JP4808172B2 - Hydrocracking catalyst and fuel substrate production method - Google Patents
Hydrocracking catalyst and fuel substrate production method Download PDFInfo
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- JP4808172B2 JP4808172B2 JP2007073193A JP2007073193A JP4808172B2 JP 4808172 B2 JP4808172 B2 JP 4808172B2 JP 2007073193 A JP2007073193 A JP 2007073193A JP 2007073193 A JP2007073193 A JP 2007073193A JP 4808172 B2 JP4808172 B2 JP 4808172B2
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- 239000003054 catalyst Substances 0.000 title claims description 54
- 238000004517 catalytic hydrocracking Methods 0.000 title claims description 23
- 239000000446 fuel Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000758 substrate Substances 0.000 title description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 38
- 239000010457 zeolite Substances 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 229930195733 hydrocarbon Natural products 0.000 claims description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 239000011973 solid acid Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 229910052697 platinum Inorganic materials 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005336 cracking Methods 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
本発明は、水素の存在下でパラフィン系炭化水素から燃料基材を製造するための触媒およびこの触媒を使用した燃料基材の製造方法に関する。 The present invention relates to a catalyst for producing a fuel substrate from paraffinic hydrocarbons in the presence of hydrogen, and a method for producing a fuel substrate using this catalyst.
硫黄分および芳香族炭化水素の含有量が少ない環境対応型液体燃料への要求が近年急速に高まってきている。また、燃料油製造業界においても既に環境対応型液体燃料の製造方法が検討されている。その中でワックス等のパラフィン系炭化水素を触媒存在下で水素化分解して環境対応型液体燃料に転換するプロセスが１つの方法として検討されている。
パラフィン系炭化水素の水素化分解プロセスにおいては、有用な中間留分を高収率で得ることがプロセスの経済性向上のために特に重要である。これに加えて得られる燃料基材（中間留分）の流動点が低いことも必要である。即ち、分解活性が高く、中間留分得率も高く、かつ燃料基材（中間留分）が低流動点を有する高性能な水素化分解触媒の開発がプロセスの経済性向上の鍵を握っている。
In recent years, there has been a rapid increase in demand for environmentally friendly liquid fuels with low sulfur and aromatic hydrocarbon contents. Also, in the fuel oil manufacturing industry, a method for producing an environmentally friendly liquid fuel has already been studied. Among them, a process of hydrocracking paraffinic hydrocarbons such as wax in the presence of a catalyst to convert it into an environmentally friendly liquid fuel is being studied as one method.
In the hydrocracking process of paraffinic hydrocarbons, obtaining a useful middle distillate in a high yield is particularly important for improving the economics of the process. In addition, the pour point of the fuel substrate (middle distillate) obtained is also required to be low. In other words, the development of a high-performance hydrocracking catalyst with high cracking activity, high middle distillate yield and low pour point in the fuel substrate (middle distillate) is the key to improving the economics of the process. Yes.
減圧軽油の水素化分解は既に商業化されており、数十年の歴史を有する確立した技術である。しかしながら、ノルマルを主成分とするパラフィン系炭化水素の反応性は減圧軽油と大きく異なり、減圧軽油の触媒をそのまま転用することが難しいため、パラフィン系炭化水素用の高性能触媒の開発を目指して研究開発が現在精力的に続けられている。少数ではあるが、既に特許や報文がある。例えば、特許文献１にはシリカアルミナを含有した担体に白金を担持した触媒が開示されている。また、特許文献２においては、ＵＳＹゼオライトに白金を担持した触媒を用いてパラフィン系炭化水素の水素化分解を行った研究例がある。
一般にゼオライトの分解活性は満足する水準にあるものの、中間留分得率が低く、また流動点が十分に低い燃料基材（中間留分）が得られないという欠点がある。一方、シリカアルミナに代表されるアモルファス固体酸触媒は、中間留分得率および燃料基材（中間留分）の流動点は満足すべき高い水準にあるものの、分解活性が低い。即ち、分解活性、中間留分得率および燃料基材（中間留分）の低流動点の三者を同時に満足する触媒はまだ開発されておらず、これがパラフィン系炭化水素の水素化分解プロセスの経済性向上に大きな障害となっている。
In general, although the cracking activity of zeolite is at a satisfactory level, there are disadvantages that the yield of middle distillate is low and a fuel base material (middle distillate) having a sufficiently low pour point cannot be obtained. On the other hand, an amorphous solid acid catalyst typified by silica alumina is low in cracking activity, although the middle distillate yield and the pour point of the fuel substrate (middle distillate) are at a satisfactory level. In other words, a catalyst that simultaneously satisfies the three requirements of cracking activity, middle distillate yield, and low pour point of the fuel substrate (middle distillate) has not been developed yet, and this is the process of hydrocracking of paraffinic hydrocarbons. This is a major obstacle to improving economic efficiency.
本発明の目的は、分解活性、中間留分得率および燃料基材（中間留分）の低流動点の三者を同時に満足する、パラフィン系炭化水素から燃料基材を製造するための触媒およびこの触媒を用いた燃料基材の製造方法を提供することによりプロセスの経済性をさらに向上させることにある。 An object of the present invention is to provide a catalyst for producing a fuel substrate from paraffinic hydrocarbons, which simultaneously satisfies the three requirements of cracking activity, middle distillate yield and low pour point of the fuel substrate (middle distillate), and The object of the present invention is to further improve the economics of the process by providing a method for producing a fuel substrate using this catalyst.
本発明者らは鋭意検討した結果、Ｘ線回折において１１１面（２θ＝５．０〜６．０°）に現れるピーク強度が３０以下であるＮａＹを原料として得られたＵＳＹゼオライトを触媒とすることで上述の課題を解決できることを見出し、本発明を完成するに至った。
ここでいうピーク強度とは、２θ＝４〜１２０°に現れるピークの高さの総和を１００としたときのピークの高さを示す。
すなわち本発明は、Ｘ線回折において１１１面に現れるピークの強度が３０以下であるＮａＹを原料として得られたＵＳＹゼオライトに周期律表第VIII族の貴金属を含むことを特徴とするパラフィン系炭化水素用水素化分解触媒に関する。
さらに本発明は、前記記載の触媒を用いて、パラフィン系炭化水素を水素化分解することを特徴とする燃料基材の製造方法に関する。
As a result of intensive studies, the present inventors used as a catalyst a USY zeolite obtained using NaY having a peak intensity of 30 or less appearing on the 111 plane (2θ = 5.0 to 6.0 °) in X-ray diffraction as a raw material. As a result, the inventors have found that the above-described problems can be solved, and have completed the present invention.
The peak intensity here refers to the peak height when the sum of the peak heights appearing at 2θ = 4 to 120 ° is taken as 100.
That is, the present invention provides a paraffinic hydrocarbon characterized in that a USY zeolite obtained using NaY having a peak intensity of 30 or less appearing on the 111 plane in X-ray diffraction as a raw material contains a Group VIII noble metal The present invention relates to a hydrocracking catalyst.
Furthermore, the present invention relates to a method for producing a fuel substrate, characterized in that paraffinic hydrocarbons are hydrocracked using the catalyst described above.
本発明の触媒をパラフィン系炭化水素の水素化分解に使用することにより、高分解活性、高い中間留分得率、燃料基材（中間留分）の低流動点の三者を同時に満足した液状炭化水素を製造することができる。 By using the catalyst of the present invention for the hydrocracking of paraffinic hydrocarbons, a liquid that satisfies the three requirements of high cracking activity, high middle distillate yield, and low pour point of the fuel substrate (middle distillate) simultaneously. Hydrocarbons can be produced.
以下に本発明を詳述する。
本発明に用いられるＵＳＹゼオライトとは、Ｘ線回折において１１１面に現れるピークの強度が３０以下、好ましくは２０〜２５であるＮａＹを原料として得られたものである。このＵＳＹゼオライトのケイバン比（シリカとアルミナのモル比）は通常２０〜１４０であり、より好ましくは３０〜８０である。
また、ＵＳＹゼオライトの平均粒子径は、１．０μｍ以下が好ましく、０．５μｍ以下がより好ましい。
The present invention is described in detail below.
The USY zeolite used in the present invention is obtained from NaY having a peak intensity of 30 or less, preferably 20 to 25, appearing on the 111 plane in X-ray diffraction. The cayban ratio (molar ratio of silica and alumina) of this USY zeolite is usually 20 to 140, more preferably 30 to 80.
Further, the average particle size of USY zeolite is preferably 1.0 μm or less, and more preferably 0.5 μm or less.
本発明の水素化分解触媒は、活性成分としてＵＳＹゼオライト単独で用いることができるが、アモルファス固体酸を含有することで更に性能を向上することができる。アモルファス固体酸としては、シリカアルミナ、シリカチタニア、シリカジルコニア、アルミナボリアなどが挙げられ、より好ましくはシリカアルミナ、シリカジルコニアおよびアルミナボリアの中から選ばれる１種類以上の固体酸が挙げられる。
このときの、触媒中のアモルファス固体酸／ＵＳＹゼオライトの質量比としては特に制限は無いが０．１〜８０の範囲であることが好ましく、１〜６０がより好ましい。
The hydrocracking catalyst of the present invention can be used alone as an active component of USY zeolite, but the performance can be further improved by containing an amorphous solid acid. Examples of the amorphous solid acid include silica alumina, silica titania, silica zirconia, and alumina boria, and more preferably one or more kinds of solid acids selected from silica alumina, silica zirconia, and alumina boria.
The mass ratio of the amorphous solid acid / USY zeolite in the catalyst at this time is not particularly limited, but is preferably in the range of 0.1 to 80, and more preferably 1 to 60.
触媒の成型の為に使用されるバインダーについては特に制限は無いが、通常、アルミナ、シリカ、チタニア、マグネシアが好ましく、最も好ましくはアルミナである。本発明で成型に使用されるバインダーの成型触媒全体に対する割合に特に制限は無いが、通常５〜９９質量％であり、好ましくは２０〜９９質量％である。 The binder used for molding the catalyst is not particularly limited, but usually, alumina, silica, titania and magnesia are preferable, and alumina is most preferable. Although there is no restriction | limiting in particular in the ratio with respect to the whole shaping | molding catalyst of the binder used for shaping | molding by this invention, Usually, it is 5-99 mass%, Preferably it is 20-99 mass%.
本発明の触媒におけるＵＳＹゼオライトの含有量は、バインダーを含む成型触媒全量基準で０．１〜１５質量％であることが好ましく、１〜１０質量％であることがより好ましい。 The content of USY zeolite in the catalyst of the present invention is preferably 0.1 to 15% by mass, and more preferably 1 to 10% by mass based on the total amount of the molded catalyst including the binder.
本発明の触媒は活性成分として周期律表第VIII族の貴金属を含むことが必要である。なお、活性成分として周期律表第VIII族の貴金属以外のものを用いた場合には、中間留分得率が著しく低下するため本発明の目的を達成することができない。
第VIII族の貴金属としては、具体的には、ロジウム、パラジウム、イリジウム、白金などが挙げられる。最も好ましくはパラジウムおよび白金である。これらの貴金属を、前述の成型体に含浸やイオン交換等の常法によって担持することにより本発明の触媒を製造することができる。
担持する貴金属は、必要に応じて２種以上を適宜組み合わせて使用することができる。例えば、白金とパラジウムの両者を担持して使用することができる。これら貴金属の担持量に特に制限はないが、通常、触媒全量基準で０．０２〜２質量％である。
The catalyst of the present invention needs to contain a noble metal of Group VIII of the periodic table as an active component. When an active ingredient other than a noble metal of Group VIII of the periodic table is used, the middle distillate yield is remarkably lowered, and the object of the present invention cannot be achieved.
The Group VIII noble metals, specifically, rhodium, palladium, iridium, and platinum. Most preferred are palladium and platinum. The catalyst of the present invention can be produced by supporting these noble metals on the aforementioned molded body by a conventional method such as impregnation or ion exchange.
Two or more kinds of noble metals to be supported can be used in appropriate combination as required. For example, both platinum and palladium can be supported and used. The amount of these noble metals supported is not particularly limited, but is usually 0.02 to 2% by mass based on the total amount of the catalyst.
本発明においてパラフィン系炭化水素とは、パラフィン分子の含有率が７０モル％以上の炭化水素を指す。パラフィン系炭化水素分子の炭素数については特に制限はないが、通常、１５〜１００程度のものが用いられる。本発明の触媒は、通常ワックスと称される炭素数２０以上のパラフィン系炭化水素の水素化分解により有効である。
原料となるパラフィン系炭化水素の製法については特に制限はなく、本発明の触媒は石油系および合成系の各種パラフィン系炭化水素に適用することができるが、特に好ましいパラフィン系炭化水素として、フィッシャー・トロプシュ合成により製造されるいわゆるＦＴ−ワックスを挙げることができる。
In the present invention, the paraffinic hydrocarbon refers to a hydrocarbon having a paraffin molecule content of 70 mol% or more. Although there is no restriction | limiting in particular about carbon number of a paraffin type hydrocarbon molecule, Usually, the thing of about 15-100 is used. The catalyst of the present invention is effective by hydrocracking a paraffinic hydrocarbon having 20 or more carbon atoms, usually called a wax.
There is no particular limitation on the method for producing the paraffinic hydrocarbon as a raw material, and the catalyst of the present invention can be applied to various petroleum and synthetic paraffinic hydrocarbons. Mention may be made of so-called FT-waxes produced by Tropsch synthesis.
本発明の触媒の使用にあたっては、従来の固定床反応装置を使用することができる。反応条件として、温度は２００〜４５０℃、水素圧は０．５〜１２ＭＰａ、パラフィン系炭化水素原料の液空間速度は０．１〜１０／ｈを挙げることができ、好ましくは温度２５０〜４００℃、水素圧は２．０〜８．０ＭＰａ、パラフィン系炭化水素原料の液空間速度は０．３〜５．０／ｈである。 In using the catalyst of the present invention, a conventional fixed bed reactor can be used. As reaction conditions, the temperature is 200 to 450 ° C., the hydrogen pressure is 0.5 to 12 MPa, and the liquid space velocity of the paraffinic hydrocarbon raw material is 0.1 to 10 / h, preferably the temperature is 250 to 400 ° C. The hydrogen pressure is 2.0 to 8.0 MPa, and the liquid space velocity of the paraffinic hydrocarbon raw material is 0.3 to 5.0 / h.
以上のようなＸ線回折において１１１面に現れるピークの強度が３０以下であるＮａＹを原料として得られたＵＳＹゼオライトを含み、かつ周期律表第VIII族の貴金属を含む触媒を、パラフィン系炭化水素の水素化分解に使用することにより、高分解活性、高い中間留分得率、燃料基材（中間留分）の低流動点の三者を同時に満足した液状炭化水素を製造することができる。 A catalyst containing USY zeolite obtained by using NaY having a peak intensity of 30 or less appearing on the 111 plane in X-ray diffraction as described above as a raw material and containing a noble metal of Group VIII of the periodic table is used as a paraffin hydrocarbon. By using this for hydrocracking, it is possible to produce a liquid hydrocarbon that simultaneously satisfies the three requirements of high cracking activity, high middle distillate yield, and low pour point of the fuel substrate (middle distillate).
以下に実施例及び比較例を挙げ、本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.
［実施例１］
Ｘ線回折において１１１面に現れるピークの強度が２３であるＮａＹ（ａ）を原料として得られたＵＳＹゼオライト（ａ）（ケイバン比が３６、平均粒子径が０．８μｍ）７０ｇとアルミナバインダー９３０ｇから成る直径１／１６インチ（約１．６ｍｍ）の円柱状担体に、白金元素として担体の０．８質量％となる量のジクロロテトラアンミン白金（II）の水溶液を含浸した後、これを１２０℃で３時間乾燥および５００℃で１時間焼成することにより、触媒を調製した。
ここで、ＵＳＹゼオライト（ａ）は、以下のようにして作製される。
[Example 1]
From 70 g of USY zeolite (a) (Caban ratio is 36, average particle size is 0.8 μm) obtained from NaY (a) having a peak intensity of 23 appearing on the 111 plane in X-ray diffraction and 930 g of alumina binder. After impregnating a cylindrical support having a diameter of 1/16 inch (about 1.6 mm) with an aqueous solution of dichlorotetraammineplatinum (II) in an amount of 0.8% by mass of the support as a platinum element, The catalyst was prepared by drying for 3 hours and calcining at 500 ° C. for 1 hour.
Here, the USY zeolite (a) is produced as follows.
（第１工程）
Ｎａ２Ｏとして１７．０質量％とＡｌ２Ｏ３として２２．０質量％を含有するアルミン酸ナトリウム水溶液０．１６４ｋｇを、撹拌しながら２２．７６質量％の水酸化ナトリウム水溶液１．２５０ｋｇに加えた。この溶液を撹拌しながら、更にＳｉＯ２の濃度が２４．０質量％の３号水硝子１．３２４ｋｇの中に加え、種子組成物を得た。この種子組成物に含まれる各成分の酸化物のモル比を（１）式に示す。
１６Ｎａ２Ｏ・Ａｌ２Ｏ３・１５ＳｉＯ２・３２０Ｈ２Ｏ・・・（１）
この種子組成物を３０分撹拌した後、３０〜３５℃で１３時間静置して熟成させ、Ｙ型ゼオライトのシード（種子）２．７３７ｋｇを得た。
(First step)
0.164 kg of sodium aluminate aqueous solution containing 17.0% by mass as Na 2 O and 22.0% by mass as Al 2 O 3 was added to 1.250 kg of 22.76% by mass sodium hydroxide aqueous solution while stirring. It was. While stirring this solution, it was further added to 1.324 kg of No. 3 water glass having a SiO 2 concentration of 24.0% by mass to obtain a seed composition. The molar ratio of the oxide of each component contained in this seed composition is shown in the formula (1).
16Na 2 O · Al 2 O 3 · 15SiO 2 · 320H 2 O ··· (1)
The seed composition was stirred for 30 minutes and then allowed to stand at 30 to 35 ° C. for 13 hours for aging to obtain 2.737 kg of Y-type zeolite seed (seed).
（第２工程）
純水１９．３８７ｋｇにＳｉＯ２の濃度が２４．０質量％の３号水硝子２２．０４３ｋｇを添加した後、撹拌して混合し、更にＳｉＯ２の濃度が３０．０質量％のシリカゲル（触媒化成工業社製 Cataloid SI-30）を１７．１６０ｋｇ加え、よく撹拌して混合した。これに、第１工程で作製したシード２．７３７ｋｇを加え、次にＮａ２Ｏとして１７．０質量％及びＡｌ２Ｏ３として２２．０質量％で示されるアルミン酸ナトリウム水溶液９．１０９ｋｇを加え、均一になるまで十分混合し、室温で３時間撹拌して熟成し、反応混合物を得た。この反応混合物の組成は、酸化物モル比で（２）式のように示される。
２．９Ｎａ２Ｏ・Ａｌ２Ｏ３・９．０ＳｉＯ２・１５０Ｈ２Ｏ・・・（２）
(Second step)
After adding 22.043 kg of No. 3 water glass having a SiO 2 concentration of 24.0% by mass to 19.387 kg of pure water, the mixture was stirred and mixed, and further silica gel (catalyst having a SiO 2 concentration of 30.0% by mass). 17.160 kg of Cataloid SI-30 manufactured by Kasei Kogyo Co., Ltd. was added and mixed with good stirring. To this was added 2.737 kg of the seed prepared in the first step, and then 9.109 kg of an aqueous sodium aluminate solution represented by 17.0% by mass as Na 2 O and 22.0% by mass as Al 2 O 3 was added. The mixture was sufficiently mixed until it became uniform, and aged by stirring at room temperature for 3 hours to obtain a reaction mixture. The composition of this reaction mixture is represented by the formula (2) in terms of oxide molar ratio.
2.9Na 2 O · Al 2 O 3 · 9.0SiO 2 · 150H 2 O ··· (2)
（第３工程）
第２工程で得られた反応混合物をコロイドミルで５回粉砕した後、結晶化槽に移して９５℃で４８時間、結晶化するまで加温して熟成を行った。熟成終了後、結晶化槽内を冷却し、熟成生成物を取り出し、濾過、洗浄、乾燥を順次行って、ＮａＹ（ａ）約９ｋｇを得た。このＮａＹ（ａ）は、Ｘ線回折において１１１面に現れるピークの強度が２３、平均粒子径が０．８μｍ、結晶化度が１．０５、格子定数が２４．６７Å、ケイバン比が５．１、比表面積が７２５ｍ２／ｇであった。
(Third step)
The reaction mixture obtained in the second step was pulverized five times with a colloid mill, then transferred to a crystallization tank and heated at 95 ° C. for 48 hours until crystallization, followed by aging. After completion of aging, the inside of the crystallization tank was cooled, the aging product was taken out, filtered, washed, and dried in order to obtain about 9 kg of NaY (a). This NaY (a) has an intensity of a peak appearing on the 111 plane in X-ray diffraction of 23, an average particle diameter of 0.8 μm, a crystallinity of 1.05, a lattice constant of 24.67Å, and a cayban ratio of 5.1. The specific surface area was 725 m 2 / g.
（第４工程）
第３工程で得られたＮａＹ（ａ）を、６０℃の温水９リットルに懸濁し、ＮａＹ（ａ）に対して等モルの硫酸アンモニウム２．６４ｋｇを加えた後、３０分間撹拌してイオン交換した。その後、母液をろ別し、イオン交換したゼオライトを再度、硫酸アンモニウム２．６４ｋｇを６０℃の温水２０リットルに溶解した溶液でイオン交換した。これを濾過し、６０℃の温水９０リットルで洗浄し、乾燥を行い、６５％イオン交換されたＮＨ４Ｙを得た。
(4th process)
The NaY (a) obtained in the third step was suspended in 9 liters of warm water at 60 ° C., and 2.64 kg of equimolar ammonium sulfate was added to NaY (a), followed by stirring for 30 minutes for ion exchange. . Thereafter, the mother liquor was filtered off, and the ion-exchanged zeolite was ion-exchanged again with a solution obtained by dissolving 2.64 kg of ammonium sulfate in 20 liters of hot water at 60 ° C. This was filtered, washed with 90 liters of warm water at 60 ° C., and dried to obtain 65% ion-exchanged NH 4 Y.
（第５工程）
第４工程で得られたＮＨ４Ｙを回転スチーミング装置に入れ、飽和水蒸気雰囲気中で６７０℃で３０分間スチーミング焼成しＨＹを得た。このＨＹ型ゼオライトを６０℃の温水９０リットルに懸濁させ、これをコロイドミルに通して固まりをほぐした。次いで、ＨＹに対して４倍モル量の硫酸アンモニウム１０．５６ｋｇを加え、撹拌しながら９０℃で１時間イオン交換した後、これを濾過し、６０℃の温水９０リットルで洗浄して、乾燥し、９０％イオン交換されたＮＨ４Ｙを得た。このＮＨ４Ｙを回転スチーミング装置に入れ、飽和水蒸気雰囲気中、７００℃で３０分間スチーミング焼成して粗ＵＳＹゼオライトを約６．５ｋｇ得た。
(5th process)
NH 4 Y obtained in the fourth step was put in a rotary steaming apparatus and steamed and fired at 670 ° C. for 30 minutes in a saturated steam atmosphere to obtain HY. This HY-type zeolite was suspended in 90 liters of hot water at 60 ° C., and passed through a colloid mill to loosen the mass. Next, after adding 10.56 kg of ammonium sulfate having a 4-fold molar amount with respect to HY and ion-exchanged at 90 ° C. for 1 hour with stirring, this was filtered, washed with 90 liters of hot water at 60 ° C., and dried. 90% ion exchanged NH 4 Y was obtained. This NH 4 Y was put in a rotary steaming device and steamed for 30 minutes at 700 ° C. in a saturated steam atmosphere to obtain about 6.5 kg of crude USY zeolite.
（第６工程）
第５工程で得られた粗ＵＳＹゼオライト５．０ｋｇを水２０リットルに懸濁し、これをコロイドミルに通して固まりをほぐした。次いで、２５％硫酸５．０２７ｋｇを加え、７０℃で１時間撹拌してアルミナを除いた。これを濾過し、水で洗浄後、乾燥して約１．５ｋｇのＵＳＹゼオライト（ａ）を得た。このＵＳＹゼオライト（ａ）は、結晶化度が１．０４、格子定数が２４．３５、ケイバン比が３６、比表面積が７５３ｍ２／ｇであった。
(Sixth step)
The crude USY zeolite (5.0 kg) obtained in the fifth step was suspended in 20 liters of water and passed through a colloid mill to loosen up the mass. Next, 5.027 kg of 25% sulfuric acid was added and stirred at 70 ° C. for 1 hour to remove alumina. This was filtered, washed with water and dried to obtain about 1.5 kg of USY zeolite (a). This USY zeolite (a) had a crystallinity of 1.04, a lattice constant of 24.35, a Keiban ratio of 36, and a specific surface area of 753 m 2 / g.
上記のように調製された触媒（２００ｍｌ）を固定床の流通式反応器に充填し、パラフィン系炭化水素の水素化分解に用いた。パラフィン系炭化水素として、パラフィン含量が９５％で２１から８０までの炭素数分布を有するＦＴワックスを原料とした。この時の水素圧は５ＭＰａ、原料の液空間速度は２．０／ｈであった。沸点３６０℃以下の留分を分解生成物とし、原料に対して８０質量％の分解生成物が得られる時の反応温度および原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。 The catalyst (200 ml) prepared as described above was charged into a fixed bed flow reactor and used for hydrocracking of paraffinic hydrocarbons. As a paraffin hydrocarbon, FT wax having a paraffin content of 95% and a carbon number distribution of 21 to 80 was used as a raw material. The hydrogen pressure at this time was 5 MPa, and the liquid space velocity of the raw material was 2.0 / h. A fraction having a boiling point of 360 ° C. or less is regarded as a decomposition product, and a reaction temperature when a decomposition product of 80% by mass is obtained with respect to the raw material, a middle distillate (boiling point is 145 to 360 ° C.) yield, and flow I asked for a point. The results are shown in Table 1.
［実施例２］
実施例１記載のＵＳＹゼオライト（ａ）７０ｇとシリカアルミナ粉末５３０ｇを４００ｇのアルミナをバインダーとして成型し、直径１／１６インチ（約１．６ｍｍ）の円柱状担体を得た。この担体に実施例１と同様の方法で白金を担体の０．８質量％となるように担持した。さらにこれを１２０℃で３時間乾燥および５００℃で１時間焼成することにより、触媒を調製した。
また、この触媒を用いて実施例１と同様に水素化分解を行い、８０質量％の分解生成物が得られる時の反応温度、原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。
[Example 2]
70 g of USY zeolite (a) described in Example 1 and 530 g of silica alumina powder were molded using 400 g of alumina as a binder to obtain a cylindrical carrier having a diameter of 1/16 inch (about 1.6 mm). Platinum was supported on this carrier in the same manner as in Example 1 so that it might be 0.8% by mass of the carrier. Furthermore, the catalyst was prepared by drying this at 120 degreeC for 3 hours, and baking at 500 degreeC for 1 hour.
In addition, hydrocracking was carried out using this catalyst in the same manner as in Example 1 to obtain a reaction temperature when a decomposition product of 80% by mass was obtained, a middle distillate (boiling point: 145 to 360 ° C.) yield relative to the raw material, And the pour point was determined. The results are shown in Table 1.
［実施例３］
実施例１記載のＵＳＹゼオライト（ａ）７０ｇとアルミナボリア５３０ｇを４００ｇのアルミナをバインダーとして成型し、直径１／１６インチ（約１．６ｍｍ）の円柱状担体を得た。この担体に実施例１と同様の方法で白金を担体の０．８質量％となるように担持した。さらにこれを１２０℃で３時間乾燥および５００℃で１時間焼成することにより、触媒を調製した。
また、この触媒を用いて実施例１と同様に水素化分解を行い、８０質量％の分解生成物が得られる時の反応温度、原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。
[Example 3]
70 g of USY zeolite (a) described in Example 1 and 530 g of alumina boria were molded using 400 g of alumina as a binder to obtain a cylindrical carrier having a diameter of 1/16 inch (about 1.6 mm). Platinum was supported on this carrier in the same manner as in Example 1 so that it might be 0.8% by mass of the carrier. Furthermore, the catalyst was prepared by drying this at 120 degreeC for 3 hours, and baking at 500 degreeC for 1 hour.
In addition, hydrocracking was carried out using this catalyst in the same manner as in Example 1 to obtain a reaction temperature when a decomposition product of 80% by mass was obtained, a middle distillate (boiling point: 145 to 360 ° C.) yield relative to the raw material, And the pour point was determined. The results are shown in Table 1.
［実施例４］
Ｘ線回折において１１１面に現れるピークの強度が２３であるＮａＹ（ｂ）を原料として得られたＵＳＹゼオライト（ｂ）（ケイバン比が３６、平均粒子径が０．４μｍ）７０ｇとアルミナボリア５３０ｇを４００ｇのアルミナをバインダーとして成型し、直径１／１６インチ（約１．６ｍｍ）の円柱状担体を得た。この担体に実施例１と同様の方法で白金を担体の０．８質量％となるように担持した。さらにこれを１２０℃で３時間乾燥および５００℃で１時間焼成することにより、触媒を調製した。
ここで、ＮａＹ（ｂ）は、実施例１の第２工程で得られた反応混合物を、コロイドミルに通して１０回繰り返し粗粒子を充分に粉砕したこと以外は実施例１同様に調製した。ＮａＹ（ｂ）の性状は、Ｘ線回折において１１１面に現れるピークの強度が２３、平均粒子径が０．４μｍ、結晶化度が１．０４、格子定数が２４．６６Å、ケイバン比が５．０、比表面積が７２８ｍ２／ｇであった。また、ＵＳＹゼオライト（ｂ）は、ＮａＹ（ｂ）を使用したこと以外は実施例１と同様に調製した。ＵＳＹゼオライト（ｂ）の性状は、結晶化度が１．０５、格子定数が２４．３６、ケイバン比が３６、比表面積が７８２ｍ２／ｇであった。
また、この触媒を用いて実施例１と同様に水素化分解を行い、８０質量％の分解生成物が得られる時の反応温度、原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。
[Example 4]
70 g of USY zeolite (b) (Caban ratio is 36, average particle size is 0.4 μm) obtained from NaY (b) having a peak intensity of 23 appearing on the 111 plane in X-ray diffraction and 530 g of alumina boria. 400 g of alumina was molded as a binder to obtain a cylindrical carrier having a diameter of 1/16 inch (about 1.6 mm). Platinum was supported on this carrier in the same manner as in Example 1 so that it might be 0.8% by mass of the carrier. Furthermore, the catalyst was prepared by drying this at 120 degreeC for 3 hours, and baking at 500 degreeC for 1 hour.
Here, NaY (b) was prepared in the same manner as in Example 1 except that the reaction mixture obtained in the second step of Example 1 was passed through a colloid mill and repeated 10 times to sufficiently pulverize coarse particles. The properties of NaY (b) are as follows: the intensity of the peak appearing on the 111 plane in X-ray diffraction is 23, the average particle size is 0.4 μm, the crystallinity is 1.04, the lattice constant is 24.66 ケ イ, and the caivan ratio is 5. 0, and the specific surface area was 728 m 2 / g. USY zeolite (b) was prepared in the same manner as in Example 1 except that NaY (b) was used. The properties of USY zeolite (b) were a crystallinity of 1.05, a lattice constant of 24.36, a Keiban ratio of 36, and a specific surface area of 782 m 2 / g.
In addition, hydrocracking was carried out using this catalyst in the same manner as in Example 1 to obtain a reaction temperature when a decomposition product of 80% by mass was obtained, a middle distillate (boiling point: 145 to 360 ° C.) yield relative to the raw material, And the pour point was determined. The results are shown in Table 1.
［実施例５］
実施例４記載のＵＳＹゼオライト（ｂ）３０ｇを９７０ｇのアルミナをバインダーとして成型し、直径１／１６インチ（約１．６ｍｍ）の円柱状担体を得た。この担体に実施例１と同様の方法で白金を担体の０．８質量％となるように担持した。さらにこれを１２０℃で３時間乾燥および５００℃で１時間焼成することにより、触媒を調製した。
また、この触媒を用いて実施例１と同様に水素化分解を行い、８０質量％の分解生成物が得られる時の反応温度、原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。
[Example 5]
30 g of USY zeolite (b) described in Example 4 was molded using 970 g of alumina as a binder to obtain a cylindrical support having a diameter of 1/16 inch (about 1.6 mm). Platinum was supported on this carrier in the same manner as in Example 1 so that it might be 0.8% by mass of the carrier. Furthermore, the catalyst was prepared by drying this at 120 degreeC for 3 hours, and baking at 500 degreeC for 1 hour.
In addition, hydrocracking was carried out using this catalyst in the same manner as in Example 1 to obtain a reaction temperature when a decomposition product of 80% by mass was obtained, a middle distillate (boiling point: 145 to 360 ° C.) yield relative to the raw material, And the pour point was determined. The results are shown in Table 1.
［実施例６］
実施例４記載のＵＳＹゼオライト（ｂ）３０ｇとアルミナボリア５３０ｇを４４０ｇのアルミナをバインダーとして成型し、直径１／１６インチ（約１．６ｍｍ）の円柱状担体を得た。この担体に実施例１と同様の方法で白金を担体の０．８質量％となるように担持した。さらにこれを１２０℃で３時間乾燥および５００℃で１時間焼成することにより、触媒を調製した。
また、この触媒を用いて実施例１と同様に水素化分解を行い、８０質量％の分解生成物が得られる時の反応温度、原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。
[Example 6]
30 g of USY zeolite (b) described in Example 4 and 530 g of alumina boria were molded using 440 g of alumina as a binder to obtain a cylindrical carrier having a diameter of 1/16 inch (about 1.6 mm). Platinum was supported on this carrier in the same manner as in Example 1 so that it might be 0.8% by mass of the carrier. Furthermore, the catalyst was prepared by drying this at 120 degreeC for 3 hours, and baking at 500 degreeC for 1 hour.
In addition, hydrocracking was carried out using this catalyst in the same manner as in Example 1 to obtain a reaction temperature when a decomposition product of 80% by mass was obtained, a middle distillate (boiling point: 145 to 360 ° C.) yield relative to the raw material, And the pour point was determined. The results are shown in Table 1.
［比較例１］
Ｘ線回折において１１１面に現れるピークの強度が３７であるＮａＹ（ｃ）を原料として得られたＵＳＹゼオライト（ｃ）（ケイバン比が３７、平均粒子径が１．３μｍ）を用いたこと以外は実施例１と同様に触媒調製および水素化分解反応を行い、８０質量％の分解生成物が得られる時の分解温度、原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。
ここで、ＮａＹ（ｃ）は、実施例１の第２工程で得られた反応混合物をコロイドミルに１回通し、固まりをほぐしたこと以外は実施例１同様に調製した。ＮａＹ（ｃ）の性状は、Ｘ線回折において１１１面に現れるピークの強度が３７、平均粒子径が１．３μｍ、結晶化度が１．０５、格子定数が２４．６６Å、ケイバン比が５．１、比表面積が７２１ｍ２／ｇであった。また、ＵＳＹゼオライト（ｃ）は、ＮａＹ（ｃ）を使用したこと以外は実施例１と同様に調製した。ＵＳＹゼオライト（ｃ）の性状は、結晶化度が１．０３、格子定数が２４．３５、ケイバン比が３７、比表面積が７５８ｍ２／ｇであった。
[Comparative Example 1]
Except for using USY zeolite (c) obtained by using NaY (c) having a peak intensity of 37 appearing on the 111 plane in X-ray diffraction as a raw material (with a Keiban ratio of 37 and an average particle size of 1.3 μm). The catalyst preparation and the hydrocracking reaction were carried out in the same manner as in Example 1, and the cracking temperature when a cracked product of 80% by mass was obtained, the middle distillate (boiling point: 145 to 360 ° C.) yield, and the pour point. Asked. The results are shown in Table 1.
Here, NaY (c) was prepared in the same manner as in Example 1 except that the reaction mixture obtained in the second step of Example 1 was passed through the colloid mill once to loosen the mass. The properties of NaY (c) are such that the peak intensity appearing on the 111 plane in X-ray diffraction is 37, the average particle diameter is 1.3 μm, the crystallinity is 1.05, the lattice constant is 24.66２４, and the caivan ratio is 5. 1. The specific surface area was 721 m 2 / g. USY zeolite (c) was prepared in the same manner as in Example 1 except that NaY (c) was used. The properties of USY zeolite (c) were a crystallinity of 1.03, a lattice constant of 24.35, a Keiban ratio of 37, and a specific surface area of 758 m 2 / g.
［比較例２］
比較例１と同じＵＳＹゼオライト（ｃ）を用いたこと以外は実施例３と同様に触媒調製および水素化分解反応を行い、８０質量％の分解生成物が得られる時の分解温度、原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。
[Comparative Example 2]
Except that the same USY zeolite (c) as in Comparative Example 1 was used, the catalyst preparation and hydrocracking reaction were carried out in the same manner as in Example 3, and the cracking temperature when an 80% by mass cracked product was obtained, The yield (boiling point: 145 to 360 ° C.) yield and pour point were determined. The results are shown in Table 1.
［比較例３］
比較例１と同じＵＳＹゼオライト（ｃ）を用いたこと以外は実施例６と同様に触媒調製および水素化分解反応を行い、８０質量％の分解生成物が得られる時の分解温度、原料に対する中間留分（沸点が１４５〜３６０℃）得率、及び流動点を求めた。その結果を表１に示した。
[Comparative Example 3]
Except that the same USY zeolite (c) as in Comparative Example 1 was used, the catalyst preparation and hydrocracking reaction were carried out in the same manner as in Example 6, and the cracking temperature at which a cracked product of 80% by mass was obtained, The yield (boiling point: 145 to 360 ° C.) yield and pour point were determined. The results are shown in Table 1.
表１から明らかなように、Ｘ線回折において１１１面に現れるピークの強度が３０以下であるＮａＹを原料として得られたＵＳＹゼオライトを用いることで、高い分解活性、高い中間留分得率および低流動点を同時に満足することがわかる。さらに、アモルファス固体酸とを組合わせることがより有効であることがわかる。 As is clear from Table 1, by using USY zeolite obtained from NaY having a peak intensity of 30 or less appearing on the 111 plane in X-ray diffraction as a raw material, high decomposition activity, high middle distillate yield and low It can be seen that the pour point is satisfied at the same time. Furthermore, it turns out that combining with an amorphous solid acid is more effective.
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