JPH055539B2 - - Google Patents
Info
- Publication number
- JPH055539B2 JPH055539B2 JP59009399A JP939984A JPH055539B2 JP H055539 B2 JPH055539 B2 JP H055539B2 JP 59009399 A JP59009399 A JP 59009399A JP 939984 A JP939984 A JP 939984A JP H055539 B2 JPH055539 B2 JP H055539B2
- Authority
- JP
- Japan
- Prior art keywords
- crystalline aluminosilicate
- fluorine
- catalyst
- containing compound
- ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 238000003682 fluorination reaction Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- -1 hexafluorosilicic acid Chemical compound 0.000 claims description 3
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 2
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 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 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
（産業上の利用分野）
本発明は、合成ガスから炭化水素を製造する方
法において、重質芳香族成分の生成を抑制するた
めの触媒成分の処理方法に関する。
（従来の技術）
一酸化炭素と水素との合成ガスから各種炭化水
素の混合物を製造する方法では、様々な触媒が使
用される。
例えば、結晶性アルミノシリケートを基体とし
これにトリウム、亜鉛などの活性金属を担持させ
た触媒を用いる方法（特公昭58−39131号公報参
照）が知られている。
また、フツ素含有化合物により液相で結晶性ア
ルミノシリケートをフツ素化処理する方法とし
て、特公昭47−14330号及び同49−38082号各公報
等に記載された方法があるが、フツ素含有化合物
の濃度は２％以下の希薄な溶液を用いており、処
理を行う結晶性アルミノシリケートもSiO2／
Al2O3のモル比が10以上のものではない。
更に、これら触媒を用いて合成ガスから炭化水
素混合物を製造した場合、炭素数10以上の重質芳
香族成分の生成割合が大きく、また炭素析出によ
り短時間で失活するという問題がある。
ガソリンの製造などを目的とした場合、上記重
質芳香族成分の生成割合を抑制できれば、触媒寿
命や精製ガソリンの性状にとつて工業的価値は非
常に高くなる。
（発明が解決しようとする課題）
本発明は、上記した問題を解決し、合成ガスか
ら炭化水素を製造する方法において、重質芳香族
成分の生成割合を抑制するための触媒成分の処理
方法を提供することを目的とする。
（課題を解決するための手段）
本発明は、SiO2／Al1O3のモル比が10以上の結
晶性アルミノシリケートを、３〜50重量％の濃度
のフツ素含有化合物の水溶液中で処理することを
特徴とする結晶性アルミノシリケートのフツ素化
処理方法である。
本発明で用いる結晶性アルミノシリケートは、
天然産又はゼオライトと称される人工産のいずれ
であつてもよく、酸素原子の共有によつて交叉結
合したSiO4四面体とAlO4四面体とから成る合成
結晶性構造で特徴づけられ、精密に規制された微
細孔を有するものである。孔径が５Å以上、
SlO2／Al2O3のモル比が10以上、好ましくは10〜
1000、拘束指数は特に限定されないが、好ましく
は１〜12である結晶性アルミノシリケートが好適
である。このような結晶性アルミノシリケート
は、フツ素含有化合物の濃厚な溶液で処理しても
結晶構造が崩れることがない。これらの具体例と
しては、ZSM−５、ZSM−11、ZSM−12、ZSM
−23、ZSM−35、ZSM−48、モルデナイト、フ
エリエライト、ISI−１などが挙げられる。
上記した結晶性アルミノシリケートにフツ素化
処理を施す方法としては、フツ化アンモニウム、
フツ酸、フツ化水素アンモニウム、ヘキサフルオ
ロケイ酸、ヘキサフルオロケイ酸アンモニウム、
フツ化ナトリウム又は／及びフツ化水素カリウム
などのフツ素含有化合物の水溶液に結晶性アルミ
ノシリケートの粉又は顆粒を浸漬攪拌する方法な
どが適用される。処理条件については特に制限は
受けないが、次のような条件が好適である。すな
わち、フツ素含有化合物の濃度は３〜50重量％、
処理温度０〜100℃、処理時間１分〜10時間がよ
い。このとき、処理温度が高いほど処理時間は短
くてよい。フツ素化処理後、水で洗浄してもよい
ししなくてもよい。乾燥後は、300〜700℃の温度
で焼成することが好適である。
このようにしてフツ素化処理が施された結晶性
アルミノシリケートはその結晶構造は変わらない
が、活性点の性質や細孔径分布が微妙に変化す
る。
なお、このフツ素化処理した結晶性アルミノシ
リケートを炭化水素製造触媒として使用するに
は、このものに一酸化炭素還元能を有する金属若
しくは金属化合物を組み合わせる。組合わせる金
属又は金属化合物としては、一酸化炭素を還元し
て水素化できる金属又は金属化合物であれば何で
もあつてもよいが、具体的には、金属としては
鉄、ニツケル、コバルトのような遷移金属、クロ
ム、銅、亜鉛などがあげられ、金属化合物として
は上記したような金属の酸化物、炭化物、窒化
物、硝酸塩、硫酸塩、塩化物、硫化物などが挙げ
られる。組合わせ方法としては、両者を物理的に
混合する方法；これら金属又は金属化合物の水溶
液にフツ素化処理した結晶性アルミノシリケート
を浸漬したり、イオン交換処理したりして担持す
る方法などがあげられる。また、これら金属又は
金属化合物を含む各種の触媒とフツ素化処理した
結晶性アルミノシリケートとを混合するという態
様であつてもよい。両者を組合わせる割合は、金
属又は金属化合物の割合が0.1〜99重量％、好ま
しくは１〜80重量％である。用いる触媒の形体は
粉状、顆粒状いずれであつてもよく格別限定され
るものではない。
上記触媒を使用する場合は、合成ガスの水素と
一酸化炭素のモル比（H2／CO）はとくに限定さ
れないが、0.5〜５のものが好適である。合成ガ
スと触媒との接触の方法としては、触媒を反応管
に充填してここに合成ガスを通流するという方法
でよい。このときの反応条件は、温度が150〜500
℃、好ましくは200〜400℃、ガス圧が常圧〜150
Kg／cm2Ｇ、好ましくは10〜100Kg/cm2Ｇ、ガスの
WHSVが0.1〜50kr-1、好ましくは0.3〜15hr-1で
ある。
（発明の効果）
フツ素含有化合物の濃厚な溶液を用いることに
より、ゼオライトの一部がヘキサフルオロケイ酸
として溶解し、その結果ゼオライトの活性点の性
質が変化するとともにゼオライトの細孔分布が変
化し、表面積も増大する。このゼオライトを合成
ガスから炭酸水素を製造するのに使用した場合、
重質芳香族成分の生成を抑制できる。
実施例
参考例 １
結晶性アルミノシリケート（Ｈ−ZSM−５）
の調製
硫酸アルミニウム（18水塩）7.52ｇ、硫酸（97
％）17.6ｇ、テトラプロピルアンモニウムブロマ
イド26.3ｇ及び水100mlからなる溶液をＡ液とし、
水ガラス（SiO229.0重量％、Na2O9.4重量％、水
61.6重量％）211ｇ及び水250mlからなる溶液をＢ
液とし、塩化ナトリウム75ｇ及び水125mlからな
る溶液をＣ液とした。このＣ液中にＡ液とＢ液を
同時に徐々に滴下、混合し、次いで50％硫酸を
6.0ｇ加えてPHを9.5に調整し、１のオートクレ
ーブに入れ、攪拌しながら170℃、自己圧力下に
て20時間反応させた。
反応混合物を冷却した後、生成物を1.5の水
で５回洗浄した。次いで濾過した固形分を120℃
で６時間乾燥して55.0ｇの結晶性アルミノシリケ
ートを得た。この生成物を空気中で550℃にて６
時間焼成した後の組成（モル比）は、0.8Na2O・
Al2O3・65.1SiO2であつた。
その後シリケート１ｇ当たり５mlの１規定硝酸
アンモニウム溶液を用いて室温にて一昼夜イオン
交換を行つた。次いで純水で洗浄し、120℃で６
時間乾燥した後、550℃で６時間焼成し、更に再
度同じ処理を行つてＨ型とした。
実施例 １
参考例１に示した方法で調製したゼオライトＨ
−ZSM−５の粉末50ｇを30重量％フツ化アンモ
ニウム水溶液500ml中に浸漬し、攪拌しながら50
℃で１時間フツ素化処理を施した。
ついで懸濁液を濾過して固形物を分離しこれを
純水で洗浄したのち、120℃で６時間乾燥し、更
に550℃で６時間焼成した。得られた粉末の特性
を参考例１のＨ−ZSM−５と比較して第１表に
示した。
(Industrial Application Field) The present invention relates to a method for treating a catalyst component to suppress the production of heavy aromatic components in a method for producing hydrocarbons from synthesis gas. (Prior Art) Various catalysts are used in methods for producing mixtures of various hydrocarbons from synthesis gas of carbon monoxide and hydrogen. For example, a method is known that uses a catalyst having a crystalline aluminosilicate as a base and supporting active metals such as thorium and zinc (see Japanese Patent Publication No. 39131/1983). In addition, as a method for fluorinating crystalline aluminosilicate in the liquid phase with a fluorine-containing compound, there is a method described in Japanese Patent Publications No. 47-14330 and No. 49-38082. A dilute solution with a compound concentration of 2% or less is used, and the crystalline aluminosilicate to be treated is also SiO 2 /
The molar ratio of Al 2 O 3 is not greater than 10. Furthermore, when a hydrocarbon mixture is produced from synthesis gas using these catalysts, there is a problem that a large proportion of heavy aromatic components having 10 or more carbon atoms are produced and that they are deactivated in a short time due to carbon precipitation. For purposes such as gasoline production, if the production rate of the above-mentioned heavy aromatic components can be suppressed, the industrial value in terms of catalyst life and properties of refined gasoline will be extremely high. (Problems to be Solved by the Invention) The present invention solves the above-mentioned problems and provides a method for treating catalyst components to suppress the production rate of heavy aromatic components in a method for producing hydrocarbons from synthesis gas. The purpose is to provide. (Means for Solving the Problems) The present invention involves treating crystalline aluminosilicate with a SiO 2 /Al 1 O 3 molar ratio of 10 or more in an aqueous solution of a fluorine-containing compound at a concentration of 3 to 50% by weight. This is a method for fluorinating crystalline aluminosilicate. The crystalline aluminosilicate used in the present invention is
It can be either naturally occurring or artificially produced, called zeolite, and is characterized by a synthetic crystalline structure consisting of SiO 4 tetrahedra and AlO 4 tetrahedra cross-linked by shared oxygen atoms, and is It has fine pores that are regulated. The pore diameter is 5 Å or more,
The molar ratio of SlO 2 /Al 2 O 3 is 10 or more, preferably 10 or more
1000, and the constraint index is not particularly limited, but crystalline aluminosilicate having preferably 1 to 12 is suitable. Such crystalline aluminosilicate does not lose its crystal structure even when treated with a concentrated solution of a fluorine-containing compound. Specific examples of these include ZSM-5, ZSM-11, ZSM-12, ZSM
-23, ZSM-35, ZSM-48, mordenite, ferrierite, ISI-1, etc. Methods for fluorination treatment of the above-mentioned crystalline aluminosilicate include ammonium fluoride,
Fluoric acid, ammonium hydrogen fluoride, hexafluorosilicic acid, ammonium hexafluorosilicate,
A method in which crystalline aluminosilicate powder or granules are immersed and stirred in an aqueous solution of a fluorine-containing compound such as sodium fluoride and/or potassium hydrogen fluoride is applied. There are no particular restrictions on the processing conditions, but the following conditions are suitable. That is, the concentration of the fluorine-containing compound is 3 to 50% by weight,
A treatment temperature of 0 to 100°C and a treatment time of 1 minute to 10 hours are preferable. At this time, the higher the treatment temperature, the shorter the treatment time may be. After the fluorination treatment, it may or may not be washed with water. After drying, it is preferable to bake at a temperature of 300 to 700°C. Crystalline aluminosilicate subjected to fluorination treatment in this manner does not change its crystal structure, but the properties of active sites and pore size distribution are slightly changed. In addition, in order to use this fluorinated crystalline aluminosilicate as a hydrocarbon production catalyst, it is combined with a metal or metal compound having carbon monoxide reducing ability. The metal or metal compound to be combined may be any metal or metal compound that can reduce carbon monoxide and hydrogenate it, but specifically metals include transition metals such as iron, nickel, and cobalt. Metals include chromium, copper, zinc, etc., and examples of metal compounds include oxides, carbides, nitrides, nitrates, sulfates, chlorides, and sulfides of the metals mentioned above. Examples of combination methods include a method of physically mixing the two; a method of immersing fluorinated crystalline aluminosilicate in an aqueous solution of these metals or metal compounds, or supporting the metal by ion exchange treatment. It will be done. Alternatively, various catalysts containing these metals or metal compounds and fluorinated crystalline aluminosilicate may be mixed. The proportion of the metal or metal compound in combination is 0.1 to 99% by weight, preferably 1 to 80% by weight. The form of the catalyst used may be either powder or granules and is not particularly limited. When using the above catalyst, the molar ratio of hydrogen to carbon monoxide (H 2 /CO) in the synthesis gas is not particularly limited, but is preferably 0.5 to 5. A method for bringing the synthesis gas into contact with the catalyst may be a method in which a reaction tube is filled with the catalyst and the synthesis gas is passed through the reaction tube. The reaction conditions at this time are a temperature of 150 to 500.
℃, preferably 200~400℃, gas pressure normal pressure ~ 150℃
Kg/cm 2 G, preferably 10-100Kg/cm 2 G, of gas
WHSV is 0.1 to 50 kr -1 , preferably 0.3 to 15 hr -1 . (Effect of the invention) By using a concentrated solution of a fluorine-containing compound, a part of the zeolite is dissolved as hexafluorosilicic acid, and as a result, the properties of the active sites of the zeolite change and the pore distribution of the zeolite changes. However, the surface area also increases. When this zeolite is used to produce hydrogen carbonate from synthesis gas,
The production of heavy aromatic components can be suppressed. Reference example 1 Crystalline aluminosilicate (H-ZSM-5)
Preparation of aluminum sulfate (18 hydrate) 7.52 g, sulfuric acid (97
%) 17.6g, tetrapropylammonium bromide 26.3g and water 100ml as solution A,
Water glass (SiO 2 29.0% by weight, Na 2 O 9.4% by weight, water
A solution consisting of 211 g (61.6% by weight) and 250 ml of water was
A solution consisting of 75 g of sodium chloride and 125 ml of water was used as Solution C. Gradually drop A and B solutions into this C solution and mix them, then add 50% sulfuric acid.
6.0g was added to adjust the pH to 9.5, and the mixture was placed in an autoclave No. 1, and reacted for 20 hours at 170°C under autogenous pressure while stirring. After cooling the reaction mixture, the product was washed 5 times with 1.5 g of water. Then, the filtered solid content was heated to 120℃.
After drying for 6 hours, 55.0 g of crystalline aluminosilicate was obtained. This product was dissolved in air at 550℃ for 6 hours.
The composition (molar ratio) after firing for an hour is 0.8Na 2 O.
It was Al2O3・65.1SiO2 . Thereafter, ion exchange was performed overnight at room temperature using 5 ml of 1N ammonium nitrate solution per 1 g of silicate. Next, wash with pure water and heat at 120℃ for 6 days.
After drying for an hour, it was fired at 550°C for 6 hours, and the same process was performed again to obtain an H type. Example 1 Zeolite H prepared by the method shown in Reference Example 1
-Immerse 50g of ZSM-5 powder in 500ml of 30% by weight ammonium fluoride aqueous solution, and add 50g of powder while stirring.
Fluorination treatment was performed at ℃ for 1 hour. The suspension was then filtered to separate solid matter, which was washed with pure water, dried at 120°C for 6 hours, and further calcined at 550°C for 6 hours. The properties of the obtained powder are shown in Table 1 in comparison with H-ZSM-5 of Reference Example 1.
【表】
また、得られた粉末のＸ線回折像はＨ−ZSM
−５とほとんど同じであり結晶構造の変化は認め
られなかつた。
参考例 ２
触媒の調製
実施例１で得た粉末にアルミナゾルを添加して
押出し成形した（アルミナ含有量35重量％）。成
形品を空気中で550℃、６時間焼成した後、粉砕
し20〜32メツシユの粒度に揃えた。
得られた成形品を、同一粒度の市販の溶融鉄触
媒（BASF社製、S6−10RED）と重量比で１：
１の割合で混合し触媒とした。
参考例 ３
合成ガスの反応
参考例２で得た触媒を反応管に充填したのち、
所定の還元、賦活処理を行い、下記の条件で
H2／CO2：１の合成ガスを通流し得られた生成
物をガスクロマトグラフ分析にかけた。
反応温度 330℃
反応圧力 20Kg/cm2Ｇ
WHSV 1.46hr-1
触媒量 0.98ｇ
反応時間を変えたときの結果を第２表に示し
た。[Table] Also, the X-ray diffraction image of the obtained powder is H-ZSM
-5, and no change in crystal structure was observed. Reference Example 2 Preparation of Catalyst Alumina sol was added to the powder obtained in Example 1 and extrusion molded (alumina content: 35% by weight). The molded product was fired in air at 550°C for 6 hours and then ground to a particle size of 20 to 32 meshes. The obtained molded product was mixed with a commercially available molten iron catalyst (manufactured by BASF, S6-10RED) of the same particle size at a weight ratio of 1:1.
They were mixed at a ratio of 1:1 to prepare a catalyst. Reference example 3 Synthesis gas reaction After filling the reaction tube with the catalyst obtained in reference example 2,
Perform the prescribed reduction and activation processing, and under the following conditions.
A synthesis gas of H2 /CO2:1 was passed through and the resulting product was subjected to gas chromatographic analysis. Reaction temperature: 330°C Reaction pressure: 20Kg/cm 2 G WHSV 1.46hr -1 Catalyst amount: 0.98g Table 2 shows the results when the reaction time was varied.
【表】
実施例 ２〜５
参考例１の方法で調製したＨ−ZMS−５につ
き、第３表に示した種々の条件でフツ素化処理を
施こし、得られた粉末の特性を同表に示した。
参考例 ４〜７
実施例２〜５で得た粉末を用いて、参考例２と
同様の方法により、それぞれ参考例４〜７の触媒
を調製した。これらの触媒につき、参考例３と同
じ条件下で合成ガスの反応を行つた。
以上の結果を一括して第３表に示した。[Table] Examples 2 to 5 H-ZMS-5 prepared by the method of Reference Example 1 was subjected to fluorination treatment under various conditions shown in Table 3, and the properties of the obtained powder are shown in the same table. It was shown to. Reference Examples 4 to 7 Using the powders obtained in Examples 2 to 5, the catalysts of Reference Examples 4 to 7 were prepared in the same manner as in Reference Example 2, respectively. Using these catalysts, a synthesis gas reaction was carried out under the same conditions as in Reference Example 3. The above results are summarized in Table 3.
【表】
以上の結果から明らかなように、本発明の方法
に基づく触媒はC10以上の重質芳香族成分の生成
割合が抑制される。また、C5以上の炭化水素の
データからも明らかなように、本発明にかかる触
媒はその使用寿命が長くなる。[Table] As is clear from the above results, the catalyst based on the method of the present invention suppresses the production rate of heavy aromatic components with C 10 or more. Furthermore, as is clear from the data for C5 and higher hydrocarbons, the catalyst according to the present invention has a longer service life.
Claims (1)
ミノシリケートを、３〜50重量％の濃度のフツ素
含有化合物の水溶液中で処理することを特徴とす
る結晶性アルミノシリケートのフツ素化処理方
法。 ２ フツ素含有化合物がフツ化アンモニウム、フ
ツ酸、フツ化水素アンモニウム、ヘキサフルオロ
ケイ酸、ヘキサフルオロケイ酸アンモニウム、フ
ツ化ナトリウム又は／及びフツ化水素カリウムで
ある特許請求の範囲第１項記載の方法。 ３ フツ素化処理条件が、処理温度０〜100℃、
処理時間１分〜10時間である特許請求の範囲第１
項記載の方法。[Claims] 1. A crystalline aluminosilicate having a SiO 2 /Al 2 O 3 molar ratio of 10 or more is treated in an aqueous solution of a fluorine-containing compound at a concentration of 3 to 50% by weight. Fluorination treatment method for crystalline aluminosilicate. 2. The fluorine-containing compound according to claim 1, wherein the fluorine-containing compound is ammonium fluoride, hydrofluoric acid, ammonium hydrogen fluoride, hexafluorosilicic acid, ammonium hexafluorosilicate, sodium fluoride or/and potassium hydrogen fluoride. Method. 3 Fluorination treatment conditions include treatment temperature of 0 to 100℃,
Claim 1: The processing time is 1 minute to 10 hours.
The method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59009399A JPS60155139A (en) | 1984-01-24 | 1984-01-24 | Preparation of hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59009399A JPS60155139A (en) | 1984-01-24 | 1984-01-24 | Preparation of hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60155139A JPS60155139A (en) | 1985-08-15 |
| JPH055539B2 true JPH055539B2 (en) | 1993-01-22 |
Family
ID=11719338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59009399A Granted JPS60155139A (en) | 1984-01-24 | 1984-01-24 | Preparation of hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60155139A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7030641B2 (en) * | 2018-07-31 | 2022-03-07 | 日本製鉄株式会社 | A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, a method for producing a hydrocarbon, and a catalyst for producing a hydrocarbon from a synthetic gas. |
-
1984
- 1984-01-24 JP JP59009399A patent/JPS60155139A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60155139A (en) | 1985-08-15 |
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