JP3737155B2 - Hydrocarbon catalytic cracking catalyst composition - Google Patents
Hydrocarbon catalytic cracking catalyst composition Download PDFInfo
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- JP3737155B2 JP3737155B2 JP06342195A JP6342195A JP3737155B2 JP 3737155 B2 JP3737155 B2 JP 3737155B2 JP 06342195 A JP06342195 A JP 06342195A JP 6342195 A JP6342195 A JP 6342195A JP 3737155 B2 JP3737155 B2 JP 3737155B2
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- rare earth
- earth metal
- zeolite
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- crystalline aluminosilicate
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- 239000003054 catalyst Substances 0.000 title claims description 63
- 239000000203 mixture Substances 0.000 title claims description 63
- 238000004523 catalytic cracking Methods 0.000 title claims description 31
- 229930195733 hydrocarbon Natural products 0.000 title claims description 28
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 155
- 239000010457 zeolite Substances 0.000 claims description 110
- 229910021536 Zeolite Inorganic materials 0.000 claims description 106
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 75
- 150000002910 rare earth metals Chemical group 0.000 claims description 48
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 39
- -1 rare earth metal ions Chemical class 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 22
- 239000011159 matrix material Substances 0.000 claims description 19
- 238000005342 ion exchange Methods 0.000 claims description 18
- 239000012013 faujasite Substances 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000011734 sodium Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical group N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、炭化水素接触分解用触媒組成物、特に重質炭化水素油の接触分解に使用して、優れた耐メタル性を有し、コークおよびガス分の生成が少なく、ガソリン留分や灯軽油留分などの液収率が高い接触分解用触媒組成物に関する。
【０００２】
【従来技術およびその問題点】
従来、結晶性アルミノシリケートゼオライト（ゼオライト）を多孔性母材物質中に分散させた構成の典型的な炭化水素接触分解用触媒組成物にあっては、予め希土類金属イオンでイオン交換した結晶性アルミノシリケートゼオライトを多孔性母材物質中に分散させたり、あるいは、当該触媒組成物に希土類成分を導入するなどして、触媒の性能向上が図られてきた。
前者の例としては、例えば特公昭５４−６５１９号公報に、（ａ）シリカのアルミナに対する比、約３．２〜７を有するフォージャサイト型ゼオライトを調製し、（ｂ）アンモニウム塩溶液による交換により、該ゼオライトのＮａ2Ｏ含量を約１．５〜４重量％まで減少させ、（ｃ）該ゼオライトをゼオライトの希土類又は金属の含量を約０．３〜１０重量％とするに充分な濃度の希土類又は金属の塩と接触させ、（ｄ）交換したゼオライトを約３７１℃（７００°Ｆ）〜８７１℃（１６００°Ｆ）の温度において約０．１〜３時間乾燥及び焼成し、（ｅ）アンモニウム塩溶液で交換してナトリウム含量を１重量％まで低下させ、（ｆ）該ゼオライトを洗浄、乾燥し、回収したゼオライトを無機マトリックス（多孔性母材物質）に分散させた接触クラッキング触媒組成物が記載されている。
【０００３】
しかし、前述の希土類金属イオンでイオン交換した希土類金属交換フォージャサイト型ゼオライトを多孔性母材物質中に分散させた触媒組成物は、耐熱性、耐水熱安定性が弱く、炭化水素の分解活性は高いもののガソリンや灯軽油留分（ＬＣＯ）の液収率が小さく、また、ガソリンのオクタン価が低いなどの欠点があった。
そこで、耐熱性、耐水熱安定に優れ、生成ガソリンのオクタン価が高い触媒組成物として、アンモニウム交換フォージャサイト型ゼオライトを水蒸気の存在下で焼成してゼオライトの骨格構造から脱アルミニウムした耐熱性、耐水熱安定性に優れた超安定性フォージャサイト型ゼオライト（ＵＳＹ）を多孔性母材物質中に分散させた触媒組成物が提案されている（例えば、特公昭４６−９１３２号）。
しかし、この様な触媒組成物も、接触分解の原料油にバナジウム、ニッケルなどを多量に含有する残渣油などの劣悪な重質炭化水素油を使用した場合には、生成ガソリンのオクタン価は高いものの、分解活性が低く、コーク及びガス分の生成量が大幅に増加し、耐メタル性に欠ける問題があった。
さらに、スチミング処理して得られた超安定性フォージャサイト型ゼオライト（ＵＳＹ）を希土類金属でイオン交換したゼオライト（ＲＥ交換ＵＳＹ）を使用した触媒組成物が提案されている。しかし、該触媒は分解活性は高いもののコークおよびガスの生成が多かった。
【０００４】
本出願人は、先に前述の問題を解決して、多量の金属汚染物を含有する劣悪な重質炭化水素油にも優れた性能を発揮する接触分解用触媒組成物の製造方法を提案した（特開昭６０−１９３５４３号公報）。該触媒組成物の製造方法は、バイヤー法で製造された水酸化アルミニウムを３５０〜７００℃の熱風と接触させて得られる気流焼成アルミナ、シリカとアルミナを主成分とする粘土、シリカ系無機酸化物の前駆物質及び結晶性アルミノシリケートからなる混合物の水性スラリーを噴霧乾燥して微小球状粒子を調製し、この粒子をアルカリ金属含有量が酸化物として１．０重量％以下になるまで洗浄した後、その粒子に希土類金属成分を導入することを特徴とする。
しかし、前述の方法で得られる触媒組成物もガソリン留分やＬＣＯ留分の液収率、コーク選択性などの点で改善の余地があった。
【０００５】
【発明の目的】
本発明の目的は、炭化水素、特に水素化処理した常圧残渣油などの重質炭化水素油の接触分解に使用して高い残油分解能を有し、ガソリン、灯軽油留分（ＬＣＯ）の収率が高く、コークおよびガスの生成が少ない新規な炭化水素接触分解用触媒組成物を提供することにある。
【０００６】
【発明の構成】
本発明の第１は、（１）フォージャサイト型結晶性アルミノシリケートゼオライトを希土類金属イオンでイオン交換して、イオン交換率が５〜７０％の範囲で希土類金属イオンを含有すると共に、ＮａイオンをＮａ ２ Ｏとして３〜６重量％含有する希土類金属交換結晶性アルミノシリケートゼオライトを水蒸気の存在下で焼成して得られた結晶性アルミノシリケートゼオライト５〜５０重量％を、（２）多孔性母材物質９５〜５０重量％中に分散してなることを特徴とする炭化水素接触分解用触媒組成物に関する。
本発明の第２は、（ｉ）フォージャサイト型結晶性アルミノシリケートゼオライトを希土類金属イオンおよびアンモニウムイオンでイオン交換して、イオン交換率が５〜７０％の範囲で希土類金属イオンを含有すると共に、ＮａイオンをＮａ ２ Ｏとして３〜６重量％含有する希土類金属交換結晶性アルミノシリケートゼオライトを水蒸気の存在下で焼成して得られた結晶性アルミノシリケートゼオライト５〜５０重量％を、（ ii ）多孔性母材物質９５〜５０重量％中に分散してなることを特徴とする炭化水素接触分解用触媒組成物に関する。
本発明の第３は、焼成後の結晶性アルミノシリケートゼオライトが、単位格子定数が２４．６５Å以下で、かつ骨格構造のＳｉＯ ２ ／Ａｌ ２ Ｏ ３ のモル比が６以上である請求項１または２記載の炭化水素接触分解用触媒組成物に関する。
本発明の第４は、フォージャサイト型結晶性アルミノシリケートゼオライトを希土類金属イオンまたは希土類金属イオンとアンモニウムイオンを含有する水溶液を用いてイオン交換して、イオン交換率が５〜７０％の範囲で希土類金属イオンを含有すると共に、ＮａイオンをＮａ ２ Ｏとして３〜６重量％含有する希土類金属交換結晶性アルミノシリケートゼオライトを水蒸気分圧０．０５ｋｇ／ｃｍ ２ 以上の水蒸気の存在下で、焼成温度４００〜９００℃で焼成し、該焼成した結晶性アルミノシリケートゼオライト５〜５０重量％を、多孔性母材物質９５〜５０重量％中に分散することを特徴とする請求項１ないし３いずれか記載の炭化水素接触分解用触媒組成物の製造法に関する。
以下に本発明について具体的に説明する。
本発明の出発材料のフォージャサイト型結晶性アルミノシリケートゼオライト（ゼオライト）は、天然および合成ゼオライトを用いることができ、通常、Ｎａ２Ｏとして約１０〜１４重量％のナトリウムを含有する状態で、約３〜６のＳｉO２／Ａｌ２Ｏ３モル比を有し、２４．６５Åよりも大きい単位格子定数を有する。また、このようなゼオライトをアンモニウムイオンでイオン交換したナトリウム−アンモニウム形、アンモニウム形、あるいはこれらを焼成した水素形のゼオライトを出発材料として用いることができる。
本発明では、前述のゼオライト出発材料を希土類金属イオンと部分的にイオン交換する。なお、イオン交換は通常の方法により行うことができる。また、希土類金属としては、例えば周期律表のランタノイド元素の１種または２種以上の金属で、ランタン、セリウム、プラセオジム、ネオジウムなどが挙げられる。
【０００７】
出発材料にナトリウム形ゼオライトを用いる場合には、希土類金属イオンとアンモニウムイオンを含有する水溶液を用いて、生成希土類交換ゼオライトは、ナトリウムがＮａ2Ｏとして６重量％以下、好ましくは３〜６重量％の範囲となるようにイオン交換することが望ましい。Ｎａ2Ｏの量が６重量％よりも多いゼオライトでは、水蒸気の存在下で焼成した際に、得られるゼオライトの単位格子定数の低下が起こりにくい傾向にある。また、出発材料にナトリウム−アンモニウム形ゼオライトを用いる場合にも、Ｎａ2Ｏの含有量が前述の範囲にあるゼオライトを用いて希土類金属イオン交換することが望ましい。
【０００８】
本発明での生成希土類交換ゼオライトは、希土類金属交換率が５〜７０％の範囲であることが好ましい。希土類交換率が５％よりも小さい場合には得られる触媒組成物は、所望の効果が得られ難い。また希土類交換率が７０％よりも高い場合には生成ガソリンのオクタン価が低下する傾向にある。好ましい希土類金属交換率は、１０〜６０％の範囲である。水蒸気の存在下で焼成した際に、最良の結果を得る生成希土類金属交換ゼオライトは、希土類金属交換率が１０〜６０％の範囲にあり、Ｎａ2Ｏを３〜６重量％含有するものである。この様なゼオライトを水蒸気の存在下で焼成して得られたゼオライトは、結晶の破壊が少なく、単位格子定数（ＵＤ）の低下が大きく、また、耐水熱安定性、耐酸性に優れており、得られる触媒組成物は所望の優れた効果を有する。
【０００９】
本発明は、前述の生成希土類交換ゼオライトを水蒸気の存在下で焼成することが重要である。該ゼオライトを水蒸気が存在しない雰囲気下で焼成した場合には、得られる触媒組成物は、所望の効果が得られない。焼成中における水蒸気分圧は０．０５ｋｇ／ｃｍ2以上、好ましくは０．１〜１．２ｋｇ／ｃｍ2の範囲であることが望ましい。水蒸気分圧が０．０５ｋｇ／ｃｍ2より小さい場合には、得られるゼオライトは、結晶度が低下し、所望の効果が得られない場合がある。また、１．２ｋｇ／ｃｍ2を越えると、結晶度が低下する傾向にある。生成希土類交換ゼオライトは、焼成温度が４００〜９００℃、好ましくは５００〜８００℃の範囲で、得られたゼオライトのＵＤの値が２４．６５Å以下となるに十分な時間、通常０．５〜１０時間、焼成されることが望ましい。
焼成して得られたゼオライトは、ＵＤの値が２４．６５Å以下、好ましくは２４．６５〜２４．５０Åの範囲で、ゼオライト骨格構造のＳｉＯ2／Ａｌ2Ｏ3モル比が６以上、好ましくは６〜９の範囲にあり、結晶化度が７０％以上、好ましくは８０％以上であることが望ましい。ゼオライトのＵＤ値が２４．６５Åより大きい場合には、耐熱性、耐水熱安定性などが改善されず、また２４．５０Åよりも小さい場合には、触媒の分解活性が低下する傾向にある。
【００１０】
本発明の炭化水素接触分解用触媒組成物は、前述のゼオライトを多孔性母材物質中に分散したものである。該多孔性母材物質としては、通常の炭化水素接触分解用触媒組成物に使用されるものを用いることができる。具体的には、シリカ、シリカ−アルミナ、アルミナ、シリカ−マグネシア、アルミナ−マグネシア、リン−アルミナ、シリカ−ジルコニア、シリカ−マグネシア−アルミナなど結合剤として作用する慣用の多孔性母材物質である。このような多孔性母材物質には、カオリン、ハロイサイト、モンモリロナイトなどの粘土やカルシウムアルミネートなどの金属捕捉剤なども含有する。
本発明の触媒組成物では、前述の焼成して得られた結晶性アルミノシリケートゼオライトは５〜５０重量％、好ましくは１０〜４０重量％の範囲で、多孔性母材物質は９５〜５０重量％、好ましくは９０〜６０重量％の範囲で含有することが望ましい。
本発明の触媒組成物では、前述の生成希土類交換ゼオライトを水蒸気の存在下で焼成して得られたゼオライトと、多孔性母材物質の前駆体とを均一に混合し、得られた混合物を噴霧乾燥して微小球状粒子とし、所望により洗浄、乾燥、焼成して得られる。また、必要に応じて該微小球状粒子に希土類成分を導入することも可能である。また、本発明の触媒組成物は、通常の炭化水素の接触分解方法にて使用可能である。
【００１１】
以下に実施例を示しさらに本発明を具体的に説明する。
【実施例】
実施例−１
シリカ／アルミナ モル比が５．０、ＵＤ値が２４．７０Åのフォージャサイト型ゼオライト（ＮａＹ）５．０ｋｇ（乾燥基準）に水４０ｋｇを加えて懸濁スラリーにした。この懸濁スラリーを６０℃に加温した後、濃度約１００％の硫酸アンモニウム２，４８２ｇを加え、更にＬａ、Ｃｅを主成分とする希土類金属塩化物をゼオライト単位重量あたりＲＥ2Ｏ3換算で３０重量％に相当する量を添加した。次いで３５％塩酸水溶液で懸濁スラリーのｐＨを５．５に調整して６０℃で１時間熟成を行ってアンモニウム交換と希土類金属交換を同時に行った。
該熟成スラリーを濾過し、ゼオライト量に対して１０倍量の６０℃温水を掛けて洗浄し、その後１２０℃で１６時間乾燥して希土類交換ゼオライト（Ａ−３）を得た。この希土類交換ゼオライト（Ａ−３）は、希土類交換率が３０％で、Ｎａ2Ｏを４．９重量％含有し、結晶化度が１００％であった。
該希土類交換ゼオライトを直径１ｍｍ以下に粉砕した後、回転焼成炉に４ｋｇ（乾燥基準）投入し、次の様にして水蒸気の存在下に焼成した。回転焼成炉の温度を徐々に昇温し、炉内の温度が３５０℃に達した所で水蒸気分圧が０．２ｋｇ／ｃｍ2の雰囲気になる様に水を添加開始し、６５０℃まで２時間で昇温し、更に６５０℃で２０分間保持した。得られたゼオライト（Ｂ−３）は、ゼオライト骨格構造のシリカ／アルミナ モル比が７．５で、ＵＤ値が２４．６３Å、結晶化度が６７％であった。
【００１２】
一方、濃度２５ｗｔ％硫酸にＳｉＯ2濃度１２．７３ｗｔ％の水硝子溶液を徐々に添加してｐＨ１．８とし、ＳｉＯ2濃度で９．９ｗｔ％のシリカヒドロゾルを調製した。このシリカヒドロゾルに、前述のゼオライト（Ｂ−３）を固形分濃度で３３ｗｔ％となる様に水に懸濁してコロイドミルを通し均質化した後、スラリーのｐＨを３．９に調整して最終触媒組成物でのゼオライト量が３０ｗｔ％となる様に添加し、同時に最終触媒組成物での量が５０ｗｔ％となる様にカオリンを添加して、混合物スラリーを調製した。
この混合物スラリーを噴霧乾燥して平均粒子径６０μｍの微小球状粒子を得た。
得られた微小球状粒子を６０℃の温水に懸濁して５分間撹拌した後、濾過、洗浄した。さらにこの微小球状粒子を濃度１０ｗｔ％硫酸アンモニウム溶液に再度懸濁し、６０℃で２０分間撹拌した後、濾過、洗浄してアルカリ分を除去し、乾燥して触媒組成物（Ｃ−３）を調製した。この触媒組成物（Ｃ−３）の性状を表２に示す。
【００１３】
前述の希土類金属交換ゼオライトの製造法において、ゼオライト単位重量あたりの希土類塩化物の量をＲＥ2Ｏ3換算で、それぞれ（１０、２０、５０ｗｔ％に相当する量を使用した以外は、同様にして希土類交換ゼオライト（Ａ−１）、（Ａ−２）、（Ａ−４）を調製した。それぞれの希土類交換ゼオライトの性状を表１に示す。また、これらの希土類交換ゼオライトを前述の焼成方法と同様にして水蒸気の存在下に焼成した。得られたそれぞれのゼオライト（Ｂ−１）、（Ｂ−２）、（Ｂ−４）の性状を表１に示す。
次に、これらのゼオライトを用いて前述の方法と同様にして、それぞれ触媒組成物（Ｃ−１）、（Ｃ−２）、（Ｃ−４）を調製した。それぞれ触媒組成物の性状を表２に示す。
【００１４】
実施例−２
実施例−１で調製した触媒組成物（Ｃ−３）の一部１．０ｋｇを、温水４．４ｋｇに懸濁し、この懸濁液に希土類金属塩化物をＲＥ2Ｏ3換算で触媒組成物の２．５ｗｔ％に相当する量添加し、次いで濃度２０ｗｔ％塩酸でｐＨ５．５に調製し、温度６０℃で２０分間撹拌して、希土類金属を触媒に導入した。その後、濾過、洗浄、乾燥して触媒組成物（Ｃ−５）を調製した。触媒組成物（Ｃ−５）の性状を表３に示す。
【００１５】
比較例−１
実施例−１で使用したＮａＹ ５．０ｋｇ（乾燥基準）に水４０ｋｇを加えて懸濁スラリーにした。この懸濁スラリーを６０℃に加温した後、濃度約１００％の硫酸アンモニウム２４８２ｇを加えた。次いで、２５ｗｔ％硫酸水溶液で懸濁スラリーのｐＨを４．５に調整して、更に８０℃に加温して１時間保持してアンモニウムイオン交換を行った。このゼオライトは、濾過、洗浄した後再度水に懸濁し、この懸濁スラリーに希土類塩化物をＲＥ2Ｏ3換算でゼオライト単位重量あたり６７重量％に相当する量添加し、更に３５％塩酸水溶液で懸濁スラリーのｐＨを５．５に調整して６０℃で１時間熟成を行って、希土類交換した。
該熟成スラリーを濾過、洗浄し、その後１２０℃で１６時間乾燥して希土類交換ゼオライト（Ａ−６）を得た。該希土類交換ゼオライト（Ａ−６）の性状を表１に示す。ゼオライト（Ａ−６）を直径１ｍｍ以下に粉砕した後、箱型の電気炉にて空気中で５５０℃で３時間焼成して希土類交換ゼオライト（Ｂ−６）を得た。その性状を表１に示す。このゼオライト（Ｂ−６）を使用して、実施例−１の方法と同様にして触媒組成物（Ｃ−６）を調製した。触媒組成物（Ｃ−６）の性状を表３に示す。
【００１６】
比較例−２
実施例−１で使用したＮａＹ ５．０ｋｇ（乾燥基準）に水４０ｋｇを加えて懸濁スラリーにした。この懸濁スラリーを６０℃に加温した後、濃度約１００％の硫酸アンモニウム２４８２ｇを加えた。次いで、２５ｗｔ％硫酸水溶液で懸濁スラリーのｐＨを４．５に調整して、更に８０℃に加温して１時間保持してアンモニウムイオン交換を行った。このゼオライトは、濾過、洗浄し、その後１２０℃で１６時間乾燥してアンモニウム交換率が７０％のゼオライトを得た。
このゼオライトを直径１ｍｍ以下に粉砕した後、実施例−１の方法と同様にして水蒸気の存在下に焼成した。焼成して得られた超安定性ゼオライト（Ａ−７）の性状を表１に示す。
【００１７】
この超安定性ゼオライト（Ａ−７）３．０ｋｇ（乾燥基準）を水２４ｋｇに懸濁し、６０℃に加温し、次いでこの懸濁スラリーに希土類塩化物をＲＥ2Ｏ3換算でゼオライト単位重量あたり３０重量％に相当する量を加え、更に２０％塩酸水溶液で懸濁スラリーのｐＨを５．５に調整して、更に６０℃で１時間熟成を行って希土類交換した。
該熟成スラリーを濾過、洗浄し、その後１２０℃で１６時間乾燥して希土類交換ゼオライトを得た。この希土類交換ゼオライトを直径１ｍｍ以下に粉砕した後、電気炉にて空気中で５５０℃で３時間焼成して希土類交換ゼオライト（Ｂ−７）を得た。その性状を表１に示す。このゼオライト（Ｂ−７）を使用して実施例−１の方法と同様にして触媒組成物（Ｃ−７）を調製した。触媒組成物（Ｃ−７）の性状を表３に示す。
【００１８】
比較例−３
比較例−２の超安定性ゼオライト（Ａ−７）と全く同様にして調製したゼオライトを使用して実施例−１の方法と同様にして触媒組成物（Ｃ−８）を調製した。その性状を表３に示す。
【００１９】
比較例−４
比較例−３で調製した触媒組成物（Ｃ−８）の一部を使用して、実施例−２と同様の方法で希土類金属を触媒に導入した触媒組成物（Ｃ−９）を調製した。その性状を表３に示す。
【００２０】
実施例−３（性能評価試験）
実施例１、２および比較例１〜４で調製した触媒組成物Ｃ−１〜Ｃ−９について性能評価試験を行った。
性能評価試験は、それぞれの触媒組成物約２００ｇを空気中で６００℃−２時間焼成した試料にナフテン酸ニッケルとナフテン酸バナジウムを均等にＶ＋Ｎｉとして１０，０００ｐｐｍ含むベンゼン溶液を含浸し、次いで減圧下でベンゼンを除去した後、６００℃で２時間焼成し、更に１００％水蒸気雰囲気中で７３２℃で１７時間処理して擬平衡化した触媒を使用して行った。
接触分解反応は原料油に水素化処理した減圧軽油（ＤＳＶＧＯ）を用いて次の反応条件で行った。
反応条件
反応温度 ５００℃
空間速度 １６ｈｒ-1
触媒／油比 ３ｗｔ／ｗｔ
評価結果を表４、表５に示す。本発明の触媒組成物は転化率が高く、しかもガソリン、灯軽油留分（ＬＣＯ）の収率が高く、水素、コークの生成が少ない。
【００２１】
【表１】
【表２】
【表３】
【表４】
【表５】
以下、本発明の具体的実施態様を示す。
１．フォージャサイト型結晶性アルミノシリケートゼオライトを希土類金属イオンでイオン交換した希土類交換結晶性アルミノシリケートゼオライトを水蒸気の存在下で焼成して得られた結晶性アルミノシリケートゼオライトを、多孔性母材物質中に分散してなる炭化水素接触分解用触媒組成物。
２．フォージャサイト型結晶性アルミノシリケートゼオライトを希土類金属イオンおよびアンモニウムイオンでイオン交換した希土類金属およびアンモニウム交換結晶性アルミノシリケートゼオライトを水蒸気の存在下で焼成して得られた結晶性アルミノシリケートゼオライトを、多孔性母材物質中に分散してなる炭化水素接触分解用触媒組成物。
３．焼成した結晶性アルミノシリケートゼオライトが、焼成温度４００〜９００℃で焼成されたものである前記第１または２の炭化水素接触分解用触媒組成物。
４．希土類交換結晶性アルミノシリケートゼオライトまたは希土類金属およびアンモニウム交換結晶性アルミノシリケートゼオライトが、希土類イオン交換率が５〜７０％、好ましくは１０〜６０％、また、ＮａイオンをＮａ2Ｏとして６重量％以下、好ましくは３〜６重量％を含有する前記第１、２または３の炭化水素接触分解用触媒組成物。
【００２７】
５．焼結後の結晶性アルミノシリケートゼオライトが、単位格子定数が２４．６５Å以下、好ましくは２４．６５〜２４．５０Å、骨格構造のＳｉＯ2／Ａｌ2Ｏ3のモル比が６以上、好ましくは６〜９、かつ結晶化度が７０％以上、好ましくは８０％以上である前記第１ないし４の炭化水素接触分解用触媒組成物。
６．焼成して得られた結晶性アルミノシリケートゼオライトを５〜５０重量％、好ましくは１０〜４０重量％、かつ多孔性母材物質を９５〜５０重量％、好ましくは９０〜６０重量％を含有するものである前記第１ないし５の炭化水素接触分解用触媒組成物。
７．フォージャサイト型結晶性アルミノシリケートゼオライトを希土類金属イオンまたは希土類金属イオンとアンモニウムイオンを含有する水溶液を用いてイオン交換し、該イオン交換した結晶性アルミノシリケートゼオライトを水蒸気分圧０．０５ｋｇ／ｃｍ2以上の水蒸気の存在下で、焼成温度４００〜９００℃で焼成し、該焼成した結晶性アルミノシリケートゼオライトを、多孔性母材物質中に分散することを特徴とする前記第１ないし６の炭化水素接触分解用触媒組成物の製造法。
【００２８】
【発明の効果】
本発明によると、炭化水素油、特に重質炭化水素油の接触分解に使用して、優れた耐メタル性を有し、コークおよびガス分の生成が少なく、ガソリン留分や灯軽油留分などの液収率が高い接触分解用触媒組成物が提供される。[0001]
[Industrial application fields]
The present invention is a catalytic composition for catalytic cracking of hydrocarbons, particularly for catalytic cracking of heavy hydrocarbon oils, has excellent metal resistance, produces little coke and gas, and produces gasoline fractions and lamps. The present invention relates to a catalytic cracking catalyst composition having a high liquid yield such as a light oil fraction.
[0002]
[Prior art and its problems]
Conventionally, in a catalyst composition for catalytic catalytic cracking of a structure in which a crystalline aluminosilicate zeolite (zeolite) is dispersed in a porous matrix material, the crystalline alumino previously ion-exchanged with rare earth metal ions is used. Improvements in catalyst performance have been achieved by dispersing silicate zeolite in a porous matrix material or introducing a rare earth component into the catalyst composition.
As an example of the former, for example, Japanese Patent Publication No. 54-6519 discloses (a) a faujasite type zeolite having a silica to alumina ratio of about 3.2 to 7, and (b) exchange with an ammonium salt solution. Reducing the Na 2 O content of the zeolite to about 1.5-4% by weight, and (c) a concentration sufficient to bring the rare earth or metal content of the zeolite to about 0.3-10% by weight. (D) drying and calcining the exchanged zeolite at a temperature of about 371 ° C. (700 ° F.) to 871 ° C. (1600 ° F.) for about 0.1 to 3 hours; ) Exchange with ammonium salt solution to reduce sodium content to 1% by weight, (f) Wash and dry the zeolite and disperse the recovered zeolite in an inorganic matrix (porous matrix material). Catalytic cracking catalyst compositions are described.
[0003]
However, the catalyst composition in which the rare earth metal exchanged faujasite-type zeolite ion-exchanged with the rare earth metal ions described above is dispersed in the porous matrix material has poor heat resistance and hydrothermal stability, and hydrocarbon decomposition activity. However, the liquid yield of gasoline and kerosene oil fraction (LCO) is small, and the octane number of gasoline is low.
Therefore, as a catalyst composition having excellent heat resistance and hydrothermal stability, and having a high octane number of the produced gasoline, ammonium-exchanged faujasite-type zeolite is calcined in the presence of water vapor and dealuminated from the framework structure of the zeolite. A catalyst composition in which ultra-stable faujasite type zeolite (USY) having excellent thermal stability is dispersed in a porous matrix material has been proposed (for example, Japanese Examined Patent Publication No. 46-9132).
However, even when such a catalyst composition uses poor heavy hydrocarbon oils such as residual oils containing a large amount of vanadium, nickel, etc. as the feedstock for catalytic cracking, the octane number of the gasoline produced is high. However, the decomposition activity is low, the amount of coke and gas produced is greatly increased, and there is a problem of lack of metal resistance.
Furthermore, a catalyst composition using a zeolite (RE exchange USY) obtained by ion exchange of a superstable faujasite type zeolite (USY) obtained by a steaming treatment with a rare earth metal has been proposed. However, although the catalyst had high cracking activity, it produced much coke and gas.
[0004]
The present applicant has previously proposed a method for producing a catalytic cracking catalyst composition that solves the above-described problems and exhibits excellent performance even in poor heavy hydrocarbon oils containing a large amount of metal contaminants. (Japanese Unexamined Patent Publication No. 60-193543). The catalyst composition is produced by air-flow calcined alumina obtained by contacting aluminum hydroxide produced by the Bayer method with hot air at 350 to 700 ° C., clay containing silica and alumina as main components, and silica-based inorganic oxide. After spray-drying an aqueous slurry of a mixture consisting of the precursor and crystalline aluminosilicate to prepare microspherical particles, the particles were washed until the alkali metal content was 1.0% by weight or less as an oxide, A rare earth metal component is introduced into the particles.
However, the catalyst composition obtained by the above-described method has room for improvement in terms of the liquid yield of gasoline fraction and LCO fraction, coke selectivity, and the like.
[0005]
OBJECT OF THE INVENTION
The object of the present invention is to use in catalytic cracking of hydrocarbons, particularly heavy hydrocarbon oils such as hydrotreated atmospheric pressure residue oils, and has a high residual oil resolution, which can be used for gasoline, kerosene oil fraction (LCO). It is an object of the present invention to provide a novel hydrocarbon catalytic cracking catalyst composition having a high yield and low coke and gas production.
[0006]
[Structure of the invention]
The first of the present invention is (1) ion exchange of faujasite type crystalline aluminosilicate zeolite with rare earth metal ions, and the rare earth metal ions are contained within an ion exchange rate of 5 to 70%, and Na ions 5 to 50% by weight of a crystalline aluminosilicate zeolite obtained by calcining rare earth metal exchanged crystalline aluminosilicate zeolite containing 3 to 6% by weight of Na 2 O in the presence of water vapor, and (2) a porous matrix The present invention relates to a catalyst composition for catalytic cracking of hydrocarbons characterized by being dispersed in 95 to 50% by weight of a material substance.
The second aspect of the present invention includes (i) ion exchange of a faujasite type crystalline aluminosilicate zeolite with rare earth metal ions and ammonium ions, and the rare earth metal ions are contained within an ion exchange rate of 5 to 70%. 5 to 50% by weight of a crystalline aluminosilicate zeolite obtained by calcining a rare earth metal-exchanged crystalline aluminosilicate zeolite containing 3 to 6% by weight of Na ions as Na 2 O in the presence of water vapor, ( ii ) The present invention relates to a catalyst composition for catalytic catalytic cracking of hydrocarbon, which is dispersed in 95 to 50% by weight of a porous matrix material.
According to a third aspect of the present invention, the crystalline aluminosilicate zeolite after calcination has a unit cell constant of 24.65% or less and a SiO 2 / Al 2 O 3 molar ratio of a framework structure of 6 or more. The catalyst composition for catalytic cracking of hydrocarbon according to 2.
In the fourth aspect of the present invention, the faujasite type crystalline aluminosilicate zeolite is ion-exchanged using an aqueous solution containing rare earth metal ions or rare earth metal ions and ammonium ions, and the ion exchange rate is in the range of 5 to 70%. A rare earth metal-exchanged crystalline aluminosilicate zeolite containing rare earth metal ions and containing 3 to 6% by weight of Na ions as Na 2 O in the presence of water vapor having a water vapor partial pressure of 0.05 kg / cm 2 or more is calcining temperature. The calcined crystalline aluminosilicate zeolite is calcined at 400 to 900 ° C, and 5 to 50 wt% of the calcined crystalline aluminosilicate zeolite is dispersed in 95 to 50 wt% of the porous matrix material. The present invention relates to a process for producing a catalytic composition for catalytic cracking of hydrocarbons.
The present invention will be specifically described below.
The starting material faujasite type crystalline aluminosilicate zeolite (zeolite) of the present invention can use natural and synthetic zeolites, usually containing about 10 to 14% by weight sodium as Na 2 O, having about 3-6 SiO 2 / Al 2 O 3 molar ratio has a larger unit cell constant than 24.65A. In addition, a sodium-ammonium form obtained by ion exchange of such zeolite with ammonium ions, an ammonium form, or a hydrogen form zeolite obtained by calcining these can be used as a starting material.
In the present invention, the aforementioned zeolite starting material is partially ion exchanged with rare earth metal ions. In addition, ion exchange can be performed by a normal method. Examples of the rare earth metal include one or more of lanthanoid elements in the periodic table, such as lanthanum, cerium, praseodymium, and neodymium.
[0007]
When sodium-type zeolite is used as a starting material, an aqueous solution containing rare earth metal ions and ammonium ions is used, and the resulting rare earth exchanged zeolite has a sodium content of Na 2 O of 6% by weight or less, preferably 3 to 6% by weight. It is desirable to ion-exchange so that it may become the range of this. When the amount of Na 2 O is more than 6% by weight, the unit cell constant of the resulting zeolite tends not to decrease when calcined in the presence of water vapor. Also, when sodium-ammonium type zeolite is used as a starting material, it is desirable to perform rare earth metal ion exchange using a zeolite whose Na 2 O content is in the above range.
[0008]
The rare earth exchanged zeolite produced in the present invention preferably has a rare earth metal exchange rate in the range of 5 to 70%. When the rare earth exchange rate is less than 5%, the obtained catalyst composition is difficult to obtain a desired effect. When the rare earth exchange rate is higher than 70%, the octane number of the produced gasoline tends to decrease. A preferable rare earth metal exchange rate is in the range of 10 to 60%. Upon firing in the presence of water vapor, generated rare earth metal exchanged zeolite to obtain the best results, in the range rare earth metal exchange ratio is 10 to 60%, those containing 3 to 6 wt% of Na 2 O . Zeolite obtained by calcining such zeolite in the presence of water vapor has little crystal breakage, a large decrease in unit cell constant (UD), and is excellent in hydrothermal stability and acid resistance. The resulting catalyst composition has the desired superior effects.
[0009]
In the present invention, it is important to calcine the produced rare earth exchanged zeolite in the presence of water vapor. When the zeolite is calcined in an atmosphere in which water vapor does not exist, the desired effect cannot be obtained in the obtained catalyst composition. Water vapor partial pressure in the firing 0.05 kg / cm 2 or more, it is desirable that preferably in the range of 0.1~1.2kg / cm 2. When the water vapor partial pressure is smaller than 0.05 kg / cm 2 , the obtained zeolite has a reduced crystallinity, and the desired effect may not be obtained. On the other hand, if it exceeds 1.2 kg / cm 2 , the crystallinity tends to decrease. The produced rare earth exchanged zeolite has a calcining temperature in the range of 400 to 900 ° C., preferably in the range of 500 to 800 ° C., and a time sufficient for the UD value of the obtained zeolite to be 24.65% or less, usually 0.5 to 10 ° C. It is desirable to be fired for hours.
The zeolite obtained by calcining has a UD value of 24.65% or less, preferably 24.65 to 24.50%, and a SiO 2 / Al 2 O 3 molar ratio of the zeolite framework structure of 6 or more, preferably It is in the range of 6 to 9, and the crystallinity is 70% or more, preferably 80% or more. When the UD value of the zeolite is larger than 24.65%, the heat resistance and hydrothermal stability are not improved, and when it is smaller than 24.50%, the decomposition activity of the catalyst tends to decrease.
[0010]
The catalyst composition for catalytic catalytic cracking of the present invention is obtained by dispersing the aforementioned zeolite in a porous matrix material. As the porous base material, those used in usual catalyst compositions for catalytic catalytic cracking of hydrocarbons can be used. Specifically, it is a conventional porous matrix material that acts as a binder, such as silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina. Such a porous matrix material contains clay such as kaolin, halloysite, montmorillonite, and a metal scavenger such as calcium aluminate.
In the catalyst composition of the present invention, the crystalline aluminosilicate zeolite obtained by the above-mentioned calcination is 5 to 50% by weight, preferably 10 to 40% by weight, and the porous matrix material is 95 to 50% by weight. It is desirable to contain in the range of 90 to 60% by weight.
In the catalyst composition of the present invention, the zeolite obtained by calcining the above-described rare earth-exchanged zeolite in the presence of water vapor and the precursor of the porous matrix material are uniformly mixed, and the resulting mixture is sprayed. It is obtained by drying to form fine spherical particles, and washing, drying and firing as desired. It is also possible to introduce a rare earth component into the microspherical particles as necessary. Further, the catalyst composition of the present invention can be used in an ordinary hydrocarbon catalytic cracking method.
[0011]
The following examples further illustrate the present invention.
【Example】
Example-1
40 kg of water was added to 5.0 kg (dry basis) of faujasite type zeolite (NaY) having a silica / alumina molar ratio of 5.0 and a UD value of 24.70 kg to form a suspended slurry. After this suspension slurry is heated to 60 ° C., 2,482 g of ammonium sulfate having a concentration of about 100% is added, and further, rare earth metal chloride mainly composed of La and Ce is converted to 30 in terms of RE 2 O 3 per unit weight of the zeolite. An amount corresponding to% by weight was added. Subsequently, the pH of the suspension slurry was adjusted to 5.5 with a 35% hydrochloric acid aqueous solution, and aging was performed at 60 ° C. for 1 hour to perform ammonium exchange and rare earth metal exchange at the same time.
The aged slurry was filtered, washed with 60 ° C. hot water of 10 times the amount of zeolite, and then dried at 120 ° C. for 16 hours to obtain rare earth exchanged zeolite (A-3). The rare earth exchanged zeolite (A-3) had a rare earth exchange rate of 30%, contained 4.9% by weight of Na 2 O, and had a crystallinity of 100%.
After the rare earth exchanged zeolite was pulverized to a diameter of 1 mm or less, 4 kg (dry basis) was charged in a rotary calciner and calcined in the presence of water vapor as follows. The temperature of the rotating calciner temperature was gradually raised, the temperature of water as the water vapor partial pressure is the atmosphere of 0.2 kg / cm 2 was started added at reaching 350 ° C. in the furnace 2 to 650 ° C. The temperature was raised over time, and the temperature was further maintained at 650 ° C. for 20 minutes. The obtained zeolite (B-3) had a silica / alumina molar ratio of the zeolite framework structure of 7.5, a UD value of 24.63%, and a crystallinity of 67%.
[0012]
Meanwhile, a silica hydrosol having a SiO 2 concentration of 9.9 wt% was prepared by gradually adding a water glass solution having a SiO 2 concentration of 12.73 wt% to 25 wt% sulfuric acid to adjust the pH to 1.8. In this silica hydrosol, the above-mentioned zeolite (B-3) is suspended in water to a solid content concentration of 33 wt%, homogenized through a colloid mill, and then the pH of the slurry is adjusted to 3.9. A mixture slurry was prepared by adding so that the amount of zeolite in the final catalyst composition was 30 wt%, and simultaneously adding kaolin so that the amount in the final catalyst composition was 50 wt%.
This mixture slurry was spray-dried to obtain fine spherical particles having an average particle size of 60 μm.
The obtained microspherical particles were suspended in 60 ° C. warm water, stirred for 5 minutes, filtered and washed. Further, the fine spherical particles were suspended again in a 10 wt% ammonium sulfate solution, stirred at 60 ° C. for 20 minutes, filtered, washed to remove the alkali, and dried to prepare a catalyst composition (C-3). . Table 2 shows the properties of the catalyst composition (C-3).
[0013]
In the above-described method for producing rare earth metal-exchanged zeolite, the amount of rare earth chloride per unit weight of zeolite was converted in the same manner as RE 2 O 3 except that amounts corresponding to 10, 20, and 50 wt% were used. Rare earth exchanged zeolites (A-1), (A-2), and (A-4) were prepared, and the properties of each rare earth exchanged zeolite are shown in Table 1. These rare earth exchanged zeolites were prepared by the above-described calcination method. The properties of the obtained zeolites (B-1), (B-2), and (B-4) are shown in Table 1.
Next, using these zeolites, catalyst compositions (C-1), (C-2), and (C-4) were prepared in the same manner as described above. Table 2 shows the properties of the catalyst compositions.
[0014]
Example-2
A portion of 1.0 kg of the catalyst composition (C-3) prepared in Example-1 was suspended in 4.4 kg of hot water, and a rare earth metal chloride was converted to RE 2 O 3 catalyst composition in this suspension. Then, an amount corresponding to 2.5 wt% was added, and then adjusted to pH 5.5 with a concentration of 20 wt% hydrochloric acid and stirred at a temperature of 60 ° C. for 20 minutes to introduce rare earth metal into the catalyst. Then, it filtered, wash | cleaned, and dried and the catalyst composition (C-5) was prepared. Table 3 shows the properties of the catalyst composition (C-5).
[0015]
Comparative Example-1
40 kg of water was added to 5.0 kg of NaY (dry basis) used in Example 1 to form a suspended slurry. After this suspension slurry was heated to 60 ° C., 2482 g of ammonium sulfate having a concentration of about 100% was added. Next, the pH of the suspension slurry was adjusted to 4.5 with a 25 wt% aqueous sulfuric acid solution, and further heated to 80 ° C. and held for 1 hour for ammonium ion exchange. This zeolite is filtered and washed, and then suspended in water again. Rare earth chloride is added to this suspended slurry in an amount corresponding to 67% by weight of zeolite unit weight in terms of RE 2 O 3 , and further with 35% hydrochloric acid aqueous solution. The pH of the suspension slurry was adjusted to 5.5, and aging was performed at 60 ° C. for 1 hour to perform rare earth exchange.
The aging slurry was filtered and washed, and then dried at 120 ° C. for 16 hours to obtain rare earth exchanged zeolite (A-6). Table 1 shows the properties of the rare earth exchanged zeolite (A-6). Zeolite (A-6) was pulverized to a diameter of 1 mm or less and then calcined in air at 550 ° C. for 3 hours in a box-type electric furnace to obtain rare earth exchanged zeolite (B-6). The properties are shown in Table 1. Using this zeolite (B-6), a catalyst composition (C-6) was prepared in the same manner as in Example-1. Table 3 shows the properties of the catalyst composition (C-6).
[0016]
Comparative Example-2
40 kg of water was added to 5.0 kg of NaY (dry basis) used in Example 1 to form a suspended slurry. After this suspension slurry was heated to 60 ° C., 2482 g of ammonium sulfate having a concentration of about 100% was added. Next, the pH of the suspension slurry was adjusted to 4.5 with a 25 wt% aqueous sulfuric acid solution, and further heated to 80 ° C. and held for 1 hour for ammonium ion exchange. This zeolite was filtered and washed, and then dried at 120 ° C. for 16 hours to obtain a zeolite having an ammonium exchange rate of 70%.
This zeolite was pulverized to a diameter of 1 mm or less and then calcined in the presence of water vapor in the same manner as in Example-1. Table 1 shows the properties of the ultrastable zeolite (A-7) obtained by calcination.
[0017]
3.0 kg (dry basis) of this ultrastable zeolite (A-7) was suspended in 24 kg of water and heated to 60 ° C., and then the rare earth chloride was added to this suspension slurry in terms of zeolite unit weight in terms of RE 2 O 3. An amount corresponding to 30% by weight was added, and the pH of the suspension slurry was further adjusted to 5.5 with a 20% aqueous hydrochloric acid solution, followed by further aging at 60 ° C. for 1 hour for rare earth exchange.
The aging slurry was filtered and washed, and then dried at 120 ° C. for 16 hours to obtain a rare earth exchanged zeolite. The rare earth exchanged zeolite was pulverized to a diameter of 1 mm or less and then calcined in air at 550 ° C. for 3 hours in an electric furnace to obtain rare earth exchanged zeolite (B-7). The properties are shown in Table 1. Using this zeolite (B-7), a catalyst composition (C-7) was prepared in the same manner as in Example-1. Table 3 shows the properties of the catalyst composition (C-7).
[0018]
Comparative Example-3
A catalyst composition (C-8) was prepared in the same manner as in Example 1 using a zeolite prepared in exactly the same manner as the ultrastable zeolite (A-7) of Comparative Example-2. The properties are shown in Table 3.
[0019]
Comparative Example-4
Using a part of the catalyst composition (C-8) prepared in Comparative Example-3, a catalyst composition (C-9) in which a rare earth metal was introduced into the catalyst in the same manner as in Example-2 was prepared. . The properties are shown in Table 3.
[0020]
Example-3 (performance evaluation test)
A performance evaluation test was performed on the catalyst compositions C-1 to C-9 prepared in Examples 1 and 2 and Comparative Examples 1 to 4.
In the performance evaluation test, a sample obtained by calcining about 200 g of each catalyst composition in air at 600 ° C. for 2 hours was impregnated with a benzene solution containing 10,000 ppm of nickel naphthenate and vanadium naphthenate as V + Ni, and then under reduced pressure. After removing benzene, the catalyst was calcined at 600 ° C. for 2 hours and further treated at 732 ° C. for 17 hours in a 100% water vapor atmosphere for 17 hours to perform quasi-equilibration.
The catalytic cracking reaction was carried out under the following reaction conditions using a vacuum gas oil (DSVGO) obtained by hydrogenating the raw material oil.
Reaction conditions Reaction temperature 500 ℃
Space velocity 16hr -1
Catalyst / oil ratio 3wt / wt
The evaluation results are shown in Tables 4 and 5. The catalyst composition of the present invention has a high conversion rate, a high yield of gasoline and kerosene oil fraction (LCO), and little generation of hydrogen and coke.
[0021]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
Hereinafter, specific embodiments of the present invention will be described.
1. Crystalline aluminosilicate zeolite obtained by calcining rare earth exchanged crystalline aluminosilicate zeolite obtained by ion exchange of faujasite type crystalline aluminosilicate zeolite with rare earth metal ions in porous matrix material. A catalyst composition for hydrocarbon catalytic cracking, which is dispersed.
2. Porous crystalline aluminosilicate zeolite obtained by calcining rare earth metal and ammonium-exchanged crystalline aluminosilicate zeolite obtained by ion exchange of faujasite type crystalline aluminosilicate zeolite with rare earth metal ions and ammonium ions in the presence of water vapor Hydrocarbon catalytic cracking catalyst composition dispersed in a conductive matrix material.
3. The catalyst composition for catalytic cracking of the first or second hydrocarbon, wherein the calcined crystalline aluminosilicate zeolite is calcined at a calcining temperature of 400 to 900 ° C.
4). The rare earth exchange crystalline aluminosilicate zeolite or the rare earth metal and ammonium exchange crystalline aluminosilicate zeolite has a rare earth ion exchange rate of 5 to 70%, preferably 10 to 60%, and Na ions are Na 2 O and 6 wt% or less. The catalyst composition for catalytic cracking of a first, second or third hydrocarbon, preferably 3 to 6% by weight.
[0027]
5. The sintered crystalline aluminosilicate zeolite has a unit cell constant of 24.65 mm or less, preferably 24.65 to 24.50 m, and a skeletal structure SiO 2 / Al 2 O 3 molar ratio of 6 or more, preferably 6 The first to fourth hydrocarbon catalytic cracking catalyst compositions having a crystallinity of ˜9 and a crystallinity of 70% or more, preferably 80% or more.
6). Containing 5 to 50% by weight, preferably 10 to 40% by weight of the crystalline aluminosilicate zeolite obtained by calcination, and 95 to 50% by weight, preferably 90 to 60% by weight of the porous matrix material The first to fifth hydrocarbon catalytic cracking catalyst compositions.
7). The faujasite type crystalline aluminosilicate zeolite is ion exchanged using a rare earth metal ion or an aqueous solution containing a rare earth metal ion and an ammonium ion, and the ion exchanged crystalline aluminosilicate zeolite is subjected to a water vapor partial pressure of 0.05 kg / cm 2. The first to sixth hydrocarbons, characterized by being calcined in the presence of the above water vapor at a calcining temperature of 400 to 900 ° C. and dispersing the calcined crystalline aluminosilicate zeolite in a porous matrix material. A process for producing a catalytic cracking catalyst composition.
[0028]
【The invention's effect】
According to the present invention, it is used for catalytic cracking of hydrocarbon oils, especially heavy hydrocarbon oils, has excellent metal resistance, produces less coke and gas, and produces gasoline fractions, kerosene oil fractions, etc. A catalytic cracking catalyst composition having a high liquid yield is provided.
Claims (4)
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| JP06342195A JP3737155B2 (en) | 1995-02-27 | 1995-02-27 | Hydrocarbon catalytic cracking catalyst composition |
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| JP06342195A JP3737155B2 (en) | 1995-02-27 | 1995-02-27 | Hydrocarbon catalytic cracking catalyst composition |
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| JP3737155B2 true JP3737155B2 (en) | 2006-01-18 |
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| RU2548362C2 (en) | 2009-06-25 | 2015-04-20 | Чайна Петролеум & Кемикал Корпорейшн | Catalyst for catalytic cracking and method of increasing catalyst selectivity (versions) |
| US8529754B2 (en) * | 2009-09-28 | 2013-09-10 | China Petroleum & Chemical Corporation | Catalytic conversion process for producing more diesel and propylene |
| JP5988875B2 (en) * | 2009-10-22 | 2016-09-07 | 中国石油化工股▲ふん▼有限公司 | Catalytic conversion method to increase cetane barrel of diesel fuel |
| CN103157507B (en) * | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN103447063B (en) * | 2012-06-01 | 2016-02-10 | 中国石油天然气股份有限公司 | Heavy oil efficient conversion catalytic cracking catalyst and preparation method thereof |
| WO2014000423A1 (en) * | 2012-06-27 | 2014-01-03 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing modified y type molecular sieve and preparation method therefor |
| WO2015020014A1 (en) | 2013-08-05 | 2015-02-12 | 三菱化学株式会社 | Zeolite, and production method and use therefor |
| CN112206809A (en) * | 2019-07-09 | 2021-01-12 | 中国石油化工股份有限公司 | Rare earth-containing Y-type molecular sieve and preparation method thereof |
| CN113318778B (en) * | 2020-02-28 | 2023-10-13 | 中国石油化工股份有限公司 | A catalytic cracking catalyst |
| CN113318777A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing rare earth Y-type molecular sieve |
| CN113318776B (en) * | 2020-02-28 | 2023-09-05 | 中国石油化工股份有限公司 | cracking catalyst |
| JP7576429B2 (en) * | 2019-11-15 | 2024-10-31 | 日揮触媒化成株式会社 | Method for producing fluid catalytic cracking catalyst |
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