea and on the basis of low coke Y molecular sieve and fibrous high activity alumina, the company's technical staff adopted high solid content of catalyst technology to develop innovative Duo You catalyst – “DYC series FCC catalyst” technology platform. The catalyst prepared by technology platform not only improves accessibility of catalyst active sites, and solves the difficult problem of high coke yield during catalytic cracking process from the reaction mechanism, but also has excellent resistance to heavy metals. The SEM Morphology and pore size distributions of DYC catalyst are listed below.
從圖3我們可以看出DYC技術(shù)平臺制備的催化劑具有很好的球形度和開放性的孔結(jié)構(gòu)（左圖），與常規(guī)裂化劑的電鏡照片比較可以明顯看出兩者的差異。在相同的放大倍數(shù)下，DYC技術(shù)平臺制備的催化劑表面可以非常清楚地看到分布在微球上的分子篩顆粒和呈階梯狀分布的孔道結(jié)構(gòu)，而傳統(tǒng)工藝生產(chǎn)的催化劑表面形貌則呈板狀結(jié)構(gòu)。
From Figure 3 we can see that catalysts prepared on DYC Technology Platform showed very good sphericity and open pore architecture (left photo)，compared to the SEM photo of common cracking catalyst, clear difference can be found.. With the same amplification factor, zeolite particles locating on microsphere and porous wall with multilevel pore-size distribution (middle photo) can be clearly seen on surface of catalyst prepared by DYC Technology Platform. However, the surface of catalyst prepared by traditional technology is platy due to binding agent. Neither zeolite nor pore structure is obvious.
DYC顆粒電鏡照片（50倍） DYC單個顆粒電鏡照片（8000倍） 常規(guī)裂化劑單個顆粒電鏡照片（15000倍） SEM photo of DYC particles（50X） SEM photo of DYC single particle(8000X) particle (15000X)
圖3 DYC技術(shù)平臺催化劑與常規(guī)裂化劑形貌對比
Figure 3 SEM Photos of DYC Catalyst and Common Cracking Catalyst
由于DYC技術(shù)平臺制備的催化劑，分子篩直接分布在其孔道表面（中圖），使得重油大分子可以直接擴(kuò)散接觸到分子篩的酸中心，提高了催化劑活性中心可接近性，有利于重油大分子的裂化反應(yīng)和產(chǎn)物的擴(kuò)散分離，可顯著提高催化劑的活性和選擇性。
As zeolites in catalyst prepared by DYC Technology Platform cover directly on surface of porous wall (middle photo), macromolecule of heavy oil can diffuse readily to acid sites of zeolites, so that the accessibility of active sites is enhanced. Meanwhile, diffusive separation of cracking product has been improved, activity and selectivity of catalyst are also significantly increased.
圖 4a 纖維狀活性氧化鋁的孔徑分布圖
Figure 4 pore size distributions of fibrous activity alumina
圖 4b低生焦催化劑孔徑分布圖
Figure 4b pore size distributions of DYC catalyst
從圖 4孔徑分布圖可以看出纖維狀活性氧化鋁的孔徑主要集中在10-20 nm，是一種大孔徑的氧化鋁材料。催化劑中引入該種氧化鋁后，不僅可以顯著提高催化劑 10～60 nm中孔比例，而且還可以形成相當(dāng)數(shù)量的60~100nm的大孔和超大孔，并且為開放性的孔結(jié)構(gòu)和階梯狀的孔分布。因此，可以認(rèn)為DYC催化劑在結(jié)構(gòu)設(shè)計上解決了活性中心的可接近性問題。
In Figure 4, we can see that the pores of fibrous activity alumina are mainly concentrated in the range of 10-20 nm, and the fibrous activity alumina is a large aperture alumina material. When the alumina was added into the catalyst, both of the proportion of 10 ~ 60 nm mesopore and the proportion of large pore and super pore of catalyst were improved significantly, and the structure of pore was open distribution. So we can say that DYC catalysts resolved the problem of accessibility of catalyst active sites in structural design.
因此，該技術(shù)平臺制備的催化劑具有以下特點(diǎn)：
Therefore, FCC catalysts produced on DYC technology platform have such characteristics:
（1） 開放性、梯度狀分布的孔道結(jié)構(gòu)：
不僅縮短了原料油和裂化產(chǎn)物分子擴(kuò)散進(jìn)出催化劑的路徑，減少了熱裂解的比例，限制了產(chǎn)物的深度裂解，增加了對產(chǎn)品和焦炭的選擇性；而且有利于汽提段水蒸汽對于待生劑中吸附分子的汽提作用，降低了可汽提焦。
（1） Open and Graded distribution of pore structure
The open pores shorten the raw oil and product molecular diffusion path in catalyst, reduce the ratio of thermal pyrolysis of raw oil, limit the deep cracking of product, improve the selectivity of products and coke was improved, make contribution to the stripper steam treatment agent of molecular adsorption stripping effect, and reduce the catalyst-to-oil coke.
（2） 特殊分布的結(jié)晶分子篩
DYC催化劑中不僅分子篩含量高，而且分子篩在催化劑微球表面和孔道中暴露的比例也高于常規(guī)FCC催化劑。利用分子篩表面酸中心的高催化活性和選擇性，能夠促進(jìn)重油大分子包括原料中部分可轉(zhuǎn)化的殘?zhí)亢蜕骨吧砦镂锓N發(fā)生催化裂化反應(yīng)，降低非選擇性反應(yīng)比例，從而有利于在增強(qiáng)重油轉(zhuǎn)化能力的同時減少催化焦和附加炭的生成。
(2) Crystal molecular sieve with special distribution
The content of molecular sieve in DYC catalyst is high, and the exposure proportion of molecular sieve on surface and in pore passage of catalyst microspheres is higher than that of conventional FCC catalyst. The high catalytic activity and electivity of surface acid site of molecular sieve are suitable for promoting catalytic cracking of heavy oil macromolecule including some convertible carbon residues and green coke precursors in raw materials, to reduce the proportion of nonselective reactions, thus conducive both to improving heavy oil conversion ability and to decreasing production of catalytic coke and additional carbon.
（3）抗堿性氮和重金屬污染能力強(qiáng)
DYC催化劑的配方中相對提高了Y型分子篩的含量，這就增加了該催化劑酸性中心的數(shù)量，使其抗堿性氮的能力大大增強(qiáng)；同時，DYC催化劑的配方中還加入了纖維狀高活性氧化鋁，該氧化鋁具有較強(qiáng)的重金屬捕集容納能力，可降低重金屬所引發(fā)的非選擇性反應(yīng)，使催化劑抗重金屬污染的能力大大增強(qiáng)。
(3) Strong basic nitrogen and heavy metal pollution resistance
The content of Y molecular sieve is increased relatively in the formula of DYC catalyst, which raises the quantity of acid sites of the catalyst, greatly strengthening its resistance to basic nitrogen; meanwhile, fibrous high-activity aluminium oxide is also included in the formula of DYC catalyst, and the aluminium oxide is of comparatively strong heavy metal trapping and containing capacity, which reduces nonselective reactions caused by heavy metal, and significantly enhances catalyst’s resistance to heavy metal pollution.
（4）輕質(zhì)油收率高
DYC催化劑具有一定數(shù)量的大孔和超大孔，能夠使重油大分子更加容易地進(jìn)入到催化劑孔道中進(jìn)行催化反應(yīng)，從而使油漿收率降低，輕質(zhì)油收率提高。同時，纖維狀高活性氧化鋁基質(zhì)材料與不同品種的改性分子篩進(jìn)行匹配，可以調(diào)變催化裂化反應(yīng)過程中不同類型反應(yīng)的比例，以適應(yīng)不同類型原料油的裂化反應(yīng)，尤其是能有效提高催化裂化反應(yīng)的比例，降低熱裂解反應(yīng)的比例，從而能較大幅度地降低生焦，增加輕質(zhì)油收率；特別是高含量的Y分子篩能促使部分柴油分子轉(zhuǎn)化為汽油分子，使汽油收率提高。
(4) High light oil yield
DYC catalyst has large pore and ultra-large pore at certain quantity, to facilitate the entry of heavy oil macromolecule to the pore passage of catalyst for catalytic reaction, thus reducing the yield of slurry oil and promoting that of light oil. Meanwhile, the matrix material of fibrous high-activity aluminium oxide is matched with various modified molecular sieves, which modulates the proportion of different reactions during catalytic cracking to adapt to cracking of different kinds of raw oils, thus decreasing green coke greatly and increasing the yield of light oil; particularly, the high-content Y molecular sieve prompts conversion of diesel oil molecules to gasoline molecules to promote the yield of gasoline.
山東多友科技有限公司可針對各個煉廠的裝置特點(diǎn)、原料油性質(zhì)、產(chǎn)品分布情況和目標(biāo)產(chǎn)品的意愿，量體裁衣、調(diào)整配方，設(shè)計生產(chǎn)滿足用戶使用要求的專用催化劑。
Catalyst of Duo You Technology is tailor-made to satisfy operating requirements of users based on device features of each refiner, feedstock properties, product distribution and target products.
