201130962 六、發明說明： L發明戶斤屬之技術領域3 發明領域 本發明係關於一種流動觸媒裂解觸媒用添加劑，係在 流動觸媒裂解裝置(FCC裝置）中，添加於流動觸媒裂解觸媒 (FCC觸媒）使用，特別是，用來裂解原料油中重油餾分（塔 底油）而製得輕顧分（特別是汽油）者。 t ^tr ^ 發明背景 向來，使用流動觸媒裂解觸媒裂解原料油而製得輕 油，但由於原油價格高騰，因而亦對較重之原料油（重油傲 分）進行處理。在此，為利用FCC觸媒有效率地裂解重油餾 分（例如殘油），而增加FCC觸媒中所含活性成分（以沸石及 氧化鋁為代表）。但是，FCC觸媒中活性成分比率若增加， 將有觸媒強度降低等物性惡化之問題。又，流動觸媒裂解 裝置中，當裂解原料油中重油館分而製得輕德分時，將增 進重油儲分之裂解而增加焦炭，再者生成之焦炭燃燒時， 將引起溫度上昇及水蒸氣產生，而有FCC觸媒品質劣化之 問題。為解決此等問題而開發有以下之添加劑做為FCC觸 媒之輔助觸媒(FCC Additive)。 例如，專利文獻1中揭示一種流動觸媒裂解觸媒用添加 劑，由碎铭氧化合物、黏土及氧化ΐ夕之粒狀混合物構成， 矽鋁氧化合物中氧化矽含量為10〜30重量％，混合物中所含 矽含量以Si02換算為10〜60重量％。 201130962 又，專利文獻2中揭示一種流動觸媒裂解觸媒用添力 劑’由石夕鋁氧化合物、黏土及氧化石夕構成，且由總石夕含旦 以Si〇2換算為10〜60重量％之粒子構成，具有3〇〜8〇m2/g之比 表面積及0.14〜0.45ml/g之總細孔容積，同時細孔半徑6〇入 以下之細孔容積為〇_〇5ml/g以下，再者，總酸量為 0·02 〜0.065mmol/g 之範圍。 專利文獻3中揭示一種流動觸媒裂解觸媒用添加劑，由 複合金屬氧化物、黏土及氧化矽構成，具有30〜8〇m2/g之比 表面積及0.14〜〇.45ml/g之總細孔容積，同時細孔直押 60〜200A之細孔容積為總細孔容積45%以上之範圍。 專利文獻4中揭示一種重油裂解用添加觸媒，由複合金 屬氧化物、黏土及氧化矽構成，比表面積30〜8〇m2/g，總酸 量0.02〜0.08mmol/g，且相對於該總酸量之強酸量比率為 10〜50% 〇 專利文獻1〜4揭示之添加劑，係由矽鋁氧化合物中氧化 矽含量為10〜30重量％，混合物中氧化矽含量為1〇〜6〇重量 % ’比表面積30~80m2/g，總酸量〇.〇2〜〇.〇8mmol/g構成者。 先行技術文獻 專利文獻 專利文獻1:日本專利第3479783號說明書 專利文獻2:日本專利第3467608號說明書 專利文獻3:日本專利第3643843號說明書 專利文獻4:日本專利第3920966號說明書 【發明内容】 4 201130962 發明概要 發明欲解決之課題 但是，習知之添加劑雖對於重油餾分之裂解有一定程 度效果，卻有必要更提高重油德分之裂解效率。在此，使 用該等添加劑將重油餾分流動觸媒裂解時，重油餾分裂解 進行同時焦炭產率將增加，而由於焦炭產率增加，引起FCC 裝置中觸媒再生塔内溫度上昇，伴隨焦炭燃燒之溫度上昇 及水蒸氣產生，而招致FCC觸媒品質劣化。 本發明係鑑於此等情形而發明，目的為提供一種流動 觸媒裂解觸媒用添加劑，可提昇重油餾分之裂解效率，並 ' 抑制焦炭產率之增加。 • 用以欲解決課題之手段 依循前述目的，關於本發明之流動觸媒裂解觸媒用添 加劑，係將含有黏合劑及石夕铭氧化合物之混合毁體藉由喷 霧乾燥製得者，比表面積為100〜400m2/g，且總固體酸量為 0.10mmol/g以上，且小於0.50mmol/g。 關於本發明之流動觸媒裂解觸媒用添加劑中，相對於 前述總固體酸量之強酸量比率宜為20%以下。 關於本發明之流動觸媒裂解觸媒用添加劑中，前述混 合漿體宜含有多孔性氧化矽或沸石。 關於本發明之流動觸媒裂解觸媒用添加劑中，前述混 合漿體中矽鋁氧化合物比率宜為20質量％以上，且小於80 質量％。 關於本發明之流動觸媒裂解觸媒用添加劑中，前述矽 5 201130962 铭氧化合物中氧化矽含量宜大於〇質量％且小於10質量0/〇。 關於本發明之流動觸媒裂解觸媒用添加劑中，前述黏 合劑宜為氧化矽化合物或鋁化合物。 發明效果 本發明之添加劑，比表面積為1〇〇〜400m2/g，且總固體 酸量為0.10~0.50mmol/g ’因此相較習知之添加劑，活性増 大’重餾分(HCO: Heavy Cycle Oil)產率減少，汽油產率增 大，焦炭產率為同等。此係由於添加劑之比表面積及總固 體酸量較習知為高，原料油與添加劑之接觸面積及活性點 增加，其結果FCC觸媒活性增大同時，HCO產率降低所致。 又可考慮為’藉減小總固體酸中強酸比率為2〇〇/0以下，而 抑制過度裂解反應，汽油及FCC裂解輕油(LCO :Light Cycle 〇il)產率增大，更抑制焦炭產率之增大。 t實施方式3 用以實施發明之形態 針對有關於本發明一實施形態之流動觸媒裂解觸媒用 添加劑做說明。 本發明之流動觸媒裂解觸媒用添加劑（以下亦簡稱為 添加劑」）’係於流動觸媒裂解裝置(FCC裝置）中，特別 疋為裂解原料油中重油傲分(塔底油）以製得輕傑分 ，而添 力口於⑺L動觸媒裂解觸媒中使用，由含有沸石之無機氧化物 多孔體所構成者。 本發明之添加劑，係將黏合劑及矽鋁氧化合物以習知 條件噴霧乾燥而製得，藉由BET法(JIS Z8830)測定之比表面 201130962 積為 100〜400m2/g，宜為 150~380m2/g，較宜為 200〜350 m2/g，且藉由氨吸附熱測定法（參照日本專利第3784852號， 實際以實施例1記載方法測定）測定之總固體酸量（吸附熱 70kJ/mol以上之氨吸附量）為0.10 mmol/g以上，小於0.50 mmol/g，宜為0.20~0.45mmol/g，較宜為0.25〜0.40mmol/g。 在此，添加劑之比表面積若小於100m2/g，由於添加劑 與原料油之反應場減少，重油餾分(HCO)裂解效率將降低， 若超過400m2/g則添加劑之體密度及強度將惡化。又，當添 加劑之固體酸量小於0.10mmol/g時，重油餾分裂解效率將 降低’ 0.50mmol/g以上時，重油餾分將過度裂解而增加焦 炭產率。 所使用之黏合劑’可使用氧化石夕化合物或|呂化合物。 在此’氧化妙化合物可舉例如使用水玻璃及矽酸溶液等， 銘化合物可舉例如使用鹼式氣化鋁及水鋁石解凝溶膠等。 石夕铭氧化合物可使用將氧化矽化合物混合或混合熟成 於假水鋁石凝膠或水鋁石凝膠者。 石夕銘氧化合物中氧化矽含量大於〇質量％且小於丨〇質 畺A且為1〜9質量VO α在此，矽鋁氧化合物中氧化矽含量 右為10質1%以上’比表面積及酸量將降低。 混合毀體亦可含黏土礦物、多孔性氧化石夕及沸石。黏 土礦物有W嶺土、蒙脫石、白雲石及方解石等，多孔性氧 化夕有水合氧化矽及無水氧化矽等，沸石有超安定化Y型沸 石⑽Υ)、Η·γ、NH4-Y、RE-Y、RE-USY、ZSM-5及絲光 弗石等ϋ添加多孔性氧化石夕或沸石，可調整(增大)添加劑 201130962 之比表面積，同時有助於活性提昇。 混合毁體中砂鋁氧化合物之比率宜為2 0質量％以上， 且小於8()質量％，且較宜為40〜70質量％。X，由石夕紹氧化 合物之比率’可控制添加劑之比表面積及固體酸量。在此， 當混合漿體中石夕紐氧化合物之比率小於2〇質量。/〇，由於裂 解重油館分之活性成分不足，將難以有效裂解重油餾分， 當80質量％以上’添加劑之強度及體密度將降低，做為流 動觸媒裂解觸媒用添加劑使用時將產生流動性惡化或粉 化’因此有難以運作流動觸媒裂解裝置之顧慮。又，混合 聚體中之黏合劑濃度為1〇〜15質量％左右，混合漿體中之固 體含量濃度為15〜30質量％左右。 相對於添加劑之總固體酸量，強酸量（氨吸附熱測定法 中吸附熱110kJ/mol以上之氨吸附量）之比率為20%以下，且 宜為10%以下’較宜為5%以下。在此，前述強酸量大於20% 時，將發生過度裂解反應，而有焦炭產率增加之傾向。 實施例 以下舉實施例及比較例做說明，唯本發明不因此受任 何限定。 《試驗例1 :固體酸量之影響》 [實施例1 :添加劑1] 將氧化矽17.5質量％之水玻璃以2 5質量％之硫酸水溶 液調整為pHl.6製作氧化矽溶膠a300g(含有氧化矽1〇質量 %。即含有氣化矽3〇g)，添加於含有氧化鋁(A12〇3)13.〇質量 〇/〇之水紹石漿體7690g(含有氧化鋁l〇〇〇g)後’以48質量。/〇之 8 201130962 氫氧化納水溶_整為pH1G 5，再於 含有氣切3質量％之砂絲化 ”=小時，製得 物聚體A ’氧她及氧切之合料度為㈣t絲化合 氧化二=_5”%之水破璃以硫酸調整^ 構成黏之氧切轉心氧切化合物所 以=_氧化合物論143%(含有仙氧化合物2〇〇g) =酸調整知勵後，添加氧切溶㈣咖g(含有氧化 〇g°以下相同）’接著添加高嶺土_g(乾燥質量。以下 =同）均勻混合後，以入口溫度46(rc，出口溫度26代，及 印留時間2G分鐘之條件噴霧錢(独下實施例亦相同），接 著藉由進行洗淨（以觸媒乾燥基準添加20質量％之硫酸銨除 驗後，以15%乱水除去硫酸。於以下實施例亦相同）去礦 貝製彳于平均粒徑60 y m之添加劑1。添加劑1之組成示於表 。再者，添加劑1之比表面積藉bet法測定，體密度藉UOP 法254-65測定（於以下實施例亦相同）。於表丨表示添加劑i 之性質。 (固體酸量之測定方法） 對於所製得添加劑1進行如下固體酸量之測定。首先， 將0_2g之添加劑1於5〇〇它燒成1小時，接著於減壓下 (lxl(T4torr)400°C熱處理4小時後，使氨氣吸附，檢測此時 產生之吸附熱，求算總固體酸量。測定使用東京理工社製 「Calorimeter」’以吸附熱7〇kJ/mol以上之氨吸附量為總固 體酸量’ 11 OkJ/mol以上為強酸量（於以下之實施例亦同樣測 201130962 疋）。於表1表示添加劑1之固體酸量測定結果。 [貫施例2 .添加劑2] 將矽鋁氧化合物漿體A2860g(含有矽鋁氧化合物4〇〇g) 以石周整為pH4〇 ,添加氧化矽溶膠bi6〇〇g(含有氧化矽 200g) ’接著添加高嶺土4〇〇§均勻混合後行喷霧乾燥接 著藉進行洗净去礦質，製得平均粒徑之添力口劑2。於 表1表示添加劑2之組成及性質。 [實施例3 :添加劑3] 將矽鋁氧化合物漿體A5〇〇〇g(含有矽鋁氧化合物7⑽幻 以ϋ調整為pH4G ,添加氧化石夕溶膠w麵&含有氧化石夕 ’接著添加高嶺土，均勻混合後，行喷霧乾燥，接 著藉進行洗净去礦質，製得平均粒徑之添加劑3。於 表1表示添加劑3之組成及性質。 [比較例1 :添加劑4] 、將抑氧化合物聚體Al〇7〇g(含有石夕紹氧化合物啊) 以整為pH4() ’添加氧化赠賴⑹㈣含有氧化石夕 2〇〇g)’接轉加高嶺土65Gg均自混合後，行喷霧乾燥，接 著藉進行料去㈣，料平均粒細 // m之添加劑4。於 表1表示添加劑4之組成及性質。 [比較例2 :添加劑5] :、呂氧化合物及體A571()g(含有石夕紹氧化合物細幻 以硫酸調“pH4_G ’添加氧切溶膠μ刪g(含有氧化石夕 •j)句勻&合後’ ^噴霧乾燥’接著藉進行洗淨去礦質， ΊΊ60#πι之添加劑5。於表】表示添加劑5之組成 10 201130962 及性質。 [活性評估] 使用添加劑1〜5，評估添加劑之固體酸量對活性之影 響。 添加劑之活性評估，使用ARC0社製試驗級反應器進 行。此裝置為使觸媒於裝置内循環並重複反應與觸媒再生 之循環式流動床，仿商業規模使用之Fcc單元。*FCC平衡 觸媒與添加劑1〜5各自混合為質量比9〇: 1〇(1 8kg: 〇2kg) ’ 使用脫硫常壓殘油（DSAR)，反應塔溫度設定為52〇t：，再 生塔溫度設定為6 7 〇 ，於裝置中調整成相對於原料油！ g觸 媒為5g或7g，進行接觸裂解反應，分析反應後生成物及殘 留物（生成液）。在此，將反應塔内生成氣體以株式會社島津 製作所製氣相層析儀[Micro GC 3000A]分析，測定氫及 C1〜C4為止之產率，同時將再生塔内生成之CO及eh以島 津製作所製紅㈣观式《分析裝置[CGTJGGG]分析並 十真,、、、厌產率。再者，將生成液以Hew丨eU packard社製蒸麵 氣相層析儀[GC System刪_]測定汽油齡、輕油餘分 (LCO)及重油餾分（HC〇)之生成量。反應前添加劑1〜$於 100%蒸氣條件下，以8贼各自處理丨2小時。表丨表示各自 之評估結果。X，於評估結果中，轉化率以未加入添加劑 時之測定結果為鱗，標記其差值，又，關於汽油、LC0、 HCO及焦厌’係將前述轉化率一定時各自之生成量，以未 加入添加_之生成量絲準，標記其差值。於以下之實 施例亦同樣地進行評估。 201130962 根據表1，當固體酸量為0.1〜〇.4mmol/g，隨固體酸量增 加，重油餾分之裂解效率提昇，HCO餾分減少，而得到良 好結果，但當固體酸量為0.08mmol/g，由於重油顧分之裂 解效率低，HCO餾分增加，又，當固體酸量為0.5mmol/g， 雖重油餾分之裂解效率提昇且HCO減少，但焦炭產率增加。 [表1] 實施例1 實施例2 實施例3 比較例1 比較例2 添加劑1 添加劑2 添加劑3 添加劑4 添加劑5 組成 黏合劑 (氧化矽） 質量％ 20 20 20 20 20 高嶺土 質量％ 60 40 10 65 - 矽鋁氧化合物 質量％ 20 40 70 15 80 性質 體密度 ml/g 0.85 0.84 0.80 0.90 0.76 比表面積 m2/g 100 200 300 85 330 總固體酸量 mmol/g 0.10 0.20 0.40 0.08 0.50 強酸量/總固體酸量％ 0 0 0 0 0 活性評估 轉化率 質量％ +0.1 +0.4 +0.7 +0.1 +0.8 汽油 質量％ +0.1 +0.3 +0.4 ±0 +0.4 LCO 質量％ +0.2 +0.4 +0.7 +0.1 +0.8 HCO 質量％ -0.3 -0.4 -0.7 -0.1 -0.8 焦炭 質量％ -0.1 -0.2 ±0 ±0 +0.3 《試驗例2 :比表面積之影響》 [實施例4 :添加劑6] 將矽鋁氧化合物漿體A2860g(含有矽鋁氧化合物400g) 以硫酸調整為pH4.0，添加氧化矽溶膠bl600g(含有氧化矽 2〇〇g)，接著添加高嶺土 l〇〇g及超安定化Y型沸石300g(乾燥 12 201130962 質量。以下相同）均勻混合後，行噴霧乾燥，接著藉洗淨去 礦質，製得平均粒徑60 μ m之添加劑6。於表2表示添加劑6 之組成及性質。 [比較例3 :添加劑7] 將矽鋁氧化合物漿體A1430g(含有矽鋁氧化合物200g) 以硫酸調整為pH4.0，添加氧化矽溶膠bl600g(含有氧化矽 200g)，接著添加高嶺土 100g及超安定化Y型沸石500g均勻 混合後，行喷霧乾燥，接著藉洗淨去礦質，製得平均粒徑 60之添加劑7。於表2表示添加劑7之組成及性質。 [活性評估] 使用添加劑1、添加劑3、添加劑4、添加劑6及添加劑7， 評估關於比表面積造成對活性之影響。於表2表示各自之評 估結果。又，關於添加劑7，由於體密度低而難以使用於實 際裝置，未進行活性評估。 根據表2，當比表面積為100〜350m2/g，由於與重油餾 分之反應場增加，HCO產率降低而得到良好結果，但當比 表面積為85m2/g，因反應場少而HCO產率增加，當410 m2/g，預期反應場多而有效率地裂解重油餾分，但由於體 密度低而不實用。 13 201130962 [表2] 實施例1 實施例4 比較例1 添加劑1 添加劑3 添加劑6 添加劑4 添加劑7201130962 VI. INSTRUCTIONS INSTRUCTIONS: FIELD OF THE INVENTION The present invention relates to an additive for a fluid catalytic cracking catalyst, which is added to a flow catalyst cracking device (FCC device) for addition to a flow catalyst cracking. Catalyst (FCC catalyst) is used, in particular, to crack down on heavy oil fractions (tower oil) in feedstocks to make a good deal (especially gasoline). t ^tr ^ BACKGROUND OF THE INVENTION In the past, light oil was produced by using a catalytic catalyst for cracking a catalyst to crack a feedstock oil, but because of the high price of crude oil, the heavier feedstock oil (heavy oil) was also treated. Here, in order to efficiently crack the heavy oil fraction (e.g., residual oil) by using the FCC catalyst, the active component (represented by zeolite and alumina) contained in the FCC catalyst is increased. However, if the ratio of the active component in the FCC catalyst increases, there is a problem that physical properties such as a decrease in catalyst strength are deteriorated. In addition, in the flow catalyst cracking device, when the heavy oil in the raw material oil is cracked and the light weight is obtained, the cracking of the heavy oil storage will be increased to increase the coke, and when the coke generated is burned, the temperature rise and the water will be caused. Steam is generated, and there is a problem that the quality of the FCC catalyst is deteriorated. In order to solve these problems, the following additives have been developed as FCC Additives for FCC catalysts. For example, Patent Document 1 discloses an additive for a fluid catalytic cracking catalyst, which is composed of a granular mixture of a crushed oxygen compound, a clay, and a cerium oxide. The cerium oxide content of the cerium aluminide compound is 10 to 30% by weight, and the mixture The content of cerium contained in the cerium is 10 to 60% by weight in terms of Si02. 201130962 Further, Patent Document 2 discloses an activator for a flow catalyst cracking catalyst, which is composed of Shixi aluminoxy compound, clay, and oxidized stone, and is converted into a total of 10 to 60 by Si〇2. It is composed of particles of weight %, and has a specific surface area of 3 〇 8 〇 m 2 /g and a total pore volume of 0.14 to 0.45 ml / g, and the pore volume of the pore radius 6 is less than or equal to 5 ml / g. Hereinafter, the total acid amount is in the range of 0·02 to 0.065 mmol/g. Patent Document 3 discloses an additive for a fluid catalytic cracking catalyst, which is composed of a composite metal oxide, clay and cerium oxide, and has a specific surface area of 30 to 8 〇m 2 /g and a total pore diameter of 0.14 to 〇.45 ml/g. The volume and the pore volume of the pores of 60 to 200 A are in the range of 45% or more of the total pore volume. Patent Document 4 discloses an additive catalyst for heavy oil cracking, which is composed of a composite metal oxide, clay and cerium oxide, and has a specific surface area of 30 to 8 〇m 2 /g, a total acid amount of 0.02 to 0.08 mmol/g, and is relative to the total. The acid amount ratio of the acid amount is 10 to 50%. The additives disclosed in Patent Documents 1 to 4 are those having a cerium oxide content of 10 to 30% by weight in the cerium aluminoxy compound and a cerium oxide content of 1 〇 to 6 〇 in the mixture. % 'specific surface area 30~80m2/g, total acid amount 〇.〇2~〇.〇8mmol/g. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document Patent Document 1: Japanese Patent No. 3,497, 783, Patent Document 2: Japanese Patent No. 3,467, 608, Patent Document 3: Japanese Patent No. 3,643,843, Patent Document 4: Japanese Patent No. 3,920,966 201130962 SUMMARY OF THE INVENTION Problem to be Solved by the Invention However, although the conventional additive has a certain effect on the cracking of the heavy oil fraction, it is necessary to further improve the cracking efficiency of the heavy oil. Here, when the heavy oil fraction flow catalyst is cracked by using the additives, the heavy oil fraction is cracked while the coke yield is increased, and the coke yield is increased, causing the temperature in the catalyst regeneration tower in the FCC unit to rise, accompanied by coke combustion. The temperature rises and the water vapor is generated, which causes the FCC catalyst quality to deteriorate. The present invention has been made in view of such circumstances, and an object thereof is to provide an additive for a flow catalyst cracking catalyst which can improve the cracking efficiency of a heavy oil fraction and which can suppress an increase in coke yield. The means for solving the problem according to the above-mentioned objects, the additive for the catalytic catalyst for catalyzing the flow of the present invention is obtained by spray-drying a mixed damaging agent containing a binder and a sulphur compound. The surface area is 100 to 400 m 2 /g, and the total solid acid amount is 0.10 mmol/g or more and less than 0.50 mmol/g. In the additive for a fluid catalytic cracking catalyst of the present invention, the ratio of the strong acid amount to the total solid acid amount is preferably 20% or less. In the additive for a fluid catalytic cracking catalyst of the present invention, the mixed slurry preferably contains porous cerium oxide or zeolite. In the additive for a fluid catalytic cracking catalyst of the present invention, the ratio of the yttrium aluminum oxide compound in the mixed slurry is preferably 20% by mass or more and less than 80% by mass. In the additive for a fluid catalytic cracking catalyst of the present invention, the cerium oxide content in the above-mentioned 矽 5 201130962 oxy-compound compound is preferably more than 〇 mass % and less than 10 mass 0 / 〇. In the additive for a fluid catalytic cracking catalyst of the present invention, the binder is preferably a cerium oxide compound or an aluminum compound. EFFECTS OF THE INVENTION The additive of the present invention has a specific surface area of 1 〇〇 to 400 m 2 /g, and the total solid acid amount is 0.10 to 0.50 mmol/g. Therefore, the activity is larger than that of the conventional additive, and the heavy duty (HCO: Heavy Cycle Oil) The yield is reduced, the gasoline yield is increased, and the coke yield is equivalent. This is because the specific surface area of the additive and the total solid acid amount are higher than conventionally, and the contact area and active point of the feedstock oil and the additive increase, and as a result, the FCC catalyst activity increases and the HCO yield decreases. It can also be considered as 'by reducing the ratio of strong acid in the total solid acid to 2〇〇/0 or less, and suppressing the excessive cracking reaction, increasing the yield of gasoline and FCC cracking light oil (LCO: Light Cycle), and inhibiting coke more. The increase in yield. t Embodiment 3 Mode for Carrying Out the Invention An additive for a fluid catalytic cracking catalyst according to an embodiment of the present invention will be described. The flow catalyst cracking catalyst additive (hereinafter also referred to as "additive") of the present invention is used in a flow catalyst cracking device (FCC device), and is particularly suitable for cracking heavy oil in a raw material oil (tower oil). It is used in the (7)L mobile catalyst cracking catalyst and is composed of an inorganic oxide porous body containing zeolite. The additive of the present invention is obtained by spray-drying a binder and a ruthenium aluminide compound under a known condition, and the specific surface area 201130962 measured by the BET method (JIS Z8830) is 100 to 400 m 2 /g, preferably 150 to 380 m 2 . /g, preferably 200 to 350 m2/g, and the total solid acid amount (adsorption heat 70 kJ/mol) measured by an ammonia adsorption calorimetry (refer to Japanese Patent No. 3848952, actually measured by the method described in Example 1) The above ammonia adsorption amount is 0.10 mmol/g or more, less than 0.50 mmol/g, preferably 0.20 to 0.45 mmol/g, and more preferably 0.25 to 0.40 mmol/g. Here, if the specific surface area of the additive is less than 100 m2/g, the reaction range of the additive and the feedstock oil is reduced, and the heavy oil fraction (HCO) cracking efficiency is lowered. If it exceeds 400 m2/g, the bulk density and strength of the additive are deteriorated. Further, when the solid acid amount of the additive is less than 0.10 mmol/g, the cracking efficiency of the heavy oil fraction is lowered by '0.50 mmol/g or more, and the heavy oil fraction is excessively cracked to increase the coke yield. The binder used may be a oxidized stone compound or a lysine compound. Here, for example, water glass, a citric acid solution, or the like can be used, and examples thereof include a basic aluminum vaporized aluminum and a diaspore condensed sol. The Shi Ximing oxygen compound can be used by mixing or mixing a cerium oxide compound into a pseudo-alumina gel or a diaspore gel. The content of yttrium oxide in the oxygen compound of Shi Ximing is greater than 〇 mass% and less than 丨〇 畺 A and is 1 to 9 mass VO α. Here, the content of yttrium oxide in yttrium aluminum oxide is 10 mass% or more 'specific surface area and The amount of acid will decrease. The mixed destructive body may also contain clay minerals, porous oxidized oxides and zeolites. The clay minerals include W-ling, montmorillonite, dolomite and calcite, porous oxidized cerium hydrated cerium oxide and anhydrous cerium oxide, etc., zeolite has ultra-stable Y-type zeolite (10) Υ), Η·γ, NH4-Y, The addition of porous oxidized oxide or zeolite to RE-Y, RE-USY, ZSM-5 and mercerized feldspar can adjust (increase) the specific surface area of additive 201130962 and contribute to the increase in activity. The ratio of the sand aluminum oxide compound in the mixed destructive body is preferably 20% by mass or more, and less than 8 (% by mass), and more preferably 40 to 70% by mass. X, the specific surface area of the additive and the amount of solid acid can be controlled by the ratio of the sulphur oxide compound. Here, the ratio of the stellite oxygen compound in the mixed slurry is less than 2 〇 mass. /〇, due to insufficient active ingredient in the cracked heavy oil store, it will be difficult to effectively crack the heavy oil fraction. When 80% by mass or more, the strength and bulk density of the additive will decrease, and it will flow when used as an additive for the flow catalyst cracking catalyst. Sexual deterioration or pulverization' is therefore a concern that it is difficult to operate a mobile catalyst cracker. Further, the binder concentration in the mixed polymer is about 1 to 15% by mass, and the solid content concentration in the mixed slurry is about 15 to 30% by mass. The ratio of the strong acid amount (the ammonia adsorption amount of the adsorption heat of 110 kJ/mol or more in the ammonia adsorption heat measurement method) to the total solid acid amount of the additive is 20% or less, and preferably 10% or less, and more preferably 5% or less. Here, when the amount of the above-mentioned strong acid is more than 20%, an excessive cleavage reaction will occur, and there is a tendency for the coke yield to increase. EXAMPLES Examples and comparative examples are described below, but the present invention is not limited thereto. "Test Example 1: Effect of Solid Acid Amount" [Example 1 : Additive 1] Water glass of 17.5% by mass of cerium oxide was adjusted to pH 1.6 with a sulfuric acid aqueous solution of 25 mass% to prepare cerium oxide sol a 300 g (containing cerium oxide) 1〇% by mass, that is, containing gasification 矽3〇g), added to 7690g (containing alumina l〇〇〇g) of water shale slurry containing alumina (A12〇3)13.〇质量〇/〇 'With 48 quality. /〇之8 201130962 Hydroxide dissolved in water _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Compound Oxidation = _5"% water broken glass is adjusted with sulfuric acid ^ constitutes a viscous oxygen-cutting cardio-cut compound so = _ oxygen compound theory 143% (containing alkaloid compound 2 〇〇 g) = acid adjustment after excitation, Add oxygen to dissolve (four) coffee g (containing yttria g below the same) 'then add kaolin _g (dry quality. The following = the same) evenly mixed, with an inlet temperature of 46 (rc, outlet temperature of 26 generations, and printing time 2 g minutes of conditional spray money (the same applies to the same example), followed by washing (after adding 20% by mass of ammonium sulfate on a catalyst drying basis, the sulfuric acid was removed by 15% water in the following example. In the following examples The same applies to the decanter to make an additive with an average particle size of 60 μm. The composition of the additive 1 is shown in the table. Furthermore, the specific surface area of the additive 1 is determined by the bet method, and the bulk density is determined by the UOP method 254-65 (in The following examples are also the same. The expression of the additive i is shown in Table 。. Method) The additive 1 prepared was subjected to the following measurement of the amount of solid acid. First, 0 to 2 g of the additive 1 was calcined at 5 Torr for 1 hour, followed by heat treatment at 1×1 (T4torr) at 400 ° C for 4 hours. The ammonia gas is adsorbed, and the heat of adsorption generated at this time is measured to calculate the total amount of solid acid. The amount of ammonia adsorbed by the "Calorimeter" manufactured by Tokyo Polytechnic Co., Ltd. with the adsorption heat of 7〇kJ/mol or more is taken as the total solid acid amount. 11 OkJ/mol or more is a strong acid amount (the same applies to the following example, 201130962 疋). Table 1 shows the solid acid amount measurement result of the additive 1. [Example 2: Additive 2] Alumite aluminum oxide slurry A2860g (containing yttrium aluminum oxide 4〇〇g) is adjusted to pH4〇, and cerium oxide sol bi6〇〇g (containing cerium oxide 200g) is added. Then kaolin is added. By washing and demineralizing, an average particle size adding agent 2 is obtained. The composition and properties of the additive 2 are shown in Table 1. [Example 3: Additive 3] Aluminium oxyaluminate slurry A5〇〇〇g (containing yttrium aluminum oxide 7 (10) 幻 ϋ adjusted to pH 4G, added oxidation The sol-gel surface & contains oxidized stone eves followed by the addition of kaolin, uniformly mixed, spray-dried, and then washed and demineralized to obtain an average particle size additive 3. Table 1 shows the composition of the additive 3 and [Comparative Example 1 : Additive 4], the oxygen-suppressing compound poly-Al 〇 7 〇 g (containing Shi Xi Shao Oxygen compound ah) to add oxygen to the whole pH4 () ' (6) (4) contains oxidized stone 夕 2 〇〇 g) 'After mixing and adding kaolin 65Gg are self-mixed, spray-drying, then take the material to go (4), the average particle size / / m of additive 4 . Table 1 shows the composition and properties of the additive 4. [Comparative Example 2: Additive 5]:, Lu oxygen compound and body A571 () g (containing Shi Xi Shao oxygen compound fine-eyed with sulfuric acid adjusted "pH4_G 'added oxygen cut sol μ delete g (including oxidized stone eve • j) sentence After the mixture & after the ' ^ spray drying ' and then by washing to remove minerals, ΊΊ 60 # πι additive 5 in the table] indicates the composition of the additive 5 10 201130962 and properties. [activity evaluation] using additives 1 ~ 5, evaluation of additives The effect of the amount of solid acid on the activity. The activity of the additive was evaluated using a test-grade reactor manufactured by ARC0. This device is a circulating fluidized bed that circulates the catalyst in the device and repeats the reaction and catalyst regeneration. Fcc unit used. *FCC balance catalyst and additive 1~5 are each mixed to mass ratio 9〇: 1〇(1 8kg: 〇2kg) ' Using desulfurization atmospheric residual oil (DSAR), the reaction tower temperature is set to 52 〇t: The temperature of the regeneration tower is set to 6 7 〇, and it is adjusted to 5 g or 7 g with respect to the raw material oil in the apparatus. The contact cleavage reaction is carried out to analyze the product and residue (forming liquid) after the reaction. Therefore, the gas generated in the reaction column is The gas chromatograph [Micro GC 3000A] manufactured by Shimadzu Corporation was used to analyze the yield of hydrogen and C1 to C4, and the CO and eh generated in the regeneration tower were made by Shimadzu Corporation. The analysis device [CGTJGGG] ] Analysis and the tenth, the, and the anaerobic yield. In addition, the production liquid was measured by the Hew丨eU Packard company's steam surface gas chromatograph [GC System _] to determine the gasoline age, light oil residual (LCO) And the amount of heavy oil fraction (HC〇) produced. The pre-reaction additive 1~$ is treated with 8 thieves for 2 hours under 100% steam conditions. The table indicates the respective evaluation results. X, in the evaluation results, the conversion rate When the additive is not added, the measurement results are scaled, and the difference is marked. Further, regarding the gasoline, the LC0, the HCO, and the Jiaoyu's, the respective conversion amounts of the above-mentioned conversion ratios are determined, and the amount of the addition is not added. The difference is marked and evaluated in the following examples. 201130962 According to Table 1, when the amount of solid acid is 0.1~〇.4mmol/g, the cracking efficiency of the heavy oil fraction increases as the amount of solid acid increases, and the HCO fraction Reduced, and get good results, but when solid acid When it is 0.08 mmol/g, the HCO fraction is increased due to the low cracking efficiency of the heavy oil, and when the solid acid amount is 0.5 mmol/g, although the cracking efficiency of the heavy oil fraction is increased and the HCO is decreased, the coke yield is increased. 1] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Additive 1 Additive 2 Additive 3 Additive 4 Additive 5 Composition binder (cerium oxide) Mass% 20 20 20 20 20 Kaolin mass% 60 40 10 65 - 矽Aluminoxy compound mass% 20 40 70 15 80 Density of body weight ml/g 0.85 0.84 0.80 0.90 0.76 Specific surface area m2/g 100 200 300 85 330 Total solid acid amount mmol/g 0.10 0.20 0.40 0.08 0.50 Strong acid amount / total solid acid amount % 0 0 0 0 0 Activity evaluation conversion mass % +0.1 +0.4 +0.7 +0.1 +0.8 Gasoline mass % +0.1 +0.3 +0.4 ±0 +0.4 LCO mass% +0.2 +0.4 +0.7 +0.1 +0.8 HCO Quality % -0.3 -0.4 -0.7 -0.1 -0.8 Coke mass% -0.1 -0.2 ±0 ±0 +0.3 "Test Example 2: Effect of specific surface area" [Example 4: Additive 6] Aluminium oxy-alumina slurry A2860g (containing bismuth aluminum oxide 400g) adjusted to pH 4.0 with sulfuric acid, Add cerium oxide sol 600g (containing cerium oxide 2〇〇g), followed by kaolin l〇〇g and super-anhydrogenated Y-type zeolite 300g (dry 12 201130962 mass. After the same mixing), the mixture was spray-dried, followed by washing to remove minerals, and an additive 6 having an average particle diameter of 60 μm was obtained. Table 2 shows the composition and properties of the additive 6. [Comparative Example 3: Additive 7] Aluminium oxyaluminate slurry A1430g (containing 200 g of yttrium aluminum oxide compound) was adjusted to pH 4.0 with sulfuric acid, 600 g of cerium oxide sol (containing 200 g of cerium oxide) was added, and then kaolin 100 g and super were added. 500 g of the stabilized Y-type zeolite was uniformly mixed, spray-dried, and then washed to remove minerals to prepare an additive 7 having an average particle diameter of 60. Table 2 shows the composition and properties of the additive 7. [Evaluation of Activity] Using the additive 1, the additive 3, the additive 4, the additive 6, and the additive 7, the effect on the activity caused by the specific surface area was evaluated. Table 2 shows the results of their respective evaluations. Further, the additive 7 was difficult to use in an actual device because of its low bulk density, and no activity evaluation was performed. According to Table 2, when the specific surface area is 100 to 350 m 2 /g, the HCO yield is lowered due to an increase in the reaction field with the heavy oil fraction, but when the specific surface area is 85 m 2 /g, the HCO yield is increased due to the small reaction field. At 410 m2/g, it is expected that the reaction field will cleave the heavy oil fraction efficiently, but it is not practical due to low bulk density. 13 201130962 [Table 2] Example 1 Example 4 Comparative Example 1 Additive 1 Additive 3 Additive 6 Additive 4 Additive 7
《試驗例3 :矽鋁氧化合物中氧化矽含量之影響》 [實施例5 :添加劑8] 於含有氧化鋁13.0質量％之水鋁石漿體7690g中，添加 氧化矽溶膠a500g(即含有氧化矽5〇g)後，以48質量％之氫氧 化鈉水’谷液調整成為pH1Q 5 ’再於95。。熟成丨小時製得含 有氧化碎5質量％之仙氧化合物㈣B。此雜氧化合物 4體B ’氧化!s及氧切合計濃度為15質量％。 將矽鋁氧化合物漿體B467〇g(含有矽鋁氧化合物7〇〇幻 以硫酸調整為pH4〇，添加氧化矽溶膠bl6〇〇g(含有氧化矽 200g) ’接著添加高嶺土 1〇〇g均勻混合後，行喷霧乾燥，接 著藉洗淨去礦質，製得平均粒徑6〇//111之添加劑8。於表3 表示添加劑8之組成及性質。 201130962 [比較例4 .添加劑9] 將含有氧化鋁13.0質量％之水鋁石漿體5385g(含有氧 化銘70〇g)以硫酸調整為pH4.0，添加氧化矽溶膠bl600g(含 有氧化矽20〇g)，接著添加高嶺土 100g均勻混合後，行噴霧 乾燥，接著藉洗淨去礦質，製得平均粒徑60"m之添加劑9。 於表3表示添加劑9之組成及性質。 [比較例5 :添加劑1〇] 於含有氧化鋁13.0質量％之水鋁石漿體769〇g中，將 17.5%之水玻璃以硫酸調整為pH16，添加氧化矽溶膠 al200g(即含有氧化矽12〇§)後，以仆質量％之氫氧化鈉水溶 液調整成為pHlG.5，再於95。(：熟成H、時，製得含有氧化石夕 11質里％之矽鋁氧化合物漿體c。此矽鋁氧化合物漿體c , 氧化鋁及氧化矽合計濃度為15質量〇/〇。 將石夕紹氧化合物焚體C467〇g(含有石夕紹氧化合物7〇〇幻 以石J “周整為pH4G ’添加氧切溶膠bi_g(含有氧化石夕 =0g) ’接著添加高嶺土 1GGg均$混合後，行賴乾燥接 4藉先I去礦I ’製得平均粒彳之添加劑⑺。於表3 表示添加劑10之組成及性質。 、 [活性評估] 用、:J、、加M3添加劑8、添加劑9及添加齊〇〇 ,坪估 自之評估結果 紹氧化合物中氧切含量造成對活性之影響。於表3表示各 ^ Λ 孔化合物中氧化矽含量增加，HCO產 率減少，Μ好結果，但當氧切含量細質量％，由於Ϊ 15 201130962 體酸量少，HCO產率減少幅度小，當氧化矽含量為11質量 /〇，焦灭產率增加。 [表3] --^ 會施例3 實施例5 比較例4 比較例5 添加劑3 添加劑8 添加劑9 添加劑10 組; ~r---- 二^氧化質量％ 20 20 20 20 _土 質量 ％ 10 10 10 10 合物質量％ 70 70 - 70 —鋁 質量％ - - 70 - 石夕恥氧化合物 μ曰 中氧化·ε夕令‘質®% 3 5 0 11 Τ生筲 -- --—.. —度 ml/g 0.80 0.80 0.78 0.81 _^積 m2/g 300 310 210 350 _酸量 mmol/g 0.40 0.40 0.20 0.50 總固體酸量％ 0 1 0 4 λ ·\±η^ _率 質量％ +0.7 +0.7 +0.2 +0.8 質量％ +0.4 +0.5 ±0 +0.3 __LC〇 質量％ +0.7 +0.4 +0.1 +0.7 -0.8 __HCO 質量％ -0.7 -0.4 -0.1 質量β/〇 ±0 +0.1 ±0 +0.3 《試驗例4:固體酸量之影響》 [實施例6 :添加劑11] 於八丨2〇3濃度為23.3質量％之鹼式氣化鋁溶液b858g(氧 化鋁化合物所構成黏合劑之一例。含有氧化鋁2⑽㈡中，添 加问嶺土5GGg’接著添加以硫酸調整為pH5.G之邦氧化合 物’灵，A214Gg(含有_ |g氧化合物獅呂)均句 混合後，行喷 ，乾燥接著藉洗淨去礦質，製得平均粒徑60,之添加劑 °料4❹之組成及性質。 16 201130962 [實施例7 :添加劑i2] 於鹼式氣化鋁溶液b858g(含有氧化鋁200g)中，添加高 嶺土3〇〇g，接著添加以硫酸調整為PH4.5之矽鋁氧化合物默 體A3570g(含有矽鋁氧化合物5〇〇g)均勻混合後，行噴霧乾 燥，接著藉洗淨去礦質，製得平均粒徑6〇"爪之添加劑。 於表4表示添加劑丨2之組成及性質。 [實施例8 :添加劑13] 於鹼式氯化鋁溶液b858g(含有氧化鋁200g)中，添力口言 嶺土 100g，接著添加以硫酸調整為pH4 〇之石夕紹氧化合物将 體A5000g(含有矽鋁氧化合物7〇〇g)均勻混合後，行嘴霧乾 燥，接著藉洗淨去礦質，製得平均粒徑60之添加劑Ο。 於表4表示添加劑13之組成及性質。 [比較例6 :添加劑14] 於驗式氣化鋁溶液b858g(含有氧化鋁200g)中，添加言 嶺土600g ’接著添加以硫酸調整為pH4.〇之石夕紹氧化合物將 體A1430g(含有矽鋁氧化合物2〇〇g)均勻混合後，行嘴霧^ 燥，接著藉洗淨去礦質，製得平均粒徑60/ζπι之添加劑u。 於表4表示添加劑14之組成及性質。 [比較例7 :添加劑15] 於鹼式氣化鋁溶液b858g(含有氧化鋁200g)中，添力〇^ 硫酸調整為pH4.0之矽鋁氧化合物聚體A571〇g(含有石夕紹氧 化合物800g)均勻混合後’行喷霧乾燥，接著藉洗淨去石产 質’製得平均粒徑60# m之添加劑15。於表4表示添加劑15 之組成及性質。 17 201130962 [活性評估] 吏用添加船丨〜〗5，評估關於添加劑 性之影響。料4以各自之料絲。^對活 根據表4 ’氧化!g溶膠黏合劑亦與氧化妙溶膠黏合劑相 同田固體酸量為0.1〜〇.4mmol/g，隨固體酸量增加，重油 德分之裂解效率提昇，HC⑽分減少，得職好結果，但 當固體酸量為o.G7mm(Dl/g，重油顧分之裂解效率提昇，hc〇 餾刀增加，當固體酸量為〇 5mm〇l/g，焦炭產率增加。 [表4] 實施例6 實施例7 實施例8 比較例6 比較例7 添加劑 11 添加劑 12 添加劑 13 添加劑 14 添加劑 15 組成 黏合劑 (氧化矽） 質量％ 20 20 20 20 20 高嶺土 質量％ 50 30 10 60 矽鋁氧化合物 質量％ 30 50 70 20 80 性質 _ 體密度 ml/g 0.80 0.75 0.70 0.82 0.65 比表面積 m2/g 100 210 280 90 310 總固體酸量 mmol/g 0.10 0.30 0.40 0.07 0.50 強酸量/總固體酸量％ 0 0 0 0 0 活性評估 轉化率 質量％ +0.1 +0.3 +0.5 +0.1 +0.8 汽油 質量％ +0.1 +0.3 +0.4 ±0 +0.4 LCO 質量％ +0.2 +0.4 +0.7 +0.1 +0.8 HCO 質量％ -0.3 -0.4 -0.7 -0.1 -0.8 焦炭 質量％ ±〇 1 +0. 1^ +0.1 ±0 +0.3 18 201130962 《試驗例5 :比表面積之影響》 [實施例9 :添加劑16] 於鹼式氣化鋁溶液b858g(含有氧化鋁2〇〇幻中，添加高 嶺土 100g，接著添加以硫酸調整為pH4 〇之矽鋁氧化合物漿 體A2860g(含有矽鋁氧化合物400g)及超安定化γ型沸石 300g均勻混合後，行噴霧乾燥，接著藉洗淨去礦質，製得 平均粒徑60/zm之添加劑16。於表5表示添加劑“之組成及 性質。 [比較例8 :添加劑17] 於鹼式氯化鋁溶液b858g(含有氧化鋁2〇〇g)中，添加高 嶺土 100g，接著添加以硫酸調整為pH4 〇之矽鋁氧化合物漿 體A1430g(含有矽鋁氧化合物2〇〇g)及超安定化γ型沸石 5〇〇g均句混合後’行喷霧乾燥，接著藉洗淨去礦質，製得 平均粒徑60#m之添加劑17。於表5表示添加劑17之組成及 性質。 [活性評估] 使用添加劑11、添加劑13、添加劑14、添加劑16及添 加劑17，评估關於比表面積造成對活性之影響。於表5表示 各自之评估結果。又，關於添加劑17 ’由於體密度低而難 以使用於實際裝置，未進行活性評估。 根據表5 ,當比表面積為1〇〇〜35〇m2/g，與重油餾分之 反應場增加使得HCO產率降低而得到良好結果，但當比表 面積為90m2/g，由於反應場少HC〇產率增加當4i〇m2/g， 預期反應場？而有效率地裂解重㈣分，但由於體密度低 19 201130962 而不實用。 [表5] 實施例6 實施例8 實施例9 比較例6 比較例8 添加劑 11 添加劑 13 添加齊J 16 添加劑 14 添加劑 17 組成 點合劑 質量％ (氡化矽） 20 20 20 20 20 兩嶺土 質量％ 50 10 10 1 60 10 矽鋁氧化合物 質量％ 30 70 40 20 20 沸石 質量％ - - 30 一 50 性質<<Test Example 3: Effect of cerium oxide content in cerium-aluminum oxy-compound>> [Example 5: Additive 8] 500 g of cerium oxide sol a (i.e., containing cerium oxide) was added to 7690 g of a boehmite slurry containing 13.0% by mass of alumina. After 5 〇 g), it was adjusted to pH 1Q 5 ' and then 95 with 48% by mass of sodium hydroxide water. . The oxidized compound (4) B containing 5 mass% of oxidized granules was obtained by aging. The concentration of the oxygen-containing compound 4 in the form of B' oxidation!s and oxygen cut was 15% by mass. The bismuth aluminide slurry B467 〇g (containing yttrium aluminum oxide 7 〇〇 以 sulfuric acid adjusted to pH 4 〇, added cerium oxide sol bl6 〇〇 g (containing cerium oxide 200g) 'then added kaolin 1 〇〇 g uniform After mixing, spray drying, followed by washing to remove minerals, to obtain an additive 8 having an average particle diameter of 6 〇//111. Table 3 shows the composition and properties of the additive 8. 201130962 [Comparative Example 4 . Additive 9] 5385 g (containing Oxide 70 〇g) containing 13.0% by mass of alumina, adjusted to pH 4.0 with sulfuric acid, 600 g of cerium oxide sol (containing 20 〇g of cerium oxide), and then uniformly mixed with 100 g of kaolin Spray drying, followed by washing to remove minerals, to obtain an additive having an average particle diameter of 60 " m 9. Table 3 shows the composition and properties of the additive 9. [Comparative Example 5: Additive 1 〇] Containing alumina 13.0 mass In the 769 〇g of the boehmite slurry, 17.5% of the water glass is adjusted to pH 16 with sulfuric acid, and after adding cerium oxide sol a 200 g (that is, containing cerium oxide 12 〇§), it is adjusted with a servative mass% sodium hydroxide aqueous solution. Become pH1G.5, then 95. (: Mature H, when, The yttrium aluminum oxide slurry c containing oxidized rock eve 11 mass% is obtained. The yttrium aluminum oxide slurry c, the total concentration of alumina and cerium oxide is 15 mass 〇 / 〇. 〇g (containing Shi Xi Shao oxygen compound 7 〇〇 以 石 stone J "weekly is pH4G 'add oxygen cutting sol bi_g (containing oxidized stone 夕 = 0g) 'then add kaolin 1GGg are mixed, then dry and dry 4 The additive (7) of the average granules was obtained by I to mine I. The composition and properties of the additive 10 are shown in Table 3. [Evaluation of activity]: J, M3 additive 8, additive 9 and addition The evaluation results from the evaluation results show that the oxygen cut content in the oxygen compound causes an effect on the activity. Table 3 shows that the content of yttrium oxide in the porphyrin compound increases, the HCO yield decreases, and the result is good, but when the oxygen cut content is fine % by mass, due to the small amount of body acid, the reduction in HCO yield is small, and when the content of yttrium oxide is 11 mass/〇, the yield of charring increases. [Table 3] --^ Example 3 Example 5 Comparison Example 4 Comparative Example 5 Additive 3 Additive 8 Additive 9 Additive 10 Group; ~r---- ^Oxidation mass% 20 20 20 20 _ soil mass% 10 10 10 10 compound mass% 70 70 - 70 - aluminum mass % - - 70 - 夕 耻 氧 氧 曰 曰 氧化 氧化 氧化 ' 质 质 质 质 质 质 质5 0 11 筲生筲-- ---..-degree ml/g 0.80 0.80 0.78 0.81 _^product m2/g 300 310 210 350 _acid amount mmol/g 0.40 0.40 0.20 0.50 total solid acid amount % 0 1 0 4 λ ·\±η^ _rate mass% +0.7 +0.7 +0.2 +0.8 mass% +0.4 +0.5 ±0 +0.3 __LC〇 mass% +0.7 +0.4 +0.1 +0.7 -0.8 __HCO mass% -0.7 -0.4 -0.1 Mass β / 〇 ± 0 + 0.1 ± 0 + 0.3 "Test Example 4: Effect of solid acid amount" [Example 6: Additive 11] Basic aluminum hydride at a concentration of 28.3 mass% at 8丨2〇3 Solution b858g (an example of a binder composed of an alumina compound). In the case of containing alumina 2 (10) (b), adding 5GGg of 'Qingling' and then adding sulfuric acid compound which is adjusted to pH 5.G with sulfuric acid, and A214Gg (containing _ |g oxygen compound lion) are mixed, sprayed, dried and then borrowed. Washed and demineralized to obtain an average particle size of 60, the composition and properties of the additive. 16 201130962 [Example 7: Additive i2] In a basic aluminized vaporized aluminum solution b858g (containing 200 g of alumina), 3 g of kaolin was added, followed by addition of a lanthanum aluminide compound A3570g adjusted to pH 4.5 with sulfuric acid. (5 〇〇g containing yttrium aluminum oxide) was uniformly mixed, spray-dried, and then demineralized by washing to obtain an additive having an average particle diameter of 6 〇" Table 4 shows the composition and properties of the additive 丨2. [Example 8: Additive 13] In a basic aluminum chloride solution b858g (containing 200 g of alumina), 100 g of Tianli Kou Lingling was added, followed by addition of sulfuric acid adjusted to pH 4 石. After uniformly mixing the cerium-containing aluminum oxide compound (7 〇〇g), the nozzle is dried by mist, and then the mineral is removed by washing to obtain an additive 平均 having an average particle diameter of 60. Table 4 shows the composition and properties of the additive 13. [Comparative Example 6: Additive 14] In the test type of vaporized aluminum solution b858g (containing 200 g of alumina), adding 600 g of Ringing soil was added, followed by addition of sulfuric acid to pH 4. The sulphuric acid compound A1430g (containing After the bismuth aluminum oxide compound 2〇〇g) is uniformly mixed, the nozzle is sprayed and dried, and then the mineral is removed by washing to obtain an additive u having an average particle diameter of 60/ζπ. Table 4 shows the composition and properties of the additive 14. [Comparative Example 7: Additive 15] In a basic type of vaporized aluminum solution b858g (containing 200 g of alumina), 矽 〇 sulfuric acid was adjusted to pH 4.0 矽 aluminoxy compound A571 〇g (containing Shi Xi Shao oxygen) Compound 800g) was uniformly mixed and then "spray-dried, followed by washing to remove the stone quality" to obtain an additive 15 having an average particle size of 60# m. Table 4 shows the composition and properties of the additive 15. 17 201130962 [Activity Evaluation] 添加Add the ship's 丨~〗 5 and evaluate the impact on additive properties. Feed 4 is in the respective filaments. ^ For the live according to Table 4 'Oxidation!g sol binder is also the same as the oxidized sol sol binder. The amount of solid acid in the field is 0.1~〇.4mmol/g. As the amount of solid acid increases, the cracking efficiency of heavy oil is increased, HC(10) Reduced, good job results, but when the amount of solid acid is o.G7mm (Dl / g, the cracking efficiency of heavy oil points increased, hc retort increases, when the amount of solid acid is 〇5mm〇l / g, coke yield [Table 4] Example 6 Example 7 Example 8 Comparative Example 6 Comparative Example 7 Additive 11 Additive 12 Additive 13 Additive 14 Additive 15 Composition binder (cerium oxide) Mass% 20 20 20 20 20 Kaolin mass% 50 30 10 60 矽 aluminum oxide mass% 30 50 70 20 80 Properties _ bulk density ml/g 0.80 0.75 0.70 0.82 0.65 specific surface area m2/g 100 210 280 90 310 total solid acid amount mmol/g 0.10 0.30 0.40 0.07 0.50 strong acid amount / Total solid acid amount % 0 0 0 0 0 Activity evaluation conversion mass % +0.1 +0.3 +0.5 +0.1 +0.8 Gasoline mass% +0.1 +0.3 +0.4 ±0 +0.4 LCO mass% +0.2 +0.4 +0.7 +0.1 +0.8 HCO mass% -0.3 -0.4 -0.7 -0.1 -0.8 Mass % ±〇1 +0. 1^ +0.1 ±0 +0.3 18 201130962 "Test Example 5: Effect of specific surface area" [Example 9: Additive 16] B858g in a basic vaporized aluminum solution (containing alumina 2〇 In the illusion, 100 g of kaolin was added, followed by adding a slurry of A2860 g (containing 400 g of lanthanum aluminide) and 300 g of super-anhydrogenated γ-type zeolite adjusted to pH 4 with sulfuric acid, followed by spray drying, followed by borrowing. The minerals were washed to obtain an additive 16 having an average particle diameter of 60/zm. The composition and properties of the additive are shown in Table 5. [Comparative Example 8: Additive 17] b858g in a basic aluminum chloride solution (containing alumina 2〇) 〇g), adding 100 g of kaolin, followed by adding a sulphuric acid-adjusted sulphur-aluminum sulphide slurry A1430g (containing yttrium aluminum oxide compound 2 〇〇g) and super-anti-defying gamma-type zeolite 5 〇〇g homogenous mixture After the spray drying, the mineral was removed by washing to obtain an additive 17 having an average particle diameter of 60 #m. The composition and properties of the additive 17 are shown in Table 5. [Evaluation of Activity] Using Additive 11, Additive 13, and Additive 14 , Additives 16 and Additives 17, to assess the ratio table Impact on the activity of the product. Table 5 shows the respective evaluation results. Further, regarding the additive 17', it was difficult to use the actual device because the bulk density was low, and no activity evaluation was performed. According to Table 5, when the specific surface area is 1〇〇~35〇m2/g, the reaction field with the heavy oil fraction is increased to lower the HCO yield, and good results are obtained, but when the specific surface area is 90 m2/g, the reaction field is less than HC〇. The yield increases when 4i〇m2/g, the expected reaction field? The heavy (four) points are efficiently lysed, but it is not practical due to the low bulk density of 19 201130962. [Table 5] Example 6 Example 8 Example 9 Comparative Example 6 Comparative Example 8 Additive 11 Additive 13 Add Qi J 16 Additive 14 Additive 17 Composition Dosing agent mass % (氡化矽) 20 20 20 20 20 Two-soil quality % 50 10 10 1 60 10 矽 aluminum oxide mass% 30 70 40 20 20 zeolite mass % - - 30 a 50 nature
如上，本發明之流動觸媒裂解觸媒用添加劑，可將原 料油中之重_分有效地贿，且抑織炭產率，以高產 率製得汽油及1X0。該添加_徵為比表面積高，_體 二中之強&比率低。-般而言強酸比率高則反應活性將提 南，但由於過度裂解反應進行而有焦炭產率提高 之問題 點。因^可知抑軸添加劑之總㈣酸中所占強酸之比 率，再藉由提高比表面積，使每單位表面積之_酸量降 低’而可抑縣_之過㈣解造·炭鮮之增加。 20 201130962 I：圖式簡單說明3 (無） 【主要元件符號說明】 (無） 21As described above, the additive for the catalytic catalyst for catalyzing the flow of the present invention can effectively bribe the weight of the raw material oil, and suppress the yield of the woven carbon, thereby producing gasoline and 1X0 at a high yield. The addition _ sign is high in specific surface area, and the ratio of strong & In general, a high acid ratio will increase the reactivity, but there is a problem that the coke yield is increased due to the excessive cleavage reaction. Since the ratio of the strong acid in the total (iv) acid of the axis-inhibiting additive is known, the amount of _acid per unit surface area is lowered by increasing the specific surface area, which can suppress the increase in the amount of carbon dioxide produced by the county. 20 201130962 I: Simple description of the diagram 3 (none) [Explanation of main component symbols] (None) 21