JP4865940B2 - Hydrotreating catalyst and method for hydrotreating heavy hydrocarbon oil using the catalyst - Google Patents
Hydrotreating catalyst and method for hydrotreating heavy hydrocarbon oil using the catalyst Download PDFInfo
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- JP4865940B2 JP4865940B2 JP2000234049A JP2000234049A JP4865940B2 JP 4865940 B2 JP4865940 B2 JP 4865940B2 JP 2000234049 A JP2000234049 A JP 2000234049A JP 2000234049 A JP2000234049 A JP 2000234049A JP 4865940 B2 JP4865940 B2 JP 4865940B2
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- Prior art keywords
- catalyst
- hydrotreating
- alumina
- heavy hydrocarbon
- metal
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- Expired - Fee Related
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- 239000003054 catalyst Substances 0.000 title claims description 104
- 238000000034 method Methods 0.000 title claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 18
- 229930195733 hydrocarbon Natural products 0.000 title claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 230000000737 periodic effect Effects 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 47
- 239000003921 oil Substances 0.000 description 39
- 230000000694 effects Effects 0.000 description 26
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000006477 desulfuration reaction Methods 0.000 description 22
- 230000023556 desulfurization Effects 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
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- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
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- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 6
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 238000007324 demetalation reaction Methods 0.000 description 5
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- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 239000001630 malic acid Substances 0.000 description 4
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 229910052721 tungsten Inorganic materials 0.000 description 2
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は水素化処理触媒及びこれを用いた重質炭化水素油の水素化処理方法に関し、より詳しくは特定の物性を有する水素化処理触媒、及びこれを用いた重質炭化水素油の水素化処理方法に関する。
【０００２】
【従来の技術】
現在、酸性雨等からの環境保護のため、燃料油中の硫黄分は水素化精製処理により低減されており、そこで脱硫触媒が一般に使用されている。しかし、特に常圧残油、減圧残油等の重質油を原料として低硫黄重油を生産する場合において、触媒の脱硫性能の限界から触媒寿命は短く、１年未満となっている。したがって、１年以内で精製装置を停止し、触媒を交換せざるを得ない。このように、重質油から低硫黄重油を生産する場合、灯軽油の水素化処理に比較して、硫黄分を低減するためには、運転初期から高い温度を必要とする。また、触媒の活性は時間とともに劣化していくため、製品の硫黄分の量を一定に維持するためには、運転温度を徐々に上げていく必要がある。特に、重質油にはバナジウム、ニッケルといった金属分が含まれ、反応中に触媒に堆積して活性を被毒するため、触媒の劣化が著しい。このため、１年以内に装置の上限温度に達し、触媒を交換することとなるわけである。したがって、より低温における高脱硫活性と耐金属蓄積性を有する触媒の開発が望まれている。
【０００３】
【発明が解決しようとする課題】
本発明は、上記観点からなされたもので、より低温における高脱硫活性と耐金属蓄積性を有する水素化処理触媒を提供するとともに、その水素化処理触媒を用いた重質炭化水素油の水素化処理方法を提供することを目的とするものである。
【０００４】
【課題を解決するための手段】
本発明者らは鋭意研究の結果、特定の物性を有する水素化処理触媒を使用することにより、上記本発明の目的を効果的に達成しうることを見出し本発明を完成したものである。
【０００５】
すなわち、本発明の要旨は下記のとおりである。
１．シリカを１〜１０質量％含有するアルミナ担体に、周期律表第６族の金属の少なくとも一種及び周期律表第８〜１０族の金属から選ばれる少なくとも一種を担持し、さらにリンを触媒基準で、酸化物基準で３〜５質量％含有する触媒であって、前記担体への金属の担持が、沸点又は分解温度２００℃以上の水溶性有機化合物を含有する含浸液を用いてなされたものであり、該触媒の平均細孔直径（ＰＤ）が１００〜１７０Åで、比表面積（ＳＡ）が１４０〜２５０ｍ2 ／ｇであり、かつ両者が下記の（１）式を満足し、さらに全細孔容量が０．４〜１．０ｃｃ／ｇであることを特徴とする水素化処理触媒。
ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１）
２．周期律表第６族金属がモリブデンであり、周期律表第８〜１０族金属がニッケルである上記１記載の水素化処理触媒。
３．水溶性有機化合物がポリエチレングリコールもしくは１，３−ブタンジオールである上記１又は２に記載の水素化処理触媒。
４．上記１〜３のいずれかに記載した水素化処理触媒を用いた重質炭化水素油の水素化処理方法。
５．上流側に脱金属触媒、下流側に上記１〜３のいずれかに記載の水素化処理触媒を用いた上記４記載の重質炭化水素油の水素化処理方法。
６．重質炭化水素油が減圧軽油、常圧残油又は減圧残油である上記４又は５に記載の重質炭化水素油の水素化処理方法。
【０００６】
【発明の実施の形態】
以下に本発明について詳細に説明する。
本発明の水素化処理触媒は、シリカを１〜１０質量％含有するアルミナ担体に、周期律表第６族の金属の少なくとも一種及び周期律表第８〜１０族の金属から選ばれる少なくとも一種を担持した触媒であって、該触媒の平均細孔直径（ＰＤ）が１００〜１７０Åで、比表面積（ＳＡ）が１４０〜２５０ｍ2 ／ｇであり、かつ両者が下記の（１）式を満足し、さらに全細孔容量が０．４〜１．０ｃｃ／ｇであることを特徴とする。
ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１）
【０００７】
まず、アルミナ担体に添加するシリカの量は１〜１０質量％である。１質量％未満であると、アルミナの表面積を大にする効果は少なく、１０質量％を超えると、特定の含浸液が担体に高分散に金属を担持する能力が低下し好ましくない。担体に担持する金属については、周期律表第６族金属として、モリブデン、タングステンなどを挙げることができるが、モリブデンが好ましい。第６族金属の担持量は、触媒基準で、酸化物基準で４〜２５質量％、好ましくは８〜２０質量％である。周期律表第８〜１０族の金属として、コバルト、ニッケルなどを挙げることができるが、ニッケルが好ましい。第８〜１０族金属の担持量は、触媒基準で、酸化物基準で１〜８質量％、好ましくは２〜５質量％である。また、その他の成分としては、特にリンが必要である。リンを添加すると、触媒の水素化活性が向上し、特に重質炭化水素油を原料とする場合においては、脱硫活性が向上する。その効果は添加量が、触媒基準で、酸化物基準で３〜５質量％で顕著となる。
【０００８】
触媒の平均細孔直径（ＰＤ）は１００〜１７０Åである。１００Å未満であると、原料の炭化水素油中のバナジウムやニッケルの金属の堆積及びコーク前駆体の堆積により、短時間で細孔が閉塞し脱硫活性が低下してしまう。１７０Åを超えると、運転初期において、脱硫活性が著しく低くなり好ましくない。触媒の比表面積（ＳＡ）は１４０〜２５０ｍ2 ／ｇである。１４０ｍ2 ／ｇ未満であると、触媒の脱硫活性が低く、２５０ｍ2 ／ｇを超えると、脱硫活性が飽和してしまい、効率が悪い。また、上記ＰＤとＳＡは前記式（１）を満足する必要がある。その式（１）を満足しないと、脱硫活性及び触媒寿命ともに劣る触媒となる。
【０００９】
次いで、上記水素化処理触媒の製造方法について説明する。
まず、担体のシリカ含有アルミナ担体の製造法としては、一般的には、アルミナ源とシリカ源を混合し、沈殿を熟成させ、乾燥させ、焼成する。
【００１０】
用いられるアルミナ源としては、硫酸アルミニウム，硝酸アルミニウム等の 水溶性酸性アルミナ塩、アルミン酸ソーダ等の水溶性塩基性アルミナ塩を挙げることができる。用いられるシリカ源としては、水ガラス，珪酸ナトリウム，シリカゾル等を挙げることができる。アルミナ源とシリカ源を混合する場合のｐＨは３〜１０、好ましくは３．３〜９．３である。混合温度は３０〜９０℃、好ましくは５０〜８０℃である。
【００１１】
生成した沈殿の熟成方法については、一般には、混合時と同じ温度にて酸性及びアルカリ性溶液を交互に加える操作（スイング）を、ｐＨ３．０〜９．３の間で３回以上、好ましくは５回以上行うことによって行うことができる。また、ｐＨ９以上にて温度７０℃以上、好ましくはｐＨ１０以上にて温度８０℃以上で、一定の時間攪拌する方法を用いることもできる。これをスイング法と組み合わせてもよい。熟成した沈殿を８０〜２００℃（好ましくは１００〜１６０℃）で乾燥させ、４００〜７００℃（好ましくは５００〜６００℃）で焼成する。
【００１２】
上記の沈殿を得る方法として、アルミナ及びシリカのゲルを各々予め製造しておき両者を混合する方法、アルミナゲルにシリカ化合物の水溶液を混合する方法、アルミニウム化合物を含む溶液とアルミニウム化合物及びシリカ化合物を混合して沈殿を得る方法、アルミニウム化合物及びシリカ化合物を含む溶液のｐＨを変化させて沈殿を得る方法などを採用することができる。
【００１３】
特に望ましい担体の沈殿を得るためには、水溶性塩基性アルミナ塩に、一旦、実質的にゲルを生じない条件で水溶性シリカを混合せしめた溶液を調製し、更に水溶性アルミナ塩を添加してゲルを生成せしめる方法を採用すればよい。さらに詳細に述べると、実質的にゲルを生じない条件で水溶性塩基性アルミナ塩と水溶性シリカの溶液を混合するには、水溶性塩基性アルミナ塩の水溶液に、予めアンモニア水や水酸化ナトリウム等の塩基を添加してｐＨを１０以上に高めてから、水溶性シリカを添加すればよい。または、ｐＨ３以下で水ガラスと硫酸アルミニウムを混合することによっても、実質的にゲルを生じない混合が可能である。このようにして得られたシリカ・アルミナの水溶液に、さらに水溶性の酸性アルミナ溶液あるいは塩基性アルミナ溶液を添加して沈殿を生じさせる。アルカリ側で調製したシリカ・アルミナ透明溶液から沈殿を得るためには、水溶性の酸性アルミナ溶液を添加することが有効であり、酸性側で調製したシリカ・アルミナ透明溶液から沈殿を得るためには、水溶性の塩基性アルミナ溶液を添加することが有効である。
【００１４】
以上のようにして得られたシリカ含有アルミナ担体に、以下の方法で金属を担持することができる。担持法は含浸法が好ましい。周期律表第６族のモリブデン化合物としては、三酸化モリブデン，パラモリブデン酸アンモニウム等が使用され、タングステン化合物としては、三酸化タングステン，タングステン酸アンモニウム等が使用される。また、周期律表第８〜１０族のニッケル化合物としては、硝酸ニッケル，塩基性炭酸ニッケル等が使用され、コバルト化合物としては、硝酸コバルト，塩基性炭酸コバルト等が使用される。さらに、リン化合物としては、五酸化リン，リン酸等が使用される。上記の金属化合物を、周期律表第６族金属は０．７〜４．３モル／リットル、周期律表第８〜１０族の金属は０．３〜２．４モル／リットル、リン化合物は１．１〜２．０モル／リットルの割合で純水に溶解させ、さらに沸点又は分解温度２００℃以上の水溶性有機化合物を５０〜２００ｇ／リットルの割合で溶解させたものを含浸液とし、担体に吸水率と等量になるように調整後含浸させる。その沸点又は分解温度２００℃以上の水溶性有機化合物として、１，３−ブタンジオール，１，４−ブタンジオール，ポリエチレングリコール，ポリオキシエチレンフェニルエーテル，ポリオキシエチレンオクチルフェニルエーテル等のエーテル基含有水溶性高分子、ポリビニルアルコール等のアルコール水溶性高分子、サッカロース，グリコース等の各種糖類、メチルセルロース，水溶性でんぷん等の水溶性多糖類及びこれらの誘導体を使用することができるが、分子量４００以上のポリエチレングリコールが好ましい。沸点又は分解温度２００℃以上の水溶性有機化合物を使用することにより、金属の担体での凝集を抑制することができる。
【００１５】
なお、含浸液のｐＨ調整は特に限定されないが、硝酸，塩酸，硫酸等の無機酸、りんご酸，エチレンジアミン４酢酸等の有機酸、アンモニアなどを使用して行うことができる。含浸後乾燥、焼成するが、乾燥温度は８０〜２００℃（好ましくは１００〜１５０℃）、焼成温度は３００〜６００℃（好ましくは４００〜５５０℃）である。焼成温度が低すぎると、担持成分と担体と十分な結合を持つことができない場合があり、高すぎると、担持成分の凝集が起こり易くなる。
【００１６】
次に、本発明の水素化処理触媒を用いて水素化処理を行う際には、予め安定化処理として予備硫化を行うことが望ましい。この予備硫化処理の条件は特に限定されないが、通常、予備硫化剤として、硫化水素，二硫化炭素，チオフェン，ジメチルジスルフィド等を挙げることができ、処理温度２００〜４００℃、処理圧力常圧〜３０ＭＰａの範囲で行われる。
【００１７】
触媒の形状については、特に重質炭化水素油の水素化処理に使用される触媒は、通常押出成形で製造されるものが多く、その形状は実質的に柱状をしている。その断面は円形のものが多いが、三葉型、四葉型など外表面を多くする工夫のあるものもある。また、球状触媒もよく用いられる。球状触媒は圧縮強度や耐磨耗性が特に要求される場合に使用される。
【００１８】
水素化処理条件については、原料油の種類や目的により異なるが、一般的には反応温度２００〜５５０℃（好ましくは２２０〜５００℃）、水素分圧５〜３０ＭＰａ（好ましくは１０〜２５ＭＰａ）の範囲で行われる。
【００１９】
反応形式は特に限定されないが、通常は、固定床，移動床，沸騰床，懸濁床等の種々のプロセスから選択できるが、固定床が好ましい。
固定床の場合の温度、圧力以外の反応条件としては、液空間速度（ＬＨＳＶ）は０．０５〜１０ｈｒ-1（好ましくは０．１〜５ｈｒ-1）、水素／オイル比は５００〜２，５００Ｎｍ3 ／ｋｌ（好ましくは７００〜２，０００Ｎｍ3 ／ｋｌ）である。
【００２０】
本願の第二発明は、前記水素化処理触媒を用いた重質炭化水素油の水素化処理方法である。
該重質炭化水素として、常圧残油，減圧残油，減圧軽油，脱蝋減圧残油，アスファルテン油，タールサンド油及びこれらを一旦予備的二水素化処理した残油を挙げることができる。また、上記残油と接触分解軽油との混合油（残油／接触分解油（容量比）は１以上、好ましくは１．５以上）も使用することができる。原料油の性状として、特に限定されないが、代表的な性状としては下記のとおりである。
【００２１】
比重（１５／４℃）：０．９５３０〜０．９９４０
動粘度（５０℃）：２５０〜３，０００ｃＳｔ
硫黄分：２．８〜４．５質量％
窒素分：１，５００〜４，２００ｐｐｍ
金属分（Ｖ，Ｎｉ）：３０〜２５０ｐｐｍ
残炭分：５〜１８質量％
アスファルテン分：０．５〜１２．０質量％
反応条件としては、上記の原料油を、単層の水素化処理触媒を充填して水素化処理してもよいが、より高脱硫活性で長寿命な触媒にするために、上流側にアルミナ担体に周期律表第６族の少なくとも一種及び周期律表第８〜１０族から選ばれる少なくとも一種を担持した脱金属触媒を用い、下流側に本発明の水素化処理触媒を用いた触媒システムにすればよい。
【００２２】
上記の上流側に使用する脱金属触媒の物性等の例を下記に示す。
周期律表第６族の金属として、モリブデン、タングステンなどを挙げることができるが、モリブデンが好ましい。第６族金属の担持量は、触媒基準で、酸化物基準で２〜１５質量、好ましくは４〜１２質量％である。周期律表第８〜１０族の金属として、コバルト、ニッケルなどを挙げることができるが、ニッケルが好ましい。第８〜１０族金属の担持量は、触媒基準で、酸化物基準で１〜４質量％、好ましくは１．５〜２．５質量％である。担体としては、アルミナが望ましく、触媒の細孔径は１００〜２５０Å（好ましくは１５０〜２２０Å）、比表面積は、８０〜２００ｍ2 ／ｇ（好ましくは１００〜１８０ｍ2 ／ｇ）、細孔容積は０．４〜１．０ｃｃ／ｇ（好ましくは０．５〜０．９ｃｃ／ｇ）である。
【００２３】
脱金属触媒と本発明の水素化処理触媒の充填割合は、脱金属触媒が１０〜５０容量％（好ましくは２０〜４０容量％）に対して、本発明の水素化処理触媒は５０〜９０容量％（好ましくは６０〜８０容量％）である。
【００２４】
【実施例】
次に、本発明を実施例により具体的に説明するが、本発明はこれらの実施例によりなんら制限されるものではない。
〔実施例１〕
純水２．３８リットルを７０℃に加温し、攪拌しながら、水ガラス１６ｇを添加してシリカ溶液Ｓ１を得た。溶液のｐＨは９．３であった。また、純水１リットルに、水酸化ナトリウム３５．４ｇを溶解させ、さらに、アルミン酸ソーダ９９．３ｇを添加して、均一なアルミナ溶液Ｂ１を得た。さらに、純水１リットルに硝酸アルミニウム５００ｇを溶解させ、アルミナ溶液Ａ１を得た。次に、シリカ溶液Ｓ１にアルミナ溶液Ａ１をｐＨ３．６になるまで添加した。この時、溶液中には白色のゲルが生成した。次にアルミナ溶液Ｂ１をｐＨ９．０になるまで添加して、５分間攪拌しながらゲルを熟成させた。続いて再びアルミナ溶液Ａ１を添加して、ｐＨを３．６とし、攪拌しながら５分間ゲルを熟成させた。このようにｐＨを３．６から９．０の間で変化させる操作を１０回繰り返した。その後、得られたゲルをろ過、洗浄してシリカ含有アルミナゲルを５８０ｇ得た。このゲルを１２０℃、１６時間乾燥させ、さらに５００℃で２時間焼成してシリカ含有アルミナ担体Ｃ１を得た。
【００２５】
三酸化モリブデン８３ｇ、塩基性炭酸ニッケル３７ｇ（ＮｉＯとして２０ｇ）、正リン酸（純度８５％）３８ｇとポリエチレングリコール（分子量４００，分解温度２００℃以上）３０ｇをイオン交換水に溶解させ、全量を２７５ｃｃの含浸液とした。次にその含浸液５５ｃｃを前記のシリカ含有アルミナ担体Ｃ１の吸水量に見合った量に調製し、１００ｇに常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、３時間焼成して触媒Ｉを得た。その物性を第１表に示す。
【００２６】
上記のようにして得られた触媒Ｉについて、下記の方法で脱硫活性試験を実施した。
超小型高圧固定床反応装置の反応管に、粉砕しメッシュにより粒径を揃えた触媒２００ｍｇを充填し、硫化水素／水素ガス（１０％硫化水素）を５０ミリリットル／分で４００℃、２時間流通させて、予備硫化した。そして、温度３５０℃でチオフェン（６％）を常圧水素気流中にて５０ミリリットル／分流通させて３時間後のチオフェンの転化率を測定した。結果を第１表に示す。なお、脱硫活性の評価としてはチオフェン転化の触媒質量あたりの速度定数を用いた。
【００２７】
〔実施例２〕
三酸化モリブデン１０８ｇ、塩基性炭酸ニッケル４８ｇ（ＮｉＯとして２６ｇ）、正リン酸（純度８５％）３８ｇ、りんご酸５ｇとポリエチレングリコール（分子量４００，分解温度２００℃以上）３０ｇをイオン交換水に溶解させ、全量を２７５ｃｃの含浸液とした。次にその含浸液５５ｃｃを実施例１で調製したシリカ含有アルミナ担体Ｃ１の吸水量に見合った量に調製し、１００ｇに常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、３時間焼成して触媒IIを得た。その物性を第１表に示す。その触媒IIについて、実施例１と同様に脱硫活性試験を実施した。結果を第１表に示す。
【００２８】
〔参考例１〕
実施例１において、ポリエチレングリコール３０ｇを添加しなかったこと以外は同様にして触媒III を得た。その物性を第１表に示す。その触媒III について、実施例１と同様に脱硫活性試験を実施した。結果を第１表に示す。
【００２９】
〔参考例２〕
実施例２において、ポリエチレングリコール３０ｇを添加しなかったこと以外は同様にして触媒IVを得た。その物性を第１表に示す。その触媒IVについて、実施例１と同様に脱硫活性試験を実施した。結果を第１表に示す。
【００３０】
〔実施例３〕
実施例２において、ポリエチレングリコール３０ｇの代わりに、１，３−ブタンジオール（沸点２０４℃）を使用したこと以外は同様にして触媒Ｖを得た。その物性を第１表に示す。その触媒Ｖについて、実施例１と同様に脱硫活性試験を実施した。結果を第１表に示す。
【００３１】
〔比較例１〕
純水１リットルに、水酸化ナトリウム３５．４ｇを溶解させ、さらに、アルミン酸ソーダ９９．３ｇを添加して、均一なアルミナ溶液Ｂ２を得た。さらに、純水１リットルに硝酸アルミニウム５００ｇを溶解させ、アルミナ溶液Ａ２を得た。純水２．３８リットルを７０℃に加温し、攪拌しながら、アルミナ溶液Ａ２をｐＨ３．６になるまで添加した。次にアルミナ溶液Ｂ２をｐＨ９．０になるまで添加して、５分間攪拌しながら熟成させた。続いて再びアルミナ溶液Ａ２を添加して、ｐＨを３．６とし、攪拌しなが５分間熟成させた。このようにｐＨを３．６から９．０の間で変化させる操作を８回繰り返した。その後、得られたゲルをろ過、洗浄してアルミナゲルを５８０ｇ得た。このゲルを１２０℃、１６時間乾燥させ、さらに５００℃で２時間焼成してアルミナ担体Ｃ２を得た。
【００３２】
三酸化モリブデン８３ｇ、塩基性炭酸ニッケル３７ｇ（ＮｉＯとして２０ｇ）、正リン酸（純度８５％）３８ｇとポリエチレングリコール（分子量４００，分解温度２００℃以上）３０ｇをイオン交換水に溶解させ、全量を２７５ｃｃの含浸液とした。次にその含浸液５５ｃｃを前記のアルミナ担体Ｃ２の吸水量に見合った量に調製し、１００ｇに常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、３時間焼成して触媒VIを得た。その物性を第１表に示す。その触媒VIについて、実施例１と同様に脱硫活性試験を実施した。結果を第１表に示す。
【００３３】
〔比較例２〕
純水２．３８リットルを７０℃に加温し、攪拌しながら、水ガラス３．３ｇを添加してシリカ溶液Ｓ２を得た。溶液のｐＨは８．５であった。また、純水１リットルに水酸化ナトリウム３５．４ｇを溶解させ、さらにアルミン酸ソーダ９９．３ｇを添加して均一なアルミナ溶液Ｂ３を得た。さらに、純水１リットルに硝酸アルミニウム５００ｇを溶解させ、アルミナ溶液Ａ３を得た。次に、シリカ溶液Ｓ２にアルミナ溶液Ａ３をｐＨ３．６になるまで添加した。この時、溶液中には白色のゲルが生成した。次に、アルミナ溶液Ｂ３をｐＨ９．０になるまで添加して、５分間攪拌しながらゲルを熟成させた。続いて再びアルミナ溶液Ａ３を添加してｐＨを３．６とし、攪拌しながら５分間ゲルを熟成させた。このようにｐＨを３．６〜９．０の間で変化させる操作を１０回繰り返した。その後、得られたゲルをろ過、洗浄してシリカ含有アルミナゲルを５８０ｇ得た。このゲルを１２０℃、１６時間乾燥させ、さらに５００℃で２時間焼成してシリカ含有アルミン担体Ｃ３を得た。
【００３４】
三酸化モリブデン１０８ｇ、塩基性炭酸ニッケル４８ｇ（ＮｉＯとして２６ｇ）、正リン酸（純度８５％）３８ｇ、りんご酸５ｇとポリエチレングリコール（分子量４００，分解温度２００℃以上）４０ｇをイオン交換水に溶解させ、全量を２７５ｃｃの含浸液とした。次にその含浸液５５ｃｃをシリカ含有アルミナ担体Ｃ３の吸水量に見合った量に調製し、１００ｇに常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、３時間焼成して触媒VII を得た。その物性を第１表に示す。その触媒VII について、実施例１と同様に脱硫活性試験を実施した。結果を第１表に示す。
【００３５】
〔比較例３〕
比較例１において、ポリエチレングリコール３０ｇを添加しなかったこと以外は同様にして触媒VIIIを得た。その物性を第１表に示す。その触媒VIIIについて、実施例１と同様に脱硫活性試験を実施した。結果を第１表に示す。
【００３６】
〔比較例４〕
比較例２において、ポリエチレングリコール３０ｇを添加しなかったこと以外は同様にして触媒IXを得た。その物性を第１表に示す。その触媒IXについて、実施例１と同様に脱硫活性試験を実施した。結果を第１表に示す。
【００３７】
【表１】
【表２】
【表３】
〔実施例４〕
上流側に充填する脱金属触媒の調製
純水１リットルに、水酸化ナトリウム３５．４ｇを溶解させ、さらに、アルミン酸ソーダ９９．３ｇを添加して、均一なアルミナ溶液Ｂ４を得た。また、純水１リットルに硝酸アルミニウム５００ｇを溶解させ、アルミナ溶液Ａ４を得た。純水２．３８リットルを７０℃に加温し、攪拌しながら、アルミナ溶液Ａ４をｐＨ２．６になるまで添加した。次にアルミナ溶液Ｂ４をｐＨ９．０になるまで添加して、５分間攪拌しながら熟成させた。続いて再びアルミナ溶液Ａ４を添加して、ｐＨを３．６とし、攪拌しながら５分間熟成させた。このようにｐＨを３．６から９．０の間で変化させる操作を１３回繰り返した。その後、得られたゲルをろ過、洗浄してアルミナゲルを１，０７５ｇ得た。このゲルを１２０℃、１６時間乾燥させ、さらに５００℃で２時間焼成してアルミナ担体Ｃ４を得た。
【００４１】
三酸化モリブデン３１ｇ、塩基性炭酸ニッケル１１ｇ（ＮｉＯとして６ｇ）、りんご酸５０ｇをイオン交換水に溶解させ、全量を２００ｃｃの含浸液とした。次にその含浸液５５ｃｃを前記のアルミナ担体Ｃ４の吸水量に見合った量に調製し、１００ｇに常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、３時間焼成して触媒Ｘを得た。その物性を第２表に示す。
【００４２】
【表４】
上流側に触媒Ｘの脱金属触媒を３０容量％、下流側に触媒Ｉの水素化処理触媒を７０容量％を反応管に充填して、下記のとおり触媒の性能を評価した。結果を第４表に示す。
【００４４】
・触媒の性能評価
小型高圧固定床反応装置の反応管に、上記の脱メタル触媒と水素化処理触媒を充填した。中東系軽質軽油（ＬＧＯ，硫黄分１．１８質量％、窒素分７０ｐｐｍ）にジメチルジスルフィドを添加して硫黄濃度を２．５質量％に調整した予備硫化油を調製した。この予備硫化油を、上記の触媒に、水素ガスとともに２５０℃で２４時間流通させて予備硫化した。また、原料油としては、金属（バナジウム，ニッケル）含有量が非常に多い中東系原油の常圧残油を用いた。その性状を第３表に示す。
【００４５】
【表５】
この原料油を、上記の予備硫化後の触媒に、水素ガスとともに流通させて、以下の条件で水素化処理を行った。
生成油のターゲット硫黄分：０．５質量％
水素分圧：１３．５ＭＰａ
液空間速度（ＬＨＳＶ）：０．６ｈｒ-1
水素／オイル比：８５０Ｎｍ3 ／ｋｌ
【００４７】
〔比較例５〕
上流側に触媒Ｘの脱メタル触媒を３０容量％、下流側に触媒VIIIの水素化処理触媒を７０容量％を反応管に充填して、実施例６と同様に触媒の性能を評価した。結果を第４表に示す。
【００４８】
【表６】
【発明の効果】
本発明は、より低温における高脱硫活性と耐金属蓄積性を有する水素化処理触媒であるので、その水素化処理触媒を使用し重質炭化水素油を水素化処理を行うと、従来より運転初期温度を低くでき、また触媒の劣化速度を緩和できるため、触媒の寿命が長くなり、原料油の増処理と触媒交換頻度の低減につながる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrotreating catalyst and a method for hydrotreating heavy hydrocarbon oil using the same, and more particularly, to a hydrotreating catalyst having specific physical properties, and hydrogenation of heavy hydrocarbon oil using the same. It relates to the processing method.
[0002]
[Prior art]
At present, in order to protect the environment from acid rain and the like, the sulfur content in fuel oil is reduced by hydrorefining treatment, and therefore, a desulfurization catalyst is generally used. However, particularly in the case of producing low-sulfur heavy oil using heavy oil such as atmospheric residual oil and reduced-pressure residual oil as a raw material, the catalyst life is short and less than one year due to the limit of the desulfurization performance of the catalyst. Therefore, the refiner must be stopped and the catalyst replaced within one year. Thus, when producing low sulfur heavy oil from heavy oil, in order to reduce a sulfur content compared with the hydrogenation process of kerosene oil, a high temperature is required from the beginning of operation. Further, since the activity of the catalyst deteriorates with time, it is necessary to gradually increase the operating temperature in order to keep the amount of sulfur in the product constant. In particular, heavy oil contains metal components such as vanadium and nickel, and deposits on the catalyst during the reaction to poison the activity. For this reason, the upper limit temperature of the apparatus is reached within one year, and the catalyst is replaced. Therefore, development of a catalyst having high desulfurization activity and metal accumulation resistance at a lower temperature is desired.
[0003]
[Problems to be solved by the invention]
The present invention was made from the above viewpoint, and provides a hydrotreating catalyst having high desulfurization activity and metal accumulation resistance at lower temperatures, and hydrogenation of heavy hydrocarbon oils using the hydrotreating catalyst. The object is to provide a processing method.
[0004]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the object of the present invention can be effectively achieved by using a hydrotreating catalyst having specific physical properties, and have completed the present invention.
[0005]
That is, the gist of the present invention is as follows.
1. The alumina support containing 1 to 10% by mass of silica carries at least one selected from Group 6 metals of the periodic table and Group 8 to 10 metals of the periodic table, and further contains phosphorus on a catalyst basis. A catalyst containing 3 to 5% by mass on the oxide basis , wherein the metal is supported on the carrier by using an impregnating liquid containing a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher. The catalyst has an average pore diameter (PD) of 100 to 170 mm, a specific surface area (SA) of 140 to 250 m @ 2 / g, both satisfy the following formula (1), and the total pore volume: Is 0.4 to 1.0 cc / g.
SA + 1.65PD> 410 (1)
2. 2. The hydrotreating catalyst according to 1 above, wherein the Group 6 metal of the periodic table is molybdenum and the Group 8-10 metal of the periodic table is nickel.
3 . 3. The hydrotreating catalyst according to 1 or 2 above, wherein the water-soluble organic compound is polyethylene glycol or 1,3-butanediol .
4 . A method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst described in any one of 1 to 3 above.
5 . 4. The method for hydrotreating heavy hydrocarbon oil according to 4 above, using the demetallation catalyst on the upstream side and the hydrotreating catalyst according to any one of 1 to 3 above on the downstream side.
6 . 6. The method for hydrotreating heavy hydrocarbon oil according to 4 or 5 above, wherein the heavy hydrocarbon oil is a vacuum gas oil, an atmospheric residue or a vacuum residue.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
In the hydrotreating catalyst of the present invention, an alumina support containing 1 to 10% by mass of silica contains at least one selected from Group 6 metals and 8 to 10 metals in the Periodic Table. The supported catalyst has an average pore diameter (PD) of 100 to 170 mm, a specific surface area (SA) of 140 to 250 m 2 / g, and both satisfy the following formula (1): Furthermore, the total pore volume is 0.4 to 1.0 cc / g.
SA + 1.65PD> 410 (1)
[0007]
First, the amount of silica added to the alumina support is 1 to 10% by mass. If it is less than 1% by mass, the effect of increasing the surface area of alumina is small, and if it exceeds 10% by mass, the ability of a specific impregnating solution to carry a metal in a highly dispersed state on the carrier is not preferred. With respect to the metal supported on the carrier, examples of the Group 6 metal of the periodic table include molybdenum and tungsten. Molybdenum is preferred. The amount of the Group 6 metal supported is 4 to 25% by mass, preferably 8 to 20% by mass, based on the catalyst and based on the oxide. Examples of metals in Groups 8 to 10 of the periodic table include cobalt and nickel, with nickel being preferred. The supported amount of the Group 8-10 metal is 1 to 8% by mass, preferably 2 to 5% by mass based on the oxide, based on the catalyst. As other components, phosphorus is particularly necessary . When phosphorus is added, the hydrogenation activity of the catalyst is improved, and particularly when heavy hydrocarbon oil is used as a raw material, the desulfurization activity is improved. The effect becomes remarkable when the addition amount is 3 to 5% by mass on the catalyst basis and on the oxide basis.
[0008]
The average pore diameter (PD) of the catalyst is 100 to 170 mm. If it is less than 100%, the deposition of vanadium or nickel metal in the raw hydrocarbon oil and the deposition of the coke precursor will clog the pores in a short time and reduce the desulfurization activity. If it exceeds 170%, the desulfurization activity is remarkably lowered in the initial stage of operation, which is not preferable. The specific surface area (SA) of the catalyst is 140 to 250 m 2 / g. If it is less than 140 m 2 / g, the desulfurization activity of the catalyst is low, and if it exceeds 250 m 2 / g, the desulfurization activity is saturated and the efficiency is poor. The PD and SA must satisfy the above formula (1). If the formula (1) is not satisfied, the catalyst is inferior in both desulfurization activity and catalyst life.
[0009]
Subsequently, the manufacturing method of the said hydroprocessing catalyst is demonstrated.
First, as a method for producing a silica-containing alumina carrier as a carrier, generally, an alumina source and a silica source are mixed, a precipitate is aged, dried and fired.
[0010]
Examples of the alumina source used include water-soluble acidic alumina salts such as aluminum sulfate and aluminum nitrate, and water-soluble basic alumina salts such as sodium aluminate. Examples of the silica source used include water glass, sodium silicate, and silica sol. When mixing the alumina source and the silica source, the pH is 3 to 10, preferably 3.3 to 9.3. The mixing temperature is 30 to 90 ° C, preferably 50 to 80 ° C.
[0011]
Regarding the aging method of the formed precipitate, generally, an operation (swing) in which an acidic solution and an alkaline solution are alternately added at the same temperature as the mixing is performed three times or more between pH 3.0 and 9.3, preferably 5 It can be done by doing more than once. Further, a method of stirring at a pH of 9 or higher and a temperature of 70 ° C. or higher, preferably a pH of 10 or higher and a temperature of 80 ° C. or higher for a certain period of time can be used. This may be combined with the swing method. The aged precipitate is dried at 80 to 200 ° C. (preferably 100 to 160 ° C.) and calcined at 400 to 700 ° C. (preferably 500 to 600 ° C.).
[0012]
As a method for obtaining the above-mentioned precipitation, a method in which an alumina gel and a silica gel are respectively prepared in advance and mixed together, a method in which an aqueous solution of a silica compound is mixed in an alumina gel, a solution containing an aluminum compound, an aluminum compound, and a silica compound A method of obtaining a precipitate by mixing, a method of obtaining a precipitate by changing the pH of a solution containing an aluminum compound and a silica compound, and the like can be employed.
[0013]
In order to obtain a particularly desirable carrier precipitate, a solution is prepared by mixing water-soluble basic alumina salt with water-soluble silica under conditions that do not substantially generate gel, and then adding water-soluble alumina salt. Thus, a method of generating a gel may be employed. More specifically, in order to mix a solution of a water-soluble basic alumina salt and a water-soluble silica under conditions that do not substantially generate a gel, an aqueous solution of water-soluble basic alumina salt is preliminarily mixed with aqueous ammonia or sodium hydroxide. The base may be added to increase the pH to 10 or more, and then water-soluble silica may be added. Alternatively, mixing with water glass and aluminum sulfate at a pH of 3 or less can also be performed without substantial gel formation. A water-soluble acidic alumina solution or basic alumina solution is further added to the silica / alumina aqueous solution thus obtained to cause precipitation. In order to obtain a precipitate from the silica-alumina transparent solution prepared on the alkali side, it is effective to add a water-soluble acidic alumina solution. To obtain a precipitate from the silica-alumina transparent solution prepared on the acidic side It is effective to add a water-soluble basic alumina solution.
[0014]
A metal can be supported on the silica-containing alumina support obtained as described above by the following method. The supporting method is preferably an impregnation method. As the molybdenum compound of Group 6 of the periodic table, molybdenum trioxide, ammonium paramolybdate or the like is used, and as the tungsten compound, tungsten trioxide, ammonium tungstate or the like is used. Moreover, nickel nitrate, basic nickel carbonate, etc. are used as a nickel compound of Group 8-10 of a periodic table, and cobalt nitrate, basic cobalt carbonate, etc. are used as a cobalt compound. Furthermore, phosphorus pentoxide, phosphoric acid, etc. are used as a phosphorus compound. In the metal compound, the group 6 metal of the periodic table is 0.7 to 4.3 mol / liter, the metal of the group 8 to 10 of the periodic table is 0.3 to 2.4 mol / liter, and the phosphorus compound is What was dissolved in pure water at a rate of 1.1 to 2.0 mol / liter, and further dissolved a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher at a rate of 50 to 200 g / liter as an impregnation solution, The carrier is impregnated after adjustment so as to have the same amount of water absorption. As a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, or other ether group-containing water-soluble Water-soluble polymers such as water-soluble polymers such as water-soluble polymers, polyvinyl alcohol and the like, various sugars such as saccharose and glycolose, methylcellulose, water-soluble starch and the like, and polyethylene having a molecular weight of 400 or more. Glycol is preferred. By using a water-soluble organic compound having a boiling point or decomposition temperature of 200 ° C. or higher, aggregation on a metal carrier can be suppressed.
[0015]
The pH adjustment of the impregnating solution is not particularly limited, but can be performed using an inorganic acid such as nitric acid, hydrochloric acid or sulfuric acid, an organic acid such as malic acid or ethylenediaminetetraacetic acid, ammonia or the like. The impregnation is followed by drying and firing. The drying temperature is 80 to 200 ° C (preferably 100 to 150 ° C), and the firing temperature is 300 to 600 ° C (preferably 400 to 550 ° C). If the calcination temperature is too low, the supported component and the carrier may not be sufficiently bonded. If it is too high, aggregation of the supported component tends to occur.
[0016]
Next, when hydrotreating using the hydrotreating catalyst of the present invention, it is desirable to perform preliminary sulfidation as a stabilization treatment in advance. The conditions for this preliminary sulfidation treatment are not particularly limited, but usually, as the presulfurization agent, hydrogen sulfide, carbon disulfide, thiophene, dimethyl disulfide and the like can be mentioned, treatment temperature 200 to 400 ° C., treatment pressure normal pressure to 30 MPa. It is done in the range.
[0017]
As for the shape of the catalyst, in particular, many of the catalysts used for the hydrogenation treatment of heavy hydrocarbon oils are usually produced by extrusion molding, and the shape thereof is substantially columnar. The cross-section is often circular, but there are also devices that devise to increase the outer surface such as a trilobal type and a four-leaf type. Also, spherical catalysts are often used. Spherical catalysts are used when compression strength and wear resistance are particularly required.
[0018]
The hydrotreating conditions vary depending on the type and purpose of the feedstock, but generally the reaction temperature is 200 to 550 ° C. (preferably 220 to 500 ° C.) and the hydrogen partial pressure is 5 to 30 MPa (preferably 10 to 25 MPa). Done in a range.
[0019]
Although the reaction mode is not particularly limited, it can be usually selected from various processes such as a fixed bed, a moving bed, a boiling bed, and a suspension bed, but a fixed bed is preferable.
As reaction conditions other than temperature and pressure in the case of a fixed bed, the liquid space velocity (LHSV) is 0.05 to 10 hr −1 (preferably 0.1 to 5 hr −1 ), and the hydrogen / oil ratio is 500 to 2. 500 Nm 3 / kl (preferably 700 to 2,000 Nm 3 / kl).
[0020]
The second invention of the present application is a method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst.
Examples of the heavy hydrocarbon include atmospheric residual oil, vacuum residual oil, vacuum gas oil, dewaxed vacuum residual oil, asphaltene oil, tar sand oil, and residual oil obtained by subjecting these to preliminary dihydrogenation. Moreover, the mixed oil (residual oil / catalyzed cracked oil (volume ratio) of 1 or more, preferably 1.5 or more) of the residual oil and the catalytically cracked light oil can be used. The properties of the feed oil are not particularly limited, but typical properties are as follows.
[0021]
Specific gravity (15/4 ° C.): 0.9530 to 0.9940
Kinematic viscosity (50 ° C.): 250 to 3,000 cSt
Sulfur content: 2.8 to 4.5% by mass
Nitrogen content: 1,500-4,200 ppm
Metal content (V, Ni): 30-250 ppm
Residual carbon content: 5 to 18% by mass
Asphaltene content: 0.5-12.0% by mass
As the reaction conditions, the above raw material oil may be hydrotreated by filling a single-layer hydrotreating catalyst. However, in order to obtain a catalyst having a higher desulfurization activity and a longer life, an upstream side of an alumina carrier is used. The catalyst system using a demetallization catalyst carrying at least one selected from the group 6 of the periodic table and at least one selected from the groups 8 to 10 of the periodic table is used on the downstream side. That's fine.
[0022]
Examples of physical properties of the demetallation catalyst used on the upstream side are shown below.
Examples of the metal of Group 6 of the periodic table include molybdenum and tungsten, but molybdenum is preferable. The amount of the Group 6 metal supported is 2 to 15% by mass, preferably 4 to 12% by mass based on the oxide, based on the catalyst. Examples of metals in Groups 8 to 10 of the periodic table include cobalt and nickel, with nickel being preferred. The supported amount of the Group 8-10 metal is 1 to 4% by mass, preferably 1.5 to 2.5% by mass based on the oxide, based on the catalyst. As the support, alumina is desirable, the catalyst has a pore diameter of 100 to 250 mm (preferably 150 to 220 mm), a specific surface area of 80 to 200 m 2 / g (preferably 100 to 180 m 2 / g), and a pore volume of 0. .4 to 1.0 cc / g (preferably 0.5 to 0.9 cc / g).
[0023]
The filling ratio of the demetallation catalyst and the hydrotreating catalyst of the present invention is such that the demetallation catalyst is 10 to 50% by volume (preferably 20 to 40% by volume), whereas the hydrotreating catalyst of the present invention is 50 to 90% by volume. % (Preferably 60 to 80% by volume).
[0024]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not restrict | limited at all by these Examples.
[Example 1]
While heating 2.38 liters of pure water to 70 ° C. and stirring, 16 g of water glass was added to obtain silica solution S1. The pH of the solution was 9.3. Further, 35.4 g of sodium hydroxide was dissolved in 1 liter of pure water, and 99.3 g of sodium aluminate was further added to obtain a uniform alumina solution B1. Furthermore, 500 g of aluminum nitrate was dissolved in 1 liter of pure water to obtain an alumina solution A1. Next, the alumina solution A1 was added to the silica solution S1 until the pH reached 3.6. At this time, a white gel was formed in the solution. Next, alumina solution B1 was added until pH 9.0 and the gel was aged while stirring for 5 minutes. Subsequently, the alumina solution A1 was added again to adjust the pH to 3.6, and the gel was aged for 5 minutes while stirring. The operation of changing the pH between 3.6 and 9.0 was repeated 10 times. Thereafter, the obtained gel was filtered and washed to obtain 580 g of silica-containing alumina gel. This gel was dried at 120 ° C. for 16 hours and further calcined at 500 ° C. for 2 hours to obtain a silica-containing alumina carrier C1.
[0025]
83 g of molybdenum trioxide, 37 g of basic nickel carbonate (20 g as NiO), 38 g of orthophosphoric acid (purity 85%) and 30 g of polyethylene glycol (molecular weight 400, decomposition temperature 200 ° C. or higher) are dissolved in ion-exchanged water, and the total amount is 275 cc. The impregnating solution was used. Next, 55 cc of the impregnating liquid was prepared in an amount commensurate with the water absorption amount of the silica-containing alumina support C1, and 100 g was impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 3 hours to obtain Catalyst I. The physical properties are shown in Table 1.
[0026]
The catalyst I obtained as described above was subjected to a desulfurization activity test by the following method.
The reaction tube of an ultra-compact high-pressure fixed bed reactor is filled with 200 mg of pulverized catalyst with a uniform particle size, and hydrogen sulfide / hydrogen gas (10% hydrogen sulfide) is flowed at 400 ml at 50 ml / min for 2 hours. And presulfided. And thiophene (6%) was distribute | circulated 50 milliliters / minute in normal-pressure hydrogen stream at the temperature of 350 degreeC, and the conversion rate of the thiophene after 3 hours was measured. The results are shown in Table 1. In addition, the rate constant per catalyst mass of thiophene conversion was used for evaluation of desulfurization activity.
[0027]
[Example 2]
108 g of molybdenum trioxide, 48 g of basic nickel carbonate (26 g as NiO), 38 g of orthophosphoric acid (purity 85%), 5 g of malic acid and 30 g of polyethylene glycol (molecular weight 400, decomposition temperature 200 ° C. or higher) are dissolved in ion-exchanged water. The total amount was 275 cc of impregnation liquid. Next, 55 cc of the impregnating solution was prepared in an amount commensurate with the water absorption of the silica-containing alumina support C1 prepared in Example 1, and 100 g was impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 3 hours to obtain Catalyst II. The physical properties are shown in Table 1. About the catalyst II, the desulfurization activity test was implemented like Example 1. FIG. The results are shown in Table 1.
[0028]
[ Reference Example 1 ]
In Example 1, Catalyst III was obtained in the same manner except that 30 g of polyethylene glycol was not added. The physical properties are shown in Table 1. The catalyst III was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
[0029]
[ Reference Example 2 ]
Catalyst IV was obtained in the same manner as in Example 2, except that 30 g of polyethylene glycol was not added. The physical properties are shown in Table 1. The catalyst IV was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
[0030]
[Example 3 ]
In Example 2, Catalyst V was obtained in the same manner except that 1,3-butanediol (boiling point 204 ° C.) was used instead of 30 g of polyethylene glycol. The physical properties are shown in Table 1. The catalyst V was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
[0031]
[Comparative Example 1]
In 1 liter of pure water, 35.4 g of sodium hydroxide was dissolved, and 99.3 g of sodium aluminate was further added to obtain a uniform alumina solution B2. Furthermore, 500 g of aluminum nitrate was dissolved in 1 liter of pure water to obtain an alumina solution A2. 2.38 liters of pure water was heated to 70 ° C., and the alumina solution A2 was added to pH 3.6 while stirring. Next, the alumina solution B2 was added until pH 9.0 and aged with stirring for 5 minutes. Subsequently, the alumina solution A2 was added again to adjust the pH to 3.6, and the mixture was aged for 5 minutes while stirring. Thus, the operation of changing the pH between 3.6 and 9.0 was repeated 8 times. Thereafter, the obtained gel was filtered and washed to obtain 580 g of alumina gel. This gel was dried at 120 ° C. for 16 hours and further calcined at 500 ° C. for 2 hours to obtain an alumina carrier C2.
[0032]
83 g of molybdenum trioxide, 37 g of basic nickel carbonate (20 g as NiO), 38 g of orthophosphoric acid (purity 85%) and 30 g of polyethylene glycol (molecular weight 400, decomposition temperature 200 ° C. or higher) are dissolved in ion-exchanged water, and the total amount is 275 cc. The impregnating solution was used. Next, 55 cc of the impregnating solution was prepared in an amount commensurate with the water absorption of the alumina carrier C2, and 100 g was impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 3 hours to obtain catalyst VI. The physical properties are shown in Table 1. The catalyst VI was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
[0033]
[Comparative Example 2]
2.38 liters of pure water was heated to 70 ° C., and while stirring, 3.3 g of water glass was added to obtain silica solution S2. The pH of the solution was 8.5. Further, 35.4 g of sodium hydroxide was dissolved in 1 liter of pure water, and 99.3 g of sodium aluminate was further added to obtain a uniform alumina solution B3. Furthermore, 500 g of aluminum nitrate was dissolved in 1 liter of pure water to obtain an alumina solution A3. Next, alumina solution A3 was added to silica solution S2 until pH 3.6 was reached. At this time, a white gel was formed in the solution. Next, the alumina solution B3 was added until pH 9.0, and the gel was aged while stirring for 5 minutes. Subsequently, the alumina solution A3 was added again to adjust the pH to 3.6, and the gel was aged for 5 minutes while stirring. Thus, operation which changes pH between 3.6-9.0 was repeated 10 times. Thereafter, the obtained gel was filtered and washed to obtain 580 g of silica-containing alumina gel. This gel was dried at 120 ° C. for 16 hours and further calcined at 500 ° C. for 2 hours to obtain a silica-containing aluminum carrier C3.
[0034]
108 g of molybdenum trioxide, 48 g of basic nickel carbonate (26 g as NiO), 38 g of normal phosphoric acid (purity 85%), 5 g of malic acid and 40 g of polyethylene glycol (molecular weight 400, decomposition temperature 200 ° C. or more) are dissolved in ion-exchanged water. The total amount was 275 cc of impregnation liquid. Next, 55 cc of the impregnating solution was prepared in an amount commensurate with the water absorption of the silica-containing alumina support C3, and 100 g was impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 3 hours to obtain catalyst VII. The physical properties are shown in Table 1. The catalyst VII was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
[0035]
[Comparative Example 3]
Catalyst VIII was obtained in the same manner as in Comparative Example 1 except that 30 g of polyethylene glycol was not added. The physical properties are shown in Table 1. The catalyst VIII was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
[0036]
[Comparative Example 4]
Catalyst IX was obtained in the same manner as in Comparative Example 2, except that 30 g of polyethylene glycol was not added. The physical properties are shown in Table 1. The catalyst IX was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
[0037]
[Table 1]
[Table 2]
[Table 3]
[Example 4 ]
Preparation of Demetallization Catalyst Filled Upstream 35.4 g of sodium hydroxide was dissolved in 1 liter of pure water, and 99.3 g of sodium aluminate was added to obtain a uniform alumina solution B4. Moreover, 500 g of aluminum nitrate was dissolved in 1 liter of pure water to obtain an alumina solution A4. 2.38 liters of pure water was heated to 70 ° C., and the alumina solution A4 was added to pH 2.6 while stirring. Next, the alumina solution B4 was added until pH 9.0 and aged with stirring for 5 minutes. Subsequently, the alumina solution A4 was added again to adjust the pH to 3.6 and aged for 5 minutes while stirring. Thus, the operation of changing the pH between 3.6 and 9.0 was repeated 13 times. Thereafter, the obtained gel was filtered and washed to obtain 1075 g of alumina gel. This gel was dried at 120 ° C. for 16 hours, and further calcined at 500 ° C. for 2 hours to obtain an alumina carrier C4.
[0041]
31 g of molybdenum trioxide, 11 g of basic nickel carbonate (6 g as NiO), and 50 g of malic acid were dissolved in ion-exchanged water to make a total of 200 cc of impregnation liquid. Next, 55 cc of the impregnating solution was prepared in an amount commensurate with the water absorption of the alumina carrier C4, and 100 g was impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 3 hours to obtain Catalyst X. The physical properties are shown in Table 2.
[0042]
[Table 4]
The reaction tube was filled with 30% by volume of the catalyst X demetallation catalyst on the upstream side and 70% by volume of the hydrotreating catalyst of Catalyst I on the downstream side, and the performance of the catalyst was evaluated as follows. The results are shown in Table 4.
[0044]
-Performance evaluation of catalyst The above-mentioned demetalization catalyst and hydrotreating catalyst were filled in a reaction tube of a small high-pressure fixed bed reactor. A preliminary sulfurized oil was prepared by adding dimethyl disulfide to a Middle Eastern light gas oil (LGO, sulfur content 1.18 mass%, nitrogen content 70 ppm) to adjust the sulfur concentration to 2.5 mass%. This pre-sulfided oil was pre-sulfided by flowing through the above catalyst together with hydrogen gas at 250 ° C. for 24 hours. Moreover, as the feedstock, a normal-pressure residual oil of Middle Eastern crude oil having a very high metal (vanadium, nickel) content was used. The properties are shown in Table 3.
[0045]
[Table 5]
This raw material oil was circulated together with hydrogen gas through the catalyst after the preliminary sulfidation, and the hydrogenation treatment was performed under the following conditions.
Target sulfur content of the product oil: 0.5% by mass
Hydrogen partial pressure: 13.5 MPa
Liquid space velocity (LHSV): 0.6 hr −1
Hydrogen / oil ratio: 850 Nm 3 / kl
[0047]
[Comparative Example 5]
The catalyst performance was evaluated in the same manner as in Example 6 by filling the reaction tube with 30% by volume of the catalyst X demetalization catalyst on the upstream side and 70% by volume of the hydrotreating catalyst of catalyst VIII on the downstream side. The results are shown in Table 4.
[0048]
[Table 6]
【Effect of the invention】
Since the present invention is a hydrotreating catalyst having high desulfurization activity and metal accumulation resistance at a lower temperature, when hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst, the operation is earlier than before. Since the temperature can be lowered and the deterioration rate of the catalyst can be mitigated, the life of the catalyst is extended, leading to an increase in the feed oil and a reduction in the frequency of catalyst replacement.
Claims (6)
ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１）The alumina support containing 1 to 10% by mass of silica carries at least one selected from Group 6 metals of the periodic table and Group 8 to 10 metals of the periodic table, and further contains phosphorus on a catalyst basis. A catalyst containing 3 to 5% by mass on the oxide basis , wherein the metal is supported on the carrier by using an impregnating liquid containing a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher. The catalyst has an average pore diameter (PD) of 100 to 170 mm, a specific surface area (SA) of 140 to 250 m 2 / g, both satisfy the following formula (1), and the total pores A hydroprocessing catalyst having a capacity of 0.4 to 1.0 cc / g.
SA + 1.65PD> 410 (1)
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| JP2000234049A JP4865940B2 (en) | 1999-09-29 | 2000-08-02 | Hydrotreating catalyst and method for hydrotreating heavy hydrocarbon oil using the catalyst |
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| FR2998488B1 (en) * | 2012-11-29 | 2015-02-06 | Ifp Energies Now | HYDROTREATMENT CATALYST FROM ALUMIN GEL AND METHOD OF PREPARING SUCH A CATALYST |
| FR2999453B1 (en) * | 2012-12-18 | 2015-02-06 | IFP Energies Nouvelles | RESIDUAL HYDROTREATMENT CATALYST COMPRISING VANADIUM AND USE THEREOF IN A RESIDUAL HYDROCONVERSION PROCESS |
| FR2999454B1 (en) * | 2012-12-18 | 2015-02-06 | IFP Energies Nouvelles | CATALYST FOR HYDROTREATING RESIDUES WITH A CONTROLLED SILICON CONTENT AND USE THEREOF IN A PROCESS FOR HYDROCONVERSION OF RESIDUES |
| CN112973717B (en) * | 2019-12-16 | 2024-01-30 | 山西腾茂科技股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN116060022A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst and production method thereof |
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| JPS5335705A (en) * | 1976-09-14 | 1978-04-03 | Toa Nenryo Kogyo Kk | Hydrogenation and purification of petroleum wax |
| JPS5437105A (en) * | 1977-08-29 | 1979-03-19 | Chiyoda Chem Eng & Constr Co Ltd | Two-stage hydrogenation of heavy oil |
| US4941964A (en) * | 1988-03-14 | 1990-07-17 | Texaco Inc. | Hydrotreatment process employing catalyst with specified pore size distribution |
| US5399259A (en) * | 1992-04-20 | 1995-03-21 | Texaco Inc. | Hydroconversion process employing catalyst with specified pore size distribution |
| MX9305801A (en) * | 1992-09-29 | 1994-07-29 | Texaco Development Corp | A NEW HYDROCONVERSION PROCESS USING A CATALYST WITH A SPECIFIED PORE SIZE DISTRIBUTION. |
| JP2854484B2 (en) * | 1993-02-03 | 1999-02-03 | 出光興産株式会社 | Hydroprocessing of kerosene oil fraction |
| JP3802939B2 (en) * | 1994-09-21 | 2006-08-02 | 東燃ゼネラル石油株式会社 | Catalyst for hydrotreating |
| JP3692207B2 (en) * | 1997-04-30 | 2005-09-07 | 東燃ゼネラル石油株式会社 | Hydrotreating catalyst and hydrocarbon oil hydrotreating method using the same |
| JP3511128B2 (en) * | 1998-03-02 | 2004-03-29 | 日立造船株式会社 | Method for producing metal fine particles and method for supporting fine particles on porous carrier |
| JP4303820B2 (en) * | 1999-01-26 | 2009-07-29 | 日本ケッチェン株式会社 | Hydrotreating catalyst and hydrotreating method |
| JP2001003066A (en) * | 1999-06-24 | 2001-01-09 | Idemitsu Kosan Co Ltd | Production of desulfurized fuel oil |
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