JP5773644B2 - Method for regenerating hydrotreating catalyst - Google Patents
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- JP5773644B2 JP5773644B2 JP2010293091A JP2010293091A JP5773644B2 JP 5773644 B2 JP5773644 B2 JP 5773644B2 JP 2010293091 A JP2010293091 A JP 2010293091A JP 2010293091 A JP2010293091 A JP 2010293091A JP 5773644 B2 JP5773644 B2 JP 5773644B2
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- 239000003054 catalyst Substances 0.000 title claims description 192
- 238000000034 method Methods 0.000 title claims description 39
- 230000001172 regenerating effect Effects 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 109
- 239000002184 metal Substances 0.000 claims description 109
- 239000002253 acid Substances 0.000 claims description 100
- 239000002738 chelating agent Substances 0.000 claims description 65
- 150000007522 mineralic acids Chemical class 0.000 claims description 65
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 9
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 9
- 239000001630 malic acid Substances 0.000 claims description 9
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- 230000000737 periodic effect Effects 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 95
- 230000000694 effects Effects 0.000 description 63
- 239000003921 oil Substances 0.000 description 30
- 239000012298 atmosphere Substances 0.000 description 25
- 238000006477 desulfuration reaction Methods 0.000 description 25
- 230000023556 desulfurization Effects 0.000 description 25
- 238000011282 treatment Methods 0.000 description 23
- 238000001354 calcination Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 230000008929 regeneration Effects 0.000 description 14
- 238000011069 regeneration method Methods 0.000 description 14
- 239000011148 porous material Substances 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 230000003993 interaction Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000006259 organic additive Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Description
本発明は、使用済みの水素化処理触媒を再生する技術に関する。 The present invention relates to a technique for regenerating a spent hydroprocessing catalyst.
灯・軽油などの燃料油中の硫黄分を水素化処理により除去する際には、水素化処理触媒が用いられている。近年、環境保護の観点から硫黄分の品質規制が強化されており、より脱硫性能の高く低コストの水素化処理触媒が望まれている。
水素化処理触媒は、使用過程で炭素（コーク）が付着し、また活性金属である第６族や第８族〜第１０族の活性金属成分の凝集が起こって、脱硫性能が徐々に低下してしまうため再生処理が必要である。一般的に水素化処理触媒の再生では、脱脂、焼成によるコーク除去といった処理が行われ、これらの処理により使用前触媒と比較してその性能が９割程度まで再生すると言われている。
また水素化処理触媒を製造する方法には、例えば活性金属成分を含む溶液を含浸させた担体を焼成せず、乾燥させる工程までで触媒の製造を終了することにより、担体上の活性金属成分を高分散状態に保つ技術がある。こうした方法により製造された水素化処理触媒を再生する場合には、一般的な水素化処理触媒の再生に加えてコーク除去時の焼成工程で凝集した活性金属成分を再分散させるため、有機添加剤やキレート剤を水溶液として再含浸させ再度乾燥させるという処理が必要であった。
しかしながら有機添加剤やキレート剤を利用する上述の手法においては、水素化処理触媒に再含浸したキレート剤や有機添加剤が活性金属成分の再分散を十分に進行させるまで、長時間の熟成工程が必要であり、商業的には生産性が悪く、コストが高くなっていた。
When removing sulfur content in fuel oil such as kerosene or light oil by hydrotreating, a hydrotreating catalyst is used. In recent years, quality control of sulfur content has been strengthened from the viewpoint of environmental protection, and a hydrotreating catalyst with higher desulfurization performance and lower cost is desired.
The hydrotreating catalyst has carbon (coke) attached in the process of use, and the active metal components of Group 6 and Group 8 to Group 10 which are active metals are aggregated, and the desulfurization performance gradually decreases. Therefore, playback processing is necessary. Generally, in the regeneration of a hydrotreating catalyst, treatments such as degreasing and coke removal by calcination are performed, and it is said that the performance is regenerated up to about 90% compared with the catalyst before use.
Further, in the method for producing a hydrotreating catalyst, for example, the active metal component on the carrier can be obtained by ending the production of the catalyst until the step of drying without baking the carrier impregnated with the solution containing the active metal component. There is a technology to maintain a highly dispersed state. When regenerating the hydrotreating catalyst produced by such a method, in addition to regenerating a general hydrotreating catalyst, an organic additive is added to redisperse the active metal component aggregated in the firing step at the time of coke removal. And a process of re-impregnating the chelating agent as an aqueous solution and drying again.
However, in the above-described method using an organic additive or a chelating agent, a long aging step is required until the chelating agent or the organic additive re-impregnated into the hydrotreating catalyst sufficiently proceeds the redispersion of the active metal component. It was necessary, and the productivity was not good commercially and the cost was high.
ここで特許文献１には、使用済み触媒を焼成し、その焼成処理触媒にモリブデンおよびニッケルのいずれか一方又は双方を再含浸させることによって活性を同等程度まで回復させる方法が記載され、その際にクエン酸やリンゴ酸などのキレート剤を利用する手法も記載されている。しかしながらこの特許文献１には、キレート剤を用いたときにおける熟成時間を短縮する手法の記述はない。
また特許文献２には、水素化処理触媒に再生処理（油分除去および焼成）を施したあと、当該触媒に所定量の有機物を担持させて、水素化処理触媒に担持された２種類の活性金属成分のうちの一方側と優先的に錯体を形成させることにより、活性金属の硫化処理を行う際に形成される活性点を増加させる技術が記載されている。そしてこの有機物としてクエン酸やリンゴ酸などの有機物が例示されているが、活性金属成分の再分散に関する詳細な記述はなく、その処理時間を短縮する手法の記載もない。
さらに特許文献３には、水素化処理触媒を酸およびエチレングリコールなどの有機添加剤と接触させることにより、当該触媒の活性の向上させる技術が記載されている。このうち酸は、触媒中の結晶質の量を低減する役割を果たし、その具体例として硝酸やリン酸などの無機酸、クエン酸やリンゴ酸などの有機酸が列挙されている。しかしながら当該特許文献３ではこれらの酸は触媒の活性を向上させるという共通の作用を発揮する添加剤として並列に列記されているものであり、クエン酸やリンゴ酸をキレート剤として使用する際の熟成時間を短縮する手法には言及されていない。
次いで特許文献４には、ＩＵＰＡＣ表記の周期表で第６族（モリブデン、タングステンなど）および第８族〜第１０族（鉄、コバルト、ニッケルなど）の活性金属につき、各族の活性金属を少なくとも１つ担体に担持して水素化処理触媒を製造する方法が記載されている。当該技術においては、担体および活性金属を含む分散液に、キレート剤（クエン酸やリンゴ酸など）とリン含有酸性成分（リン酸など）とを添加して活性金属の分散性を向上させている。しかしながら、本技術は活性金属が担持されていない担体へ新たに活性金属を担持する技術であり、使用済みの水素化処理触媒を再生する技術についての言及はない。
Here, Patent Document 1 describes a method of recovering the activity to an equivalent level by calcining a used catalyst and reimpregnating either or both of molybdenum and nickel into the calcined catalyst. Techniques using chelating agents such as citric acid and malic acid are also described. However, this Patent Document 1 does not describe a method for shortening the aging time when a chelating agent is used.
Further, Patent Document 2 discloses that two types of active metals supported on the hydrotreating catalyst are obtained by subjecting the hydrotreating catalyst to regeneration (oil removal and calcination), and then supporting a predetermined amount of organic substances on the catalyst. A technique is described that increases the active sites formed when sulfiding an active metal by preferentially forming a complex with one of the components. Examples of the organic substance include citric acid and malic acid, but there is no detailed description about redispersion of the active metal component, and no description of a method for shortening the processing time.
Further, Patent Document 3 describes a technique for improving the activity of the catalyst by bringing the hydrotreating catalyst into contact with an acid and an organic additive such as ethylene glycol. Among these, the acid plays a role of reducing the amount of the crystalline substance in the catalyst, and specific examples thereof include inorganic acids such as nitric acid and phosphoric acid, and organic acids such as citric acid and malic acid. However, in the said patent document 3, these acids are listed in parallel as an additive which exhibits the common effect | action which improves the activity of a catalyst, Aging at the time of using a citric acid or malic acid as a chelating agent. There is no mention of time saving techniques.
Next, Patent Document 4 discloses at least an active metal of each group for active metals of Group 6 (molybdenum, tungsten, etc.) and Groups 8-10 (iron, cobalt, nickel, etc.) in the periodic table of IUPAC notation. A method for producing a hydrotreating catalyst supported on one carrier is described. In this technique, a chelating agent (such as citric acid or malic acid) and a phosphorus-containing acidic component (such as phosphoric acid) are added to a dispersion containing a carrier and an active metal to improve the dispersibility of the active metal. . However, this technology is a technology for newly supporting an active metal on a carrier on which no active metal is supported, and there is no mention of a technology for regenerating a used hydroprocessing catalyst.
本発明は、このような事情を鑑みてなされたものであり、その目的は比較的短い熟成時間で活性金属成分を再分散させ、高い水素化処理活性を得ることが可能な水素化処理触媒の再生方法を提供することにある。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a hydroprocessing catalyst capable of redispersing active metal components in a relatively short aging time and obtaining high hydroprocessing activity. It is to provide a reproduction method.
第１の発明は、担体に、周期表第６族および第８〜１０族から選ばれる少なくとも１種の活性金属成分が担持された、使用済みの炭化水素油の水素化処理触媒を、３００℃を超える温度で焼成する第１工程と、
この第１工程にて焼成された水素化処理触媒を無機酸とキレート剤との双方を含む酸溶液に接触させて、前記活性金属成分を担体上に分散させる第２工程と、を含み、無機酸がリン酸または硝酸であり、キレート剤が多価カルボン酸であるクエン酸またはリンゴ酸であることを特徴とする水素化処理触媒の再生方法である。
第２の発明は、前記第２工程で用いる酸溶液に含まれるキレート剤のモル数に対する無機酸のモル数の比が０．０１〜０．２の範囲内にあることを特徴とする。
第３の発明は、前記第２工程にて無機酸とキレート剤との双方を含む酸溶液に接触させた水素化処理触媒に対し、乾燥または焼成の少なくとも一方の処理を行う第３工程を含むことを特徴とする。
第４の発明は、前記活性金属成分は、モリブデン、コバルト、およびニッケルから選択された少なくとも１つ以上の金属であることを特徴とする。
In a first aspect of the invention, there is provided a used hydrocarbon oil hydrotreating catalyst having a carrier on which at least one active metal component selected from Groups 6 and 8 to 10 of the periodic table is supported. A first step of firing at a temperature exceeding
The hydrotreating catalysts calcined at the first step into contact with an acid solution containing both an inorganic acid and a chelating agent, wherein the second step of dispersing onto the support of the active metal component, an inorganic A method for regenerating a hydrotreating catalyst, wherein the acid is phosphoric acid or nitric acid, and the chelating agent is citric acid or malic acid, which is a polyvalent carboxylic acid.
The second invention is characterized in that the ratio of the number of moles of the inorganic acid to the number of moles of the chelating agent contained in the acid solution used in the second step is in the range of 0.01 to 0.2.
The third invention includes a third step of performing at least one treatment of drying or calcination on the hydrotreatment catalyst brought into contact with the acid solution containing both the inorganic acid and the chelating agent in the second step. It is characterized by that.
The fourth invention is characterized in that the active metal component is at least one metal selected from molybdenum, cobalt, and nickel.
第５の発明は、前記第２工程の無機酸とキレート剤との双方を含む酸溶液には、前記周期表第６族および第８〜１０族から選ばれる少なくとも１種の活性金属成分が添加されており、当該第２工程では、これら活性金属成分を含む酸溶液に水素化処理触媒を接触させることにより、前記担体に担持されている活性金属成分の分散と、酸溶液に添加されている活性金属成分の当該担体への担持と、が行われることを特徴とする。
第６の発明は、第６の発明における酸溶液には、モリブデン、コバルト、およびニッケルから選択された少なくとも１つ以上の活性金属成分が、第１工程で得た水素化処理触媒の質量を基準にして、活性金属成分の酸化物に換算して１質量％以下に相当する量だけ含まれていることを特徴とする。
According to a fifth aspect of the invention, in the acid solution containing both the inorganic acid and the chelating agent in the second step, at least one active metal component selected from Groups 6 and 8 to 10 of the periodic table is added. In the second step, the hydrotreating catalyst is brought into contact with the acid solution containing these active metal components, whereby the active metal components supported on the carrier are dispersed and added to the acid solution. The active metal component is supported on the carrier.
According to a sixth aspect of the invention, in the acid solution according to the sixth aspect, at least one active metal component selected from molybdenum, cobalt, and nickel is based on the mass of the hydrotreating catalyst obtained in the first step. Thus, it is characterized by being contained in an amount corresponding to 1% by mass or less in terms of the oxide of the active metal component.
本発明によれば、焼成した後の水素化処理触媒を、無機酸とキレート剤との双方を含む酸溶液に接触させるので、無機酸により担体の細孔内への活性金属成分の浸透を促進させる効果および酸溶液の粘性を低減する効果と、キレート剤による担体−活性金属成分間の相互作用を軽減する効果とが発揮され、比較的短い時間で活性金属成分を再分散させることができる。 According to the present invention, since the hydrotreated catalyst after firing is brought into contact with an acid solution containing both an inorganic acid and a chelating agent, the inorganic acid promotes the penetration of the active metal component into the pores of the support. And the effect of reducing the viscosity of the acid solution and the effect of reducing the interaction between the carrier and the active metal component due to the chelating agent, and the active metal component can be redispersed in a relatively short time.
本発明の実施の形態に係る水素化処理触媒の再生方法について説明する。
（水素化処理触媒）
本発明が適用される炭化水素油の水素化処理触媒は、高温高圧雰囲気下で、炭化水素油である軽質油や重質油と水素とを当該触媒の存在下で接触させることにより、脱硫や脱窒素、脱メタルや水素化分解などの反応を進行させる一般的な水素化処理触媒である。軽質油の例としてはナフサ、灯油、軽質軽油（Light Gas Oil、ＬＧＯ）、重質軽油（Heavy Gas Oil、ＨＧＯ）、減圧軽油（Vacuum Gas Oil、ＶＧＯ）等が挙げられ、重質油の例としては常圧残油（Atmospheric Residue、ＡＲ）、減圧残油（Vacuum Residue、ＶＲ）などが挙げられる。
前記水素化処理触媒を構成する担体としては、無機酸化物から構成され、例えば、アルミナ、シリカ、チタニア、シリカ−アルミナ、アルミナ−チタニア、アルミナ−ジルコニア、アルミナ−ボリア、リン−アルミナ、シリカ−アルミナ−ボリア、リン−アルミナ−ボリア、リン−アルミナ−シリカ、シリカ−アルミナ−チタニア、シリカ−アルミナ−ジルコニアなどを例示することができる。
A method for regenerating a hydroprocessing catalyst according to an embodiment of the present invention will be described.
(Hydroprocessing catalyst)
The hydrotreating catalyst for hydrocarbon oil to which the present invention is applied is a desulfurization or desulfurization catalyst by contacting light oil or heavy oil that is hydrocarbon oil with hydrogen in the presence of the catalyst under a high temperature and high pressure atmosphere. It is a general hydroprocessing catalyst that promotes reactions such as denitrification, demetalization and hydrocracking. Examples of light oil include naphtha, kerosene, light gas oil (LGO), heavy gas oil (HGO), vacuum gas oil (Vacuum Gas Oil, VGO), etc. Examples of heavy oil Examples thereof include atmospheric residual oil (Atmospheric Residue, AR) and vacuum residual oil (Vacuum Residue, VR).
The carrier constituting the hydrotreating catalyst is composed of an inorganic oxide, such as alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina. -Boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, silica-alumina-zirconia and the like can be exemplified.
前記担体に担持される活性金属成分は、周期表の第６族および第８族〜第１０族から少なくとも１種類の活性金属成分が選ばれ、より好適には第６族および第８族〜第１０族の各族からすくなくとも１種類ずつの活性金属成分が選ばれる。第６族の活性金属成分としてはモリブデン（Ｍｏ）、タングステン（Ｗ）、クロム（Ｃｒ）などが挙げられ、第８族〜第１０族の活性金属成分としてはニッケル（Ｎｉ）、コバルト（Ｃｏ）などが挙げられる。またこれらの活性金属成分に加え、リンやホウ素などの他の元素を適宜添加してもよい。選択される活性金属成分の種類やその担持量は、処理対象の炭化水素油の種類やプロセス条件などに応じて適宜設定される。
また使用済み触媒とは、炭化水素油の水素化処理に使用された後の水素化処理触媒を意味し、具体例としては水素化処理装置から回収された水素化処理触媒などを挙げることができる。使用済み触媒の表面には、炭化水素油から析出したコークなどの炭素質や、重質油に多く含まれるバナジウム（Ｖ）や鉄（Ｆｅ）、ニッケル（Ｎｉ）などの金属不純物などが付着している。
As the active metal component supported on the carrier, at least one active metal component is selected from Group 6 and Group 8 to Group 10 of the periodic table, and more preferably Group 6 and Group 8 to Group 8 are selected. At least one active metal component is selected from each of the 10 groups. Examples of Group 6 active metal components include molybdenum (Mo), tungsten (W), and chromium (Cr), and Group 8 to Group 10 active metal components include nickel (Ni) and cobalt (Co). Etc. In addition to these active metal components, other elements such as phosphorus and boron may be added as appropriate. The type of active metal component selected and the amount of the active metal component selected are appropriately set according to the type of hydrocarbon oil to be treated and the process conditions.
The used catalyst means a hydrotreating catalyst after being used for hydrotreating hydrocarbon oil, and specific examples include a hydrotreating catalyst recovered from a hydrotreating apparatus. . Carbon impurities such as coke deposited from hydrocarbon oil and metal impurities such as vanadium (V), iron (Fe), nickel (Ni), etc., which are abundant in heavy oil, adhere to the surface of the used catalyst. ing.
（第１工程）
本工程では、使用済みの水素化処理触媒を、３００℃を超える温度で焼成する。使用済み触媒を焼成する場合には、前処理として例えば１８０〜２２０℃の窒素などの不活性ガス雰囲気中で触媒に付着している油分（軽質油分）を除去する処理を行った後に焼成を行ってもよい。ここで例えば窒素雰囲気の場合、空気よりも酸素濃度が低い状態、すなわち、窒素濃度が８０容量％以上、好ましくは９０容量％以上、より好ましくは９５容量％以上の状態で前処理を行うとよい。
必要に応じて前処理が行われた使用済み触媒は、空気（酸素濃度約２１容量％）などの含酸素雰囲気中で焼成されることにより、表面に付着している炭素質などを燃焼して除去する。また焼成雰囲気としては、空気に酸素を添加して、焼成時の酸素濃度が２１容量％を超える富酸素雰囲気としてもよい。焼成温度は、３００℃以上、好ましくは３２０〜５００℃、より好ましくは３５０℃を超え４５０℃以下の温度範囲にて行う場合が好適である。焼成時間は、焼成前後に水素化処理触媒に付着している炭素質の量により、適宜変化するが、例えば６０〜３００分間、好ましくは１２０〜２４０分間程度の焼成が行われる。これらの焼成条件は、焼成後の水素化処理触媒に付着している炭素質が、当該炭素質を含む水素化処理触媒の全重量の３質量％以下、好ましくは１質量％以下、より好ましくは０．１質量％程度となるように設定される。
(First step)
In this step, the used hydrotreatment catalyst is calcined at a temperature exceeding 300 ° C. When the used catalyst is calcined, it is calcined as a pretreatment after removing the oil (light oil) adhering to the catalyst in an inert gas atmosphere such as nitrogen at 180 to 220 ° C. May be. Here, for example, in the case of a nitrogen atmosphere, the pretreatment may be performed in a state where the oxygen concentration is lower than that of air, that is, in a state where the nitrogen concentration is 80% by volume or higher, preferably 90% by volume or higher, more preferably 95% by volume or higher. .
The used catalyst, which has been pretreated as necessary, is baked in an oxygen-containing atmosphere such as air (oxygen concentration of about 21% by volume) to burn carbonaceous matter adhering to the surface. Remove. The firing atmosphere may be an oxygen-rich atmosphere in which oxygen is added to air and the oxygen concentration during firing exceeds 21% by volume. The baking temperature is preferably 300 ° C. or higher, preferably 320 to 500 ° C., more preferably 350 ° C. or higher and 450 ° C. or lower. The calcination time varies as appropriate depending on the amount of carbonaceous matter attached to the hydroprocessing catalyst before and after calcination, but for example, calcination is performed for 60 to 300 minutes, preferably about 120 to 240 minutes. These calcination conditions are such that the carbonaceous matter adhering to the hydrotreated catalyst after calcination is 3% by mass or less, preferably 1% by mass or less, more preferably, of the total weight of the hydrotreating catalyst containing the carbonaceous matter. It is set to be about 0.1% by mass.
（第２工程）
次に、第１工程にて得られた焼成処理後の水素化処理触媒（以下、焼成触媒という）を無機酸とキレート剤との双方を含む酸溶液に接触させる処理について説明する。例えば使用済みの触媒は、実運転や焼成処理により触媒内の活性金属成分が凝集した状態となっているため、これら凝集した活性金属成分を再分散させる必要がある。この点、担体に担持された活性金属成分を酸溶液などに溶解してから同担体に再含浸させることにより、活性金属成分の分散性を向上させ、高活性の水素化処理触媒を得ることができる。
ここで、発明者らは、硝酸やリン酸などの無機酸は水素化処理触媒を構成する担体の細孔内を拡散して浸透する速度が大きいことを把握している。その一方で、無機酸溶液中に溶解して触媒表面から脱離した活性金属成分は、例えば担体表面の塩基性水酸基と、活性金属のカチオンが静電気的に引き合って活性金属が強く固定される等、担体から受ける相互作用が大きく、細孔内部への拡散が遅くなってしまうという現象が発生することも判明している。
この点、キレート剤を含むキレート溶液は、溶液中に溶解した活性金属成分とキレート剤とが錯体を形成することにより、活性金属成分と担体との相互作用を小さくし、活性金属成分の細孔の内部への拡散を妨げる力を低減する作用を持っている。しかしながらキレート剤は溶液の粘性を増大させるため、活性金属成分を担体の細孔の内部にまで十分に拡散させるためには長い熟成時間を必要とするという問題がある。
(Second step)
Next, the process which makes the hydrotreating catalyst after baking processing obtained at the 1st process (henceforth a baking catalyst) contact the acid solution containing both an inorganic acid and a chelating agent is demonstrated. For example, a used catalyst is in a state in which active metal components in the catalyst are aggregated due to actual operation or calcination treatment, and thus these aggregated active metal components need to be redispersed. In this regard, it is possible to improve the dispersibility of the active metal component and obtain a highly active hydrotreating catalyst by dissolving the active metal component supported on the support in an acid solution and then reimpregnating the support. it can.
Here, the inventors have grasped that inorganic acids such as nitric acid and phosphoric acid have a high rate of diffusing and permeating through the pores of the carrier constituting the hydrotreating catalyst. On the other hand, the active metal component dissolved in the inorganic acid solution and desorbed from the catalyst surface, for example, the basic hydroxyl group on the support surface and the cation of the active metal attract each other electrostatically and the active metal is strongly fixed, etc. It has also been found that the phenomenon that the interaction received from the carrier is large and the diffusion into the pores is delayed occurs.
In this regard, the chelating solution containing the chelating agent reduces the interaction between the active metal component and the carrier by forming a complex between the active metal component dissolved in the solution and the chelating agent, and the pores of the active metal component. It has the effect of reducing the force that hinders the diffusion into the interior. However, since the chelating agent increases the viscosity of the solution, there is a problem that a long aging time is required to sufficiently diffuse the active metal component into the pores of the support.
そこで、本発明者らは、無機酸とキレート剤との双方を含む酸溶液を調製し、この酸溶液に水素化処理触媒を分散（接触）させることにより、キレート剤による活性金属成分と担体との相互作用の低減効果、無機酸によるキレート剤を含む溶液の粘性を低下させる効果、および無機酸により酸溶液が担体の細孔内に浸透する効果を並行に発揮させることが可能となることを見いだした。この結果、キレート剤単独の溶液を使用して活性金属成分を再分散させる場合と比較して、短い時間で担体の細孔内部まで活性金属成分を再分散させることが可能となる。
酸溶液に添加される無機酸としては、リン酸、硝酸、塩酸、硫酸などを採用することができ、キレート剤としては、リンゴ酸、クエン酸、酒石酸、シュウ酸などの多座配位子を持つ有機酸（カルボン酸）などが選択される。無機酸およびキレート剤は、例えば水に溶解された水溶液として調製される。酸溶液に添加するキレート剤の量は、第１工程にて得られた焼成触媒の重量を基準として、１〜２０質量％、好ましくは３〜１５質量％、より好ましくは５〜１２質量％程度添加される。キレート剤の添加量が、３質量％未満では、活性金属成分を再分散させるのに十分な作用が得られ難くなる一方で、添加量が２０質量％を超えると、経済性が悪くなると共に、触媒の活性が低下するおそれがある。
Therefore, the present inventors prepare an acid solution containing both an inorganic acid and a chelating agent, and disperse (contact) the hydrotreating catalyst in the acid solution, whereby the active metal component and the carrier by the chelating agent are mixed with each other. It is possible to exhibit the effect of reducing the interaction of the acid, the effect of reducing the viscosity of the solution containing the chelating agent by the inorganic acid, and the effect of the acid solution penetrating into the pores of the support by the inorganic acid. I found it. As a result, it is possible to redisperse the active metal component into the pores of the support in a shorter time compared to the case where the active metal component is redispersed using a solution of the chelating agent alone.
As the inorganic acid added to the acid solution, phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid and the like can be adopted, and as the chelating agent, a multidentate ligand such as malic acid, citric acid, tartaric acid, oxalic acid or the like can be used. An organic acid (carboxylic acid) or the like is selected. The inorganic acid and the chelating agent are prepared, for example, as an aqueous solution dissolved in water. The amount of the chelating agent added to the acid solution is 1 to 20% by mass, preferably 3 to 15% by mass, more preferably about 5 to 12% by mass, based on the weight of the calcined catalyst obtained in the first step. Added. When the addition amount of the chelating agent is less than 3% by mass, it is difficult to obtain an effect sufficient to redisperse the active metal component. On the other hand, when the addition amount exceeds 20% by mass, the economical efficiency is deteriorated. The activity of the catalyst may be reduced.
一方、酸溶液に添加される無機酸の量は、第１工程にて得られた焼成触媒の重量を基準として、０．０５〜２．０質量％、好ましくは０．１〜１．７質量％、より好ましくは０．１５〜１．４質量％程度添加される。無機酸の添加量が、０．０５質量％未満では、酸溶液を担体の細孔内に浸透させる作用や酸溶液の粘性を低下させる作用が十分に得られなくなる。また添加量が２．０質量％を超えると、触媒の活性が低下するおそれがある。
ここで、既述のように、本発明においては酸溶液中に無機酸とキレート剤とが同時に存在している相乗効果により、活性金属成分の再分散と熟成工程に要する時間の短縮が図られている。このため、前記酸溶液においては、無機酸およびキレート剤の各々の添加量が上述の範囲内の値に調整されるのみならず、キレート剤のモル数に対する無機酸のモル数の比も所定の範囲内の値となっていることがより好ましい。後述する実施例によれば、当該モル比の範囲は、０．０１〜０．２の範囲内とすることが好ましい。前記モル比が０．０１を下回ると、無機酸の添加効果が低下し、０．２を超えると、キレート剤の作用が十分に得られなくなってしまうものと考えられる。また、無機酸としてリン酸を採用する場合には、リンは再生された触媒上にＰ２Ｏ５として担持される。このことから、前記の比の値が０．２を超えると、既に表面積が小さくなっている使用済み触媒において、Ｐ２Ｏ５が担持されることによるさらなる表面積の低下の影響が大きくなって好ましくない。
On the other hand, the amount of the inorganic acid added to the acid solution is 0.05 to 2.0 mass%, preferably 0.1 to 1.7 mass%, based on the weight of the calcined catalyst obtained in the first step. %, More preferably about 0.15 to 1.4% by mass. When the added amount of the inorganic acid is less than 0.05% by mass, the effect of allowing the acid solution to penetrate into the pores of the carrier and the effect of reducing the viscosity of the acid solution cannot be obtained sufficiently. On the other hand, if the amount added exceeds 2.0% by mass, the activity of the catalyst may decrease.
Here, as described above, in the present invention, the synergistic effect of the presence of the inorganic acid and the chelating agent in the acid solution simultaneously reduces the time required for the redispersion of the active metal component and the aging step. ing. For this reason, in the acid solution, not only the addition amount of each of the inorganic acid and the chelating agent is adjusted to a value within the above range, but also the ratio of the number of moles of the inorganic acid to the number of moles of the chelating agent is predetermined. More preferably, the value is within the range. According to the examples described later, the molar ratio is preferably in the range of 0.01 to 0.2. If the molar ratio is less than 0.01, the effect of adding an inorganic acid is reduced, and if it exceeds 0.2, it is considered that the action of the chelating agent cannot be sufficiently obtained. When phosphoric acid is employed as the inorganic acid, phosphorus is supported as P 2 O 5 on the regenerated catalyst. For this reason, if the ratio value exceeds 0.2, in the used catalyst whose surface area has already been reduced, the effect of further reduction of the surface area due to the loading of P 2 O 5 is preferably increased. Absent.
また、使用済み触媒の場合には、炭化水素油を処理する際の摩耗やシンタリングにより水素化処理触媒の比表面積が低下したり、活性金属成分の一部が炭化水素油中に流出したりすることにより、水素化処理触媒の活性が低下することがある。このような理由により、水素化処理触媒の活性が低下した場合には、炭素質を除去したり、活性金属成分を際分散したりするだけでは水素化処理触媒の活性が未使用触媒と同等程度まで回復できない場合もある。そこで、活性金属成分を再分散するために使用する前記酸溶液中に活性金属成分を新たに添加し、上述の理由による水素化処理触媒の活性の低下を補ってもよい。 In the case of a used catalyst, the specific surface area of the hydrotreating catalyst decreases due to wear and sintering during the processing of the hydrocarbon oil, or a part of the active metal component flows into the hydrocarbon oil. By doing so, the activity of the hydrotreating catalyst may decrease. For these reasons, when the activity of the hydrotreating catalyst is reduced, the activity of the hydrotreating catalyst is almost the same as that of an unused catalyst simply by removing carbonaceous matter or dispersing the active metal component. In some cases, it cannot be recovered. Therefore, an active metal component may be newly added to the acid solution used for redispersing the active metal component to compensate for the decrease in the activity of the hydrotreating catalyst due to the above-described reason.
このとき酸溶液には、水素化処理触媒に担持されている活性金属成分の全種類を添加してもよいし、その一部の種類を添加してもよく、さらには活性金属成分の種類を追加して添加してもよい。酸溶液に添加する活性金属成分は、例えば酸溶液に活性金属成分の酸化物を溶解してもよいし、活性金属成分の各種の塩を添加してもよい。
焼成触媒を投入する前の酸溶液に添加される活性金属成分の量は、第１工程で得られた焼成触媒の重量を基準にして、活性金属成分の酸化物に換算して１質量％以下の範囲が好適である。ここでは、第６族の活性金属成分としてモリブデン（Ｍｏ）が担持され、第８族〜第１０族の活性金属成分としてニッケル（Ｎｉ）、コバルト（Ｃｏ）の少なくとも一方が担持されている水素化処理触媒を例に挙げて説明する。
この場合にモリブデンやニッケル、コバルトを酸化物の状態で担持する場合には、ＭｏＯ３、ＮｉＯ、ＣｏＯなどを焼成触媒の１質量％以下の範囲内で酸溶液に添加する。一方、これらの活性金属成分を他の塩の状態で添加する場合には、上述の各酸化物に換算したとき焼成触媒の１質量％以下に相当する量を添加する。このように酸溶液に活性金属成分を加えることにより、焼成触媒上に既に担持されている活性金属成分を再分散させるだけでは回復できない触媒活性を補うことができる。第２工程にて酸溶液に添加する活性金属成分は、酸化物として焼成触媒の１質量％を超えて担持したとしても、水素化処理触媒の活性の回復の幅が小さくなり新たな活性金属成分を添加するというコスト以上のメリットが得られない場合がある。
モリブデンやニッケル、コバルト以外の活性金属成分を担持する場合についても同様の考え方に基づいて酸溶液への活性金属成分の添加量が調整される。
At this time, all kinds of active metal components supported on the hydrotreating catalyst may be added to the acid solution, or some of them may be added, and further, the kinds of active metal components may be added. You may add in addition. For the active metal component added to the acid solution, for example, an oxide of the active metal component may be dissolved in the acid solution, or various salts of the active metal component may be added.
The amount of the active metal component to be added to the acid solution before charging the calcined catalyst is 1% by mass or less in terms of the oxide of the active metal component based on the weight of the calcined catalyst obtained in the first step. The range of is preferable. Here, molybdenum (Mo) is supported as an active metal component of Group 6, and at least one of nickel (Ni) and cobalt (Co) is supported as an active metal component of Groups 8 to 10. The processing catalyst will be described as an example.
In this case, when molybdenum, nickel, or cobalt is supported in an oxide state, MoO 3 , NiO, CoO, or the like is added to the acid solution within a range of 1% by mass or less of the calcined catalyst. On the other hand, when these active metal components are added in the form of other salts, an amount corresponding to 1% by mass or less of the calcined catalyst is added when converted into the above-mentioned oxides. By adding the active metal component to the acid solution in this way, it is possible to supplement the catalytic activity that cannot be recovered simply by redispersing the active metal component already supported on the calcined catalyst. Even if the active metal component added to the acid solution in the second step is supported in excess of 1% by mass of the calcined catalyst as an oxide, the range of recovery of the activity of the hydrotreating catalyst is reduced, and a new active metal component In some cases, it is not possible to obtain a merit more than the cost of adding.
Even when an active metal component other than molybdenum, nickel, or cobalt is supported, the amount of the active metal component added to the acid solution is adjusted based on the same concept.
以上に説明した考え方に基づいて、酸溶液（必要に応じて活性金属成分を含んでいる）が調製されたら、第１工程にて得られた焼成触媒に当該酸溶液を含浸させる。そして例えば室温〜８０℃の温度範囲で０．５〜３時間熟成させることにより、焼成触媒上に担持されていた活性金属成分が酸溶液中に溶解し、担体表面に分散する。また酸溶液に予め活性金属成分が添加されている場合には、当該活性金属成分も担体に含浸される。ここで酸溶液を含浸させる法は所定の手法に限定されるものではなく、減圧含浸法、ポアフィリング法、平衡吸着法など、どのような手法を使用してもよい。
このとき酸溶液中に無機酸とキレート剤とを含んでいることにより、キレート剤による活性金属成分と担体との相互作用の低減効果、無機酸による酸溶液の粘性を低下させる効果、および無機酸により酸溶液が担体の細孔内に浸透する効果が並行に発揮される。この結果、活性金属成分の再分散の進行速度が向上し、比較的短い時間で熟成工程を終えることができる。
When an acid solution (containing an active metal component as necessary) is prepared based on the above-described concept, the calcined catalyst obtained in the first step is impregnated with the acid solution. For example, by aging for 0.5 to 3 hours in a temperature range of room temperature to 80 ° C., the active metal component supported on the calcined catalyst is dissolved in the acid solution and dispersed on the surface of the support. When an active metal component is added in advance to the acid solution, the active metal component is also impregnated in the support. Here, the method of impregnating the acid solution is not limited to a predetermined method, and any method such as a reduced pressure impregnation method, a pore filling method, an equilibrium adsorption method or the like may be used.
At this time, by containing an inorganic acid and a chelating agent in the acid solution, the effect of reducing the interaction between the active metal component and the carrier by the chelating agent, the effect of reducing the viscosity of the acid solution by the inorganic acid, and the inorganic acid As a result, the effect that the acid solution penetrates into the pores of the carrier is exhibited in parallel. As a result, the progress speed of redispersion of the active metal component is improved, and the aging step can be completed in a relatively short time.
（第３工程）
第２工程にて所定時間の熟成を終えたら、酸溶液を含浸させた水素化処理触媒（以下、含浸触媒という）を乾燥し、焼成する処理を行う。ここで本発明における含浸触媒の乾燥は、担体の表面や細孔内など、含浸触媒触媒上に存在する酸溶液の液体分を蒸発させることを意味する。従って含浸触媒の液体分を蒸発させるのに十分な条件下で乾燥が行われればよく、活性金属成分やキレート剤、無機酸は乾燥の過程において化学的な性状の変化が起こってもよいし、起こらなくてもよい。乾燥処理は、例えば室温から３００℃まで、好ましくは室温から２７０℃まで、更に好ましくは室温から２５０℃までの温度範囲内で液体分を蒸発させるのに十分な時間行われる。また乾燥処理が行われる雰囲気は、大気雰囲気など、含酸素雰囲気でもよいし、酸素ガスを含まない不活性ガス雰囲気でもよい。そして、乾燥処理を終えた水素化処理触媒上の活性金属成分は、キレート剤と錯体を形成した状態のまま担持されている場合もあるし、乾燥処理によりキレート剤が分解して金属の状態で担持されている場合もある。また、含酸素雰囲気中で乾燥した場合には、活性金属成分の一部が酸化していてもよい。
これに対して含浸触媒の焼成は、含浸触媒やこれを乾燥させた触媒を大気雰囲気などの含酸素雰囲気中で加熱し、活性金属成分を酸化させて酸化物を得る処理である。焼成処理は、例えば４００〜７００℃、好ましくは５００〜６００℃までの温度範囲で行われ、酸化物を得るのに十分な時間、例えば３０〜１２０分間、好ましくは４５〜９０分間程度、焼成が行われる。このような高温の雰囲気下では、キレート剤や無機酸は燃焼、分解してしまう場合があり、例えば無機酸を構成していたリンや窒素などの元素は水素化処理触媒上に残留してもよいし、焼成雰囲気中に流出してもよい。また、例えば酸化物中の酸素を利用する場合などには、焼成は不活性ガス雰囲気下で行ってもよい。
(Third step)
After aging for a predetermined time in the second step, the hydrotreating catalyst impregnated with the acid solution (hereinafter referred to as impregnated catalyst) is dried and fired. Here, the drying of the impregnated catalyst in the present invention means that the liquid component of the acid solution existing on the impregnated catalyst catalyst, such as the surface of the support and the pores, is evaporated. Therefore, drying should be performed under conditions sufficient to evaporate the liquid content of the impregnated catalyst, and the active metal component, the chelating agent, and the inorganic acid may undergo chemical changes during the drying process. It does not have to happen. The drying treatment is performed for a time sufficient to evaporate the liquid component, for example, within a temperature range from room temperature to 300 ° C., preferably from room temperature to 270 ° C., more preferably from room temperature to 250 ° C. The atmosphere in which the drying treatment is performed may be an oxygen-containing atmosphere such as an air atmosphere or an inert gas atmosphere that does not contain oxygen gas. The active metal component on the hydrotreating catalyst after the drying treatment may be supported in a state of forming a complex with the chelating agent, or the chelating agent is decomposed by the drying treatment in a metal state. Sometimes it is supported. Further, when dried in an oxygen-containing atmosphere, a part of the active metal component may be oxidized.
On the other hand, the calcination of the impregnated catalyst is a treatment in which an impregnated catalyst or a catalyst obtained by drying the impregnated catalyst is heated in an oxygen-containing atmosphere such as an air atmosphere to oxidize an active metal component to obtain an oxide. The baking treatment is performed, for example, in a temperature range of 400 to 700 ° C., preferably 500 to 600 ° C., and the baking is performed for a time sufficient to obtain an oxide, for example, 30 to 120 minutes, preferably about 45 to 90 minutes. Done. In such a high-temperature atmosphere, the chelating agent or inorganic acid may burn and decompose. For example, elements such as phosphorus and nitrogen that constitute the inorganic acid may remain on the hydrotreating catalyst. It may flow out into the firing atmosphere. For example, when oxygen in the oxide is used, the firing may be performed in an inert gas atmosphere.
以上に説明した手法により再生した水素化処理触媒は、炭化水素油の水素化処理装置の反応塔などに充填され、担体上の活性金属成分を硫化する予備硫化処理などが行われる。そして、所定の温度、圧力条件に調整された反応塔に炭化水素油と水素との混合流体を供給することにより、脱硫や水素化分解などの水素化処理が実行される。
本実施の形態に関わる水素化処理触媒の再生方法によれば以下の効果がある。焼成した後の水素化処理触媒を、無機酸とキレート剤との双方を含む酸溶液に接触させるので、無機酸により担体の細孔内への活性金属成分の浸透を促進させる効果および酸溶液の粘性を低減する効果と、キレート剤による担体−活性金属成分間の相互作用を軽減する効果とが発揮され、比較的短い時間で活性金属成分を再分散させることができる。
The hydrotreating catalyst regenerated by the above-described method is filled in a reaction tower of a hydrocarbon oil hydrotreating apparatus and subjected to a presulfidation process for sulfiding an active metal component on a support. Then, a hydrogenation process such as desulfurization or hydrocracking is performed by supplying a mixed fluid of hydrocarbon oil and hydrogen to a reaction tower adjusted to a predetermined temperature and pressure conditions.
The method for regenerating a hydroprocessing catalyst according to the present embodiment has the following effects. Since the hydrotreated catalyst after calcination is brought into contact with an acid solution containing both an inorganic acid and a chelating agent, the effect of promoting the penetration of the active metal component into the pores of the support by the inorganic acid and the acid solution The effect of reducing the viscosity and the effect of reducing the interaction between the carrier and the active metal component by the chelating agent are exhibited, and the active metal component can be redispersed in a relatively short time.
（炭化水素油の水素化処理触媒の再生処理試験）
炭化水素油である軽質軽油（以下、ＬＧＯという）または減圧軽油（以下、ＶＧＯという）の水素化処理触媒について、キレート剤および無機酸を含む溶液と、キレート剤、無機酸のいずれか一方のみを含む酸溶液を用いて再生処理を行い、触媒活性の向上の程度を調べた。
(Regeneration test of hydrocarbon oil hydrotreating catalyst)
About hydrotreating catalyst of light diesel oil (hereinafter referred to as LGO) or vacuum gas oil (hereinafter referred to as VGO) which is a hydrocarbon oil, a solution containing a chelating agent and an inorganic acid, and only one of the chelating agent and the inorganic acid Regeneration treatment was performed using the acid solution contained, and the degree of improvement in catalyst activity was examined.
１．水素化処理触媒
触媒Ａ：モリブデンおよびコバルトの前駆体と、無機酸（リン酸）とキレート剤（クエン酸）とを含む酸溶液を、アルミナ担体に含浸させ、１１０℃の大気雰囲気下で乾燥させてＬＧＯ用の水素化処理触媒を得た。リン酸の添加量は、アルミナ担体重量に対して１．０質量％、キレート剤の添加量は、キレート剤に対する無機酸のモル比（無機酸モル数／キレート剤モル数）が０．０９となるように調製した。得られたモリブデンの酸化物（ＭｏＯ３）換算の担持量は、全触媒質量の１８質量％、同じくコバルト酸化物（ＣｏＯ）換算の担持量は４．５質量％であった。
触媒Ｂ：モリブデンおよびコバルトの前駆体と、無機酸（リン酸）とを含む酸溶液（キレート剤は含んでいない）を、アルミナ担体に含浸させ、２５０℃の大気雰囲気下で乾燥させ、次いで５５０℃の大気雰囲気下で１時間、焼成処理を行ってＬＧＯ用の水素化処理触媒を得た。リン酸の添加量は、アルミナ担体重量に対して３．０質量％となるように調製した。モリブデン酸化物（ＭｏＯ３）の担持量は、全触媒質量の１９質量％、同じくコバルト酸化物（ＣｏＯ）の担持量は３．５質量％であった。
触媒Ｃ：モリブデン、コバルトおよびニッケルの前駆体と、無機酸（リン酸）とを含む酸溶液（キレート剤は含んでいない）を、アルミナ担体に含浸させ、２５０℃の大気雰囲気下で乾燥させ、次いで５５０℃の大気雰囲気下で１時間、焼成処理を行ってＶＧＯ用の水素化処理触媒を得た。リン酸の添加量は、アルミナ担体重量に対して３．０質量％となるように調製した。モリブデン酸化物（ＭｏＯ３）の担持量は、全触媒質量の１９質量％、同じくコバルト酸化物（ＣｏＯ）の担持量は３．０質量％、同じくニッケル酸化物（ＮｉＯ）の担持量は０．５質量％であった。
1. Hydrotreating catalyst
Catalyst A: An alumina carrier is impregnated with an acid solution containing a precursor of molybdenum and cobalt, an inorganic acid (phosphoric acid), and a chelating agent (citric acid), and dried in an air atmosphere at 110 ° C. for LGO. A hydrotreating catalyst was obtained. The addition amount of phosphoric acid is 1.0 mass% with respect to the weight of the alumina carrier, and the addition amount of the chelating agent is 0.09 as the molar ratio of the inorganic acid to the chelating agent (number of moles of inorganic acid / number of moles of chelating agent). It was prepared as follows. The obtained molybdenum oxide (MoO 3 ) equivalent loading was 18% by mass of the total catalyst mass, and the cobalt oxide (CoO) equivalent loading was 4.5% by mass.
Catalyst B: An acid solution (containing no chelating agent) containing a precursor of molybdenum and cobalt and an inorganic acid (phosphoric acid) is impregnated on an alumina support, dried in an air atmosphere at 250 ° C., and then 550 A calcination treatment was performed for 1 hour in an air atmosphere at 0 ° C. to obtain a hydrotreating catalyst for LGO. The amount of phosphoric acid added was adjusted to 3.0 mass% with respect to the alumina support weight. The supported amount of molybdenum oxide (MoO 3 ) was 19% by mass of the total catalyst mass, and the supported amount of cobalt oxide (CoO) was 3.5% by mass.
Catalyst C: An alumina carrier is impregnated with an acid solution containing molybdenum, cobalt and nickel precursors and an inorganic acid (phosphoric acid) (without a chelating agent), and dried in an air atmosphere at 250 ° C. Next, a calcination treatment was performed in an air atmosphere at 550 ° C. for 1 hour to obtain a hydrogenation catalyst for VGO. The amount of phosphoric acid added was adjusted to 3.0 mass% with respect to the alumina support weight. The supported amount of molybdenum oxide (MoO 3 ) was 19% by mass of the total catalyst mass, the supported amount of cobalt oxide (CoO) was 3.0% by mass, and the supported amount of nickel oxide (NiO) was 0.00%. It was 5 mass%.
２．使用済み触媒の調製
触媒Ａ〜Ｃの未使用触媒に対し、（表１）に示す性状のＬＧＯ（触媒Ａ、Ｂ）、またはＶＧＯ（触媒Ｃ）を、（表２）に示す脱硫条件で、１６０００時間通油して水素化処理を行い、使用済みの水素化処理触媒（使用済み触媒）を得た。各水素化処理の反応温度は、反応器出口のＬＧＯの硫黄含有量が７質量ｐｐｍ、同じくＶＧＯの硫黄含有量が０．２質量％となるように調整した。
2. Preparation of used catalyst With respect to the unused catalysts of catalysts A to C, LGO (catalysts A and B) or VGO (catalyst C) having the properties shown in (Table 1) are subjected to desulfurization conditions shown in (Table 2). The oil was passed through for 16000 hours to perform a hydrogenation treatment, and a used hydrotreatment catalyst (used catalyst) was obtained. The reaction temperature of each hydrogenation treatment was adjusted so that the sulfur content of LGO at the outlet of the reactor was 7 mass ppm and the sulfur content of VGO was 0.2 mass%.
３．再生処理
（１）第１工程
上述の１、２の条件で調製された使用済みの触媒Ａ〜Ｃについて以下の要領で再生処理をおこなった。まず前処理として、使用済みの触媒Ａ〜Ｃについては、２００℃に保持された窒素雰囲気中に配置し、表面に付着した油分を除去した。しかる後、４３０℃に保持された空気雰囲気中で３時間焼成した（第１工程）。この焼成により、使用済みの触媒に付着していたコークなどの炭素質は、触媒Ａでは０．３質量％、触媒Ｂでは０．３質量％、触媒Ｃでは０．５質量％となった。
3. Playback processing
(1) First step
The used catalysts A to C prepared under the above-described conditions 1 and 2 were regenerated in the following manner. First, as a pretreatment, the used catalysts A to C were placed in a nitrogen atmosphere maintained at 200 ° C. to remove oil adhering to the surface. Thereafter, firing was performed in an air atmosphere maintained at 430 ° C. for 3 hours (first step). As a result of the calcination, the carbonaceous matter such as coke adhered to the used catalyst was 0.3% by mass in the catalyst A, 0.3% by mass in the catalyst B, and 0.5% by mass in the catalyst C.
（２）第２工程
第１工程にて得られた使用済みの焼成触媒Ａ〜Ｃについて、炭素質を除いた条件で１０００ｇに相当する量を秤量し、各焼成触媒の細孔容積に相当する量の酸溶液を減圧含浸法によって含浸させた。各焼成触媒に含浸させた酸溶液の組成（使用済み触媒、添加活性金属、無機酸量の合計を１００質量％とする）を（表３）に示す。各触媒は、室温の大気雰囲気下で２時間熟成させて、使用済みの含浸触媒を得た。ここで、無機酸がリン酸の場合には、焼成後の触媒にはリンがＰ２Ｏ５として担持される一方、硝酸は焼成後の触媒に残らないことを考慮し、モル換算の無機酸添加量は、下記式に基づいて計算した。
ａ．無機酸がリン酸の場合
（無機酸添加量［ｍｏｌ］）＝
（使用済み触媒１０００［ｇ］）×（無機酸添加量［質量％］）
／｛１００−（活性金属添加量［質量％］＋無機酸添加量［質量％］）｝
／（リン酸分子量９８［ｇ／ｍｏｌ］） …（１）
ｂ．無機酸が硝酸の場合
（無機酸添加量［ｍｏｌ］）＝
（使用済み触媒１０００［ｇ］）×（無機酸添加量［質量％］）
／（１００−活性金属添加量［質量％］）
／（硝酸分子量６３［ｇ／ｍｏｌ］） …（２）
(2) Second step
For the used calcined catalysts A to C obtained in the first step, an amount corresponding to 1000 g is weighed under the condition excluding carbonaceous matter, and an acid solution corresponding to the pore volume of each calcined catalyst is decompressed. Impregnation was performed by an impregnation method. Table 3 shows the composition of the acid solution impregnated in each calcined catalyst (the total amount of used catalyst, added active metal, and inorganic acid is 100% by mass). Each catalyst was aged for 2 hours in an air atmosphere at room temperature to obtain a used impregnated catalyst. Here, in the case where the inorganic acid is phosphoric acid, in consideration of the fact that phosphorus is supported as P 2 O 5 on the catalyst after calcination, nitric acid does not remain in the catalyst after calcination. The addition amount was calculated based on the following formula.
a. When the inorganic acid is phosphoric acid
(Inorganic acid addition amount [mol]) =
(Used catalyst 1000 [g]) × (addition amount of inorganic acid [mass%])
/ {100- (active metal addition [mass%] + inorganic acid addition [mass%])}
/ (Phosphoric acid molecular weight 98 [g / mol]) (1)
b. When the inorganic acid is nitric acid (addition amount of inorganic acid [mol]) =
(Used catalyst 1000 [g]) × (addition amount of inorganic acid [mass%])
/ (100-active metal addition amount [mass%])
/ (Nitric acid molecular weight 63 [g / mol]) (2)
（３）第３工程
第２工程にて得られた含浸触媒につき、触媒Ａについては１１０℃の大気雰囲気下で乾燥させ、触媒Ｂ、Ｃについては２５０℃の大気雰囲気下で乾燥させ、さらに５５０℃の大気雰囲気中で１時間焼成した。こうして（第１工程）〜（第３工程）の再生処理が行われた未使用触媒、および使用済み触媒Ａ〜Ｃを得た。
(3) Third step
Regarding the impregnated catalyst obtained in the second step, catalyst A is dried in an air atmosphere of 110 ° C., catalysts B and C are dried in an air atmosphere of 250 ° C., and further in an air atmosphere of 550 ° C. Baked for 1 hour. Thus, an unused catalyst and used catalysts A to C that were subjected to the regeneration treatment in the (first step) to (third step) were obtained.
（脱硫活性評価試験）
再生処理を行った触媒Ａ〜Ｃを反応器に充填し、硫化水素を通流させて硫化処理を行った後、（表２）に示した水素化処理条件にて、（表１）に示したＬＧＯ、ＶＧＯの水素化脱硫処理を行った。反応器を通過する前後での炭化水素油中の硫黄濃度の変化から、下記（３）式に基づいて反応速度定数を求めた。そして、未使用触媒Ａ〜Ｃの反応速度定数（Ｋｎ０）に対する、再生触媒の反応速度定数（Ｋｎ）の比をパーセント表示で表した値（（Ｋｎ／Ｋｎ０）×１００［％］）を相対活性とした。
Ｋｎ＝ＬＨＳＶ×１／（ｎ−１）×（１／Ｓｎ−1−１／Ｓ０ ｎ−１） …（３）
ここで、
Ｋｎ：反応速度定数
ｎ：脱硫反応速度が原料油の硫黄濃度の何乗に比例するか（ＬＧＯでは１．５、ＶＧＯでは２．０）
Ｓ：処理油中の硫黄濃度（％）
Ｓ０：原料油中の硫黄濃度（％）
ＬＨＳＶ：液空間速度（ｈｒ−１）
(Desulfurization activity evaluation test)
After the regenerated catalyst A to C is charged into the reactor, hydrogen sulfide is passed through and subjected to sulfurization treatment, the hydrotreatment conditions shown in (Table 2) are shown in (Table 1). Then, hydrodesulfurization treatment of LGO and VGO was performed. From the change in the sulfur concentration in the hydrocarbon oil before and after passing through the reactor, the reaction rate constant was determined based on the following formula (3). A value ((K n / K n0 ) × 100 [%]) representing the ratio of the reaction rate constant (Kn) of the regenerated catalyst to the reaction rate constant (K n0 ) of the unused catalysts A to C. Was defined as relative activity.
K n = LHSV × 1 / (n−1) × (1 / S n−1 −1 / S 0 n−1 ) (3)
here,
K n : Reaction rate constant
n: The desulfurization reaction rate is proportional to the power of the sulfur concentration of the feedstock (1.5 for LGO, 2.0 for VGO)
S: Sulfur concentration in treated oil (%)
S 0 : Sulfur concentration (%) in the feedstock
LHSV: Liquid space velocity (hr −1 )
（実施例１〜８）使用済み触媒Ａに、各々酸溶液ａ〜ｈを含浸させて再生処理を行い、ＬＧＯを処理して触媒の相対脱硫活性を求めた。
（実施例９〜１６）使用済み触媒Ｂに、各々酸溶液ａ〜ｈを含浸させて再生処理を行い、ＬＧＯを処理して触媒の相対脱硫活性を求めた。
（実施例１７〜２４）使用済み触媒Ｃに、各々酸溶液ａ〜ｈを含浸させて再生処理を行い、ＶＧＯを処理して触媒の相対脱硫活性を求めた。
（比較例１、２）使用済み触媒Ａに、各々酸溶液ｉ、ｊを含浸させて再生処理を行い、ＬＧＯを処理して触媒の相対脱硫活性を計測した。
（比較例３、４）使用済み触媒Ｂに、各々酸溶液ｉ、ｊを含浸させて再生処理を行い、ＬＧＯを処理して触媒の相対脱硫活性を計測した。
（比較例５、６）使用済み触媒Ｃに、各々酸溶液ｉ、ｊを含浸させて再生処理を行い、ＶＧＯを処理して触媒の相対脱硫活性を計測した。
(Examples 1 to 8) The spent catalyst A was impregnated with acid solutions a to h, respectively, and regenerated, and LGO was treated to determine the relative desulfurization activity of the catalyst.
(Examples 9 to 16) The used catalyst B was impregnated with acid solutions a to h, respectively, and regenerated, and LGO was processed to determine the relative desulfurization activity of the catalyst.
(Examples 17 to 24) The used catalyst C was impregnated with acid solutions a to h, respectively, and regenerated, and VGO was processed to determine the relative desulfurization activity of the catalyst.
(Comparative Examples 1 and 2) The spent catalyst A was impregnated with acid solutions i and j, respectively, and regenerated, and LGO was treated to measure the relative desulfurization activity of the catalyst.
(Comparative Examples 3 and 4) The spent catalyst B was impregnated with acid solutions i and j, respectively, and regenerated, and LGO was treated to measure the relative desulfurization activity of the catalyst.
(Comparative Examples 5 and 6) The spent catalyst C was impregnated with acid solutions i and j, respectively, regenerated, VGO was treated, and the relative desulfurization activity of the catalyst was measured.
上述の（実施例１〜２４）、（比較例１〜６）の結果を（表４）にまとめた。（表４）において、同じ行に示した実施例は、共通の酸溶液を用いて再生処理が行われている。（実施例１〜８）、（比較例１〜２）は、触媒Ａ（乾燥処理品）にてＬＧＯを処理した結果を示しており、（実施例９〜１６）、（比較例３〜４）は触媒Ｂ（焼成品）にてＬＧＯを処理した結果を示している。また（実施例１７〜２４）、（比較例５〜６）は触媒Ｃ（焼成品）にてＶＧＯを処理した結果である。（表３）に示したように、全ての実施例に関わる触媒の再生処理に用いた酸溶液（酸溶液ａ〜ｈ）には、無機酸（リン酸または硝酸）とキレート剤（クエン酸またはリンゴ酸）の双方が含まれている。これに対して比較例に関わる触媒を再生処理した酸溶液には、無機酸（酸溶液ｊ（硝酸））またはキレート剤（酸溶液ｉ（クエン酸））のいずれか一方が含まれている。 The results of the above-mentioned (Examples 1 to 24) and (Comparative Examples 1 to 6) are summarized in (Table 4). In Table 4, the examples shown in the same row are regenerated using a common acid solution. (Examples 1 to 8) and (Comparative Examples 1 and 2) show the results of treating LGO with Catalyst A (dried product), (Examples 9 to 16) and (Comparative Examples 3 to 4). ) Shows the result of treating LGO with catalyst B (calcined product). Further, (Examples 17 to 24) and (Comparative Examples 5 to 6) are results of treating VGO with catalyst C (calcined product). As shown in (Table 3), the acid solution (acid solutions a to h) used for the regeneration treatment of the catalyst according to all examples includes an inorganic acid (phosphoric acid or nitric acid) and a chelating agent (citric acid or citric acid). Both of malic acid) are included. On the other hand, the acid solution obtained by regenerating the catalyst according to the comparative example contains either an inorganic acid (acid solution j (nitric acid)) or a chelating agent (acid solution i (citric acid)).
（表４）に示した各実施例の結果によれば、無機酸とキレート剤との双方を含む酸溶液ａ〜ｈを利用して再生処理を行った場合の相対的脱硫活性は、使用済み触媒Ａの場合で８１〜１０３％（実施例１〜８）、使用済み触媒Ｂの場合で８３〜１０１％（実施例９〜１６）、使用済み触媒Ｃの場合で８０〜９６％（実施例１７〜２４）であった。
実施例に関わる再生処理の結果を概観すると、同じ酸溶液を使用した場合使用済み触媒Ａ〜Ｃ（実施例１〜２４）においては、より重質の炭化水素油を処理している使用済み触媒Ｃ（実施例１７〜２４）にてやや再生処理の効果が低い。これは、ＬＧＯに比べてＶＧＯの水素化処理の条件が過酷なため、ＬＧＯを処理した触媒（使用済み触媒Ａ、Ｂ）と同じ熟成時間では、活性金属成分の再分散の効果が十分でないためではないかと考えられる。また、同じＬＧＯを処理した使用済み触媒Ａ、Ｂの間では、乾燥品であるか焼成品であるかにかかわらず、酸溶液が同じであれば、ほぼ同等の相対的脱硫活性が得られている。
According to the result of each Example shown in (Table 4), the relative desulfurization activity at the time of performing a reproduction | regeneration process using the acid solution ah containing both an inorganic acid and a chelating agent is used. In the case of catalyst A, 81 to 103% (Examples 1 to 8), in the case of used catalyst B, 83 to 101% (Examples 9 to 16), in the case of used catalyst C, 80 to 96% (Examples) 17-24).
An overview of the results of the regeneration treatment related to the examples shows that when the same acid solution is used, in the used catalysts A to C (Examples 1 to 24), a used catalyst that is treating a heavier hydrocarbon oil. In C (Examples 17 to 24), the effect of the reproduction process is slightly low. This is because the VGO hydrotreating conditions are harsh compared to LGO, and the effect of redispersing the active metal component is not sufficient at the same aging time as the LGO-treated catalysts (used catalysts A and B). It is thought that. In addition, between the used catalysts A and B treated with the same LGO, regardless of whether the catalyst is a dry product or a calcined product, almost the same relative desulfurization activity can be obtained if the acid solution is the same. Yes.
これに対して、無機酸のみを含む酸溶液ｊを利用して再生処理を行った触媒の相対的脱硫活性を見ると、使用済み触媒Ａでは７５％（比較例２）、使用済み触媒Ｂでは８３％（比較例４）、使用済み触媒触媒Ｃでは７３％（比較例６）であった。これらの結果は、相対的脱硫活性の値が等しい（実施例１６）と（比較例４）の場合を除き、無機酸とキレート剤の双方を含む酸溶液ａ〜ｈを用いて再生処理を行った方が、無機酸のみを含む酸溶液ｊを用いる場合よりも、処理後の相対的脱硫活性が高くなることを示している。これは、無機酸のみを含む酸溶液ｊでは、水素化処理触媒の担体と活性金属成分との間に働く相互作用が抑制されず、活性金属成分を十分に分散させることができなかったためではないかと考えられる。
また、キレート剤のみを含む酸溶液ｉを利用して再生処理を行った触媒の相対的脱硫活性を見ると、使用済み触媒Ａでは８４％（比較例１）、使用済み触媒Ｂでは８６％（比較例３）、使用済み触媒触媒Ｃでは７８％（比較例５）であった。
In contrast, when the relative desulfurization activity of the catalyst that was regenerated using the acid solution j containing only the inorganic acid was seen, it was 75% for the used catalyst A (Comparative Example 2) and for the used catalyst B. 83% (Comparative Example 4) and 73% (Comparative Example 6) of the used catalyst catalyst C. These results show that the regeneration treatment was performed using the acid solutions a to h containing both the inorganic acid and the chelating agent, except in the cases of the comparative desulfurization activity values (Example 16) and (Comparative Example 4). Shows that the relative desulfurization activity after the treatment is higher than that in the case of using the acid solution j containing only the inorganic acid. This is not because the acid solution j containing only the inorganic acid did not suppress the interaction between the support of the hydrotreating catalyst and the active metal component, and the active metal component could not be sufficiently dispersed. It is thought.
Further, when the relative desulfurization activity of the catalyst which was regenerated using the acid solution i containing only the chelating agent was observed, it was 84% for the used catalyst A (Comparative Example 1) and 86% for the used catalyst B ( In Comparative Example 3), the spent catalyst catalyst C was 78% (Comparative Example 5).
これらの結果は、酸溶液ｈを用いた（実施例８、１６、２４）の場合を除いて、無機酸とキレート剤の双方を含む酸溶液ａ〜ｈを用いて再生処理を行った方が、キレート剤のみを含む酸溶液ｉを用いる場合よりも、同じ時間熟成を行った場合の相対的脱硫活性が高くなることを示している。そして発明者らは、酸溶液ｉを利用した場合においても、各比較例よりも長い熟成時間を確保することによって相対的脱硫活性の値を向上させることが可能であることを確認している。
ここで酸溶液ｈが無機酸とキレート剤との双方を含んでいるにもかかわらず、キレート剤のみを含む酸溶液ｉと比較して触媒を再生する効果が低い理由について検討する。酸溶液ｈは実施例に関わる酸溶液の中では無機酸（リン酸）の添加量が最も多く、キレート剤に対する無機酸のモル比（無機酸／キレート剤）の値も０．４２８と最も高い。このため、キレート剤の添加効果が弱まり、高い再生効果が発揮されなかったのではないかと考えられる。この観点から、既述のように前記モル比の値は、０．０１〜０．２の範囲内が好適であり、さらには０．０４〜０．１８がより好ましいといえる。但し、酸溶液ｈを用いた場合であっても無機酸のみを含む酸溶液ｊと同等かそれ以上の再生効果が得られていることから、酸溶液ｈが触媒の活性を向上させる効果を備えていることは否定されない。
These results are obtained when the regeneration treatment is performed using the acid solutions a to h containing both the inorganic acid and the chelating agent except in the case of using the acid solution h (Examples 8, 16, and 24). It shows that the relative desulfurization activity is higher when the aging is performed for the same time than when the acid solution i containing only the chelating agent is used. The inventors have confirmed that even when the acid solution i is used, it is possible to improve the relative desulfurization activity value by securing a longer aging time than each comparative example.
Here, the reason why the effect of regenerating the catalyst is low as compared with the acid solution i containing only the chelating agent although the acid solution h contains both the inorganic acid and the chelating agent will be examined. The acid solution h has the highest added amount of inorganic acid (phosphoric acid) among the acid solutions related to the examples, and the highest molar ratio (inorganic acid / chelating agent) of the inorganic acid to the chelating agent is 0.428. . For this reason, it is thought that the addition effect of a chelating agent weakened and the high regeneration effect was not exhibited. From this viewpoint, as described above, the value of the molar ratio is preferably in the range of 0.01 to 0.2, and more preferably 0.04 to 0.18. However, even when the acid solution h is used, since the regeneration effect is equal to or higher than that of the acid solution j containing only the inorganic acid, the acid solution h has an effect of improving the activity of the catalyst. That is not denied.
次いで、活性金属成分の添加効果について確認する。酸溶液ｄは、酸化物としてモリブデンを０．５質量％、コバルトを０．２５質量％、ニッケルを０．２５質量％含んでいる。一方でこの酸溶液ｄと「無機酸（リン酸）／キレート剤（クエン酸）」のモル比がほぼ同じ値となっている酸溶液ａは、活性金属成分の添加量がゼロである。そこで、両実施例（酸溶液ｄ；実施例４、１２、２０、酸溶液ａ；実施例１、９、１７）を比較すると、いずれの実施例も酸溶液ｄを用いた方の相対的脱硫活性が高く、活性金属成分を添加することによる再生処理効果の向上を確認できる。
一方で、酸化物としてモリブデンおよびコバルトを３質量％ずつ添加した酸溶液ｇについては、（実施例７、１５、２３）の相対化脱硫活性の値は８９〜１０１程度である。この値は他の実施例における脱硫活性（酸溶液ｈを利用した実施例は除く）の値である９０〜１０７と比較して低めの活性値となっている。従って、活性金属成分の添加量を増やすだけで、無機酸およびキレート剤の添加効果を上回る触媒の再生効果が得られる訳ではないことが確認できる。
Next, the effect of adding the active metal component will be confirmed. The acid solution d contains 0.5% by mass of molybdenum, 0.25% by mass of cobalt, and 0.25% by mass of nickel as oxides. On the other hand, in the acid solution d in which the molar ratio of the acid solution d and “inorganic acid (phosphoric acid) / chelating agent (citric acid)” is substantially the same, the amount of the active metal component added is zero. Therefore, when both examples (acid solution d; Examples 4, 12, and 20, acid solution a; Examples 1, 9, and 17) are compared, in each example, relative desulfurization using the acid solution d is performed. The activity is high, and it can be confirmed that the regeneration treatment effect is improved by adding the active metal component.
On the other hand, with respect to the acid solution g to which molybdenum and cobalt are added in an amount of 3% by mass as oxides, the value of the relative desulfurization activity of (Examples 7, 15, and 23) is about 89 to 101. This value is a lower activity value compared to 90 to 107, which is the value of desulfurization activity (excluding examples using the acid solution h) in other examples. Therefore, it can be confirmed that the catalyst regeneration effect exceeding the effect of adding the inorganic acid and the chelating agent cannot be obtained only by increasing the addition amount of the active metal component.
Claims (6)
この第１工程にて焼成された水素化処理触媒を無機酸とキレート剤との双方を含む酸溶液に接触させて、前記活性金属成分を担体上に分散させる第２工程と、を含み、無機酸がリン酸または硝酸であり、キレート剤が多価カルボン酸であるクエン酸またはリンゴ酸であることを特徴とする水素化処理触媒の再生方法。 A used hydrocarbon oil hydrotreating catalyst in which at least one active metal component selected from Groups 6 and 8 to 10 of the periodic table is supported on a support is calcined at a temperature exceeding 300 ° C. The first step;
The hydrotreating catalysts calcined at the first step into contact with an acid solution containing both an inorganic acid and a chelating agent, wherein the second step of dispersing onto the support of the active metal component, an inorganic A method for regenerating a hydrotreatment catalyst, wherein the acid is phosphoric acid or nitric acid, and the chelating agent is citric acid or malic acid, which is a polyvalent carboxylic acid.
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