JPS6126836B2 - - Google Patents
Info
- Publication number
- JPS6126836B2 JPS6126836B2 JP14915079A JP14915079A JPS6126836B2 JP S6126836 B2 JPS6126836 B2 JP S6126836B2 JP 14915079 A JP14915079 A JP 14915079A JP 14915079 A JP14915079 A JP 14915079A JP S6126836 B2 JPS6126836 B2 JP S6126836B2
- Authority
- JP
- Japan
- Prior art keywords
- coal
- oil
- catalyst
- metals
- reaction
- 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
Links
- 238000000034 method Methods 0.000 claims description 76
- 239000003245 coal Substances 0.000 claims description 72
- 239000003054 catalyst Substances 0.000 claims description 69
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000000391 magnesium silicate Substances 0.000 claims description 24
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 23
- 235000019792 magnesium silicate Nutrition 0.000 claims description 23
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 23
- 150000002739 metals Chemical class 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000004113 Sepiolite Substances 0.000 claims description 18
- 229910052624 sepiolite Inorganic materials 0.000 claims description 18
- 235000019355 sepiolite Nutrition 0.000 claims description 18
- 229910052625 palygorskite Inorganic materials 0.000 claims description 13
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229960000892 attapulgite Drugs 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 56
- 238000006243 chemical reaction Methods 0.000 description 32
- 230000008569 process Effects 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- 238000004517 catalytic hydrocracking Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 9
- 238000002309 gasification Methods 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002956 ash Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002734 clay mineral Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- -1 iron group metals Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052612 amphibole Inorganic materials 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000006173 Larrea tridentata Nutrition 0.000 description 1
- 244000073231 Larrea tridentata Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QPUYECUOLPXSFR-UHFFFAOYSA-N alpha-methyl-naphthalene Natural products C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052885 anthophyllite Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 229960002126 creosote Drugs 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003476 subbituminous coal Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は新規な触媒を用いる石炭類の水素化分
解による液状炭化水素油への転換方法に関する。
さらに詳しくは、石炭類を高温・高水素圧下、ヤ
グネシウムシリケートを主成分とする鉱物、就
中、セピオライト、パリゴルスカイトおよびアタ
パルジヤイトから選らばれた1種以上からなる担
体に遷移金属類および錫を担持してなる触媒と接
触せしめることを特徴とする石炭液化方法に関す
る。
近年、石油に対する需要が著しく増加している
のに対して新規油田の発見および開発が頭打ち傾
向を示していることから、世界的なエネルギー不
足が到来している。これに対して新エネルギーあ
るいは代替エネルギーに関する研究および開発が
活発に行なわれ、就中、化石エネルギー中最大の
埋蔵量を有する石炭類のガス化および液化による
代替燃料の製造については多数のプロセスが検討
されている。
石炭類のガス化による天然ガス代替燃料の製造
は、灰分等の多い、かつ広範囲の性状の石炭を原
料とすることができ、且古くから開発された石炭
ガス化技術を応用できるなどの理由から技術的に
は最も完成されており、かつ信頼度も高いとされ
ている。しかしながらガス化法による、あるいは
ガス化工程を経由する石炭類からの代替燃料の大
規模製造は(1)ガス化工程に高価な酸素を多量に消
費し、消費された酸素はエネルギー源として再利
用されない;(2)石炭類がN,O,Sなどの多量の
ヘテロ元素を含み、このために発生ガスに含まれ
るこれらの化合物を除去し、精製ガスを得るため
にきわめて繁雑かつ、技術的に困難な工程を要す
る;(3)ガス化を経由して液化するためにはさらに
繁雑な工程を要しながら、液化油の収率がきわめ
て低い;(4)製品が気体である場合には貯蔵および
長距離輸送に適さない、などの理由から技術的に
も経済的にも必ずしも有利とは考えられない。
他方、石炭類の水素化分解による直接液化法は
(1)大量の水素を消費する;(2)石炭類の水素化反応
性が小さく、かつ種類,産地などによつて大巾に
変動する;(3)液化油中の灰分がきわめて微細(数
μ〜数拾μ)であり、固液分離が技術的に困難で
ある;(4)反応条件が苛酷であり、しかも気,液,
固体からなる原料および生成物を同時に処理しな
ければならない、などの多くの欠点を持つことが
指摘されている。しかしながら、(1)現在、資源が
枯渇しつつある石油類と組成および性状において
最も近似した液体燃料が得られ、従つて精製・輸
送・貯蔵・消費などのあらゆる面において従来の
石油類に対するシステムがほとんどそのまま利用
できる。これによる社会的・経済的メリツトは膨
大であると考えられる;(2)石炭類は相当量の水素
を含むが(H/C原子比=0.5〜1.0)、水添液化工
程において消費された水素と共に、これらの相当
部分が液化油に移行するので、実質的にエネルギ
ー源として有効利用されることになる;(3)石炭の
ガス化工程を経由する間接的液化方法にくらべて
液化油の収率が2〜3倍高い;(4)石炭中のヘテロ
元素が、H2S,NH3,H2Oなどとして容易に脱離
され、精製油を直接得ることもできる;などの優
れた特長があり、このために少なくとも総合経済
性からみれば直接液化法はガス化法に較べて優れ
ていると考えられる。このために古くから石炭類
の直接液化法に関して多数のプロセスが提案さ
れ、一部はかつて既に工業的にも実施されたこと
がある。
石炭の直接水素化処理による液化法は大別して
無触媒法と触媒法に分類される。前者は触媒を用
いないこと、および水素消費量が少ないなどの特
長があるものの、(1)生成物(油)中に窒素、硫
黄、酸素、アスフアルテン類などが多く、残留炭
素もきわめて大きくこのために良質油への精製が
非常に難しい;(2)生成物はピツチ状の高沸点物の
比率が高く、留出油収率が低い、などの主として
生成物の性状に関する多くの欠点を有する。これ
らの欠点を補うべく、例えばSRC―法におい
ては液化生成物から分離した灰分の多い残渣分の
少なくとも1文を水素化分解工程に循環せしめる
ことによつて石炭灰分のもつ触媒作用を利用し、
脱硫・脱窒素率などを高め、液化油の収率の向上
をはかつている。またEDS法においては水素加
圧下、テトラリンの如き、いわゆる水素ドナー溶
剤を用いて石炭類を抽出液化せしめたのち、灰分
と未反応炭を固液分離し、かくして得た液化生成
油を、固定触媒層を用いて水素化処理している。
この2段水素化処理法では、水素ドナー溶剤は水
素化処理油から分離されて抽出液化工程にそのま
ま循環され使用することが出来ること、および触
媒が液化工程において間接的に用いられることの
ために、石炭中の灰分による触媒の劣化の問題は
全く起らずしかも比較的良質な液化油が得られる
等の利点を有する。しかしながら、これらの無触
媒法はいずれも液化油の収率および液化油の性状
などに関しては必ずしも充分と言えない。これに
対して、石炭類を触媒存在下に直接水素化処理す
る触媒法は、液化油の収率が高く、かつ良質油が
得られることが期待されることから、多くの提案
が行なわれている。H―石炭法では石炭粉末―媒
体油スラリーは沸騰触媒床を用いて水素化分解さ
れ、反応条件の苛酷度に応じて合成原油あるいは
重質燃料油に転換される。またシンソイル
(Synthoil)法では石炭―媒体油スラリーが高度
の乱流条件下、固定触媒床を用いて水素化分解さ
れる。これらの方法においてはいずれも通常の活
性アルミナにMo,Co,Niなどを担持した高価な
脱硫触媒が用いられているために良質油が得られ
る反面、触媒への炭素,鉄,チタンなどの堆積に
よる活性の低下、あるいは石炭微粉末などとの衝
突による摩耗のために、劣化した触媒を頻繁に新
触媒と交換しなければならず触媒の占めるコスト
の大巾な上昇をもたらしている。このためかかる
高価な触媒の代りに赤泥などのきわめて安価な微
粉末触媒を用いる方法が古くから提案されてい
る。しかし従来知られているこれらの安価な触媒
は活性が低く、石炭に対して多量に添加する必要
があり、また良質油が得られないなどの欠点が認
められている。即ち、赤泥は、触媒費用が安いも
のの、石炭への添加比率を高くしなければならな
いことによる種々の機械的トラブルが予想され、
さらに良質油が得られないなどの不都合が問題と
されている。
一方発明者らは長年にわたり重質油の水素化処
理方法、就中、脱メタル、アスフアルテン分解触
媒の開発に従事し、これらの成果を多数の特許出
願として公開している。特に脱メタル触媒に関し
ては多孔質マグネシウムシリケートを担体とする
新規触媒を見出し、特開昭52―73193,同52―
68033,同52―68890,同52―71403,同52―
92891,同52―95598,同53―7592,同53―
30996,同53―34691,同53―102888,同54―
31099および特願昭53―108122(特公昭57―
16859)などにその技術内容を開示している。こ
こに開示された触媒の担体には天然および合成の
多孔質マグネシウムシリケート鉱物が用いられ、
特にこれらの中で珪素結合がいわゆる複鎖結合か
らなる繊維状マグネシウムシリケート粘土鉱物
〔粘土ハンドブツク,日本粘土学会,1967〕が好
ましいことを認めている。具体的鉱物としては、
例えば特願昭53―108122に示した角閃石アスベス
ト鉱物,就中,直閃石のほか、セピオライト,ア
タパルジヤイトあるいはパリゴルスカイトのごと
き多孔質粘土鉱物である。これら鉱物ならびにそ
の変性物を担体(以下マグネシウムシリケート担
体という)とする触媒が、いわゆる脱硫活性が小
さいにも拘わらず、重質油の水素化処理、特に脱
メタル処理用触媒として高活性、長寿命であるこ
とは、前述の各特許出願の明細書にも詳しく述べ
てある。
発明者らは、これまでに行なつてきたマグネシ
ウムシリケート担体触媒に関する一連の実験結果
から、この触媒が従来の触媒にはない全く特異な
性質を有することに着目し、これを石炭の液化に
使用したところ、マグネシウムシリケートを担体
とし、これに遷移金属および錫から選ばれる1種
以上の成分を担持した触媒が、極めて高活性、長
寿命であり、従来の何れの触媒による方法と比較
しても、良質の液化油が極めて大きい収率で得ら
れることを得たものである。
石炭の液化反応は、固体の分解反応であり、重
質油の水素化処理とは全く別異の反応であり、し
かも使用する触媒は、いわゆる水添能の大きい触
媒でなければならないということが技術常識とな
つており、脱硫活性によつて代表されるいわゆる
水添能の小さいマグネシウムシリケート担体触媒
が、石炭の液化にこのような高い活性を示したこ
とは、将に驚異に値するものである。
本発明方法に係わる石炭類の水素化分解の特徴
は、金属を担持した多孔質マグネシウムシリケー
ト触媒を用いたところにある。ここで多孔質マグ
ネシウムシリケートとは、セピオライト,パリゴ
ルスカイト,およびアタパルジヤイトの様な多孔
質粘土鉱物と、これを粉砕、混練あるいは酸抽出
等の化学的あるいは物理的処理を加えて変成した
物、あるいは水酸化アルミニウムゾル、アルミナ
シリカゾル、チタニアゾルあるいは他の粘土鉱物
等添加物を加え成形した物等の全てを含むものを
言う。角閃石アスベスト鉱物はそのまゝでは細孔
容積が極めて小さいマグネシウムシリケート鉱物
であるが、公知の方法によつて容易に多孔質化す
ることが出来、本発明の目的を満足する担体の1
つである。最も望ましい多孔質マグネシウムシリ
ケートは、得られる触媒の性能あるいは触媒調整
の容易さを考慮するとセピオライト,パリゴルス
カイトおよびアタパルジヤイトということができ
る。これらはいずれも珪素の結合様式がいわゆる
複鎖構造を有する繊維状粘土鉱物として知られ、
セピオライトは、マグネシウムあるいは土類元素
の一部が、他の金属によつて置換されたものも知
られているが主としてマグネシアおよびシリカか
ら構成され、また、パリゴルスカイトおよびアタ
パルジヤイトは、いずれも多孔質粘土鉱物で、シ
リカの1部がアルミナに置換されてアルミナの多
いマグネシウムシリケートとなつている。更に、
これらのうちでは特にセピオライトが、担体とし
て優れた特徴を有し、最も望ましい。即ち(1)得ら
れる触媒が、比表面積および細孔容積が大きく、
高活性であり、しかも鉄,チタン等の金属類の堆
積によつて劣化しにくいこと;(2)セピオライト中
のマグネシウムの1部が他の金属によつて容易に
交換され易く、担持する金属の分散が極めて良好
であり、高活性触媒が安価に得られる、等を挙げ
ることができる。
多孔質マグネシウムシリケート触媒に、担持す
る金属類は、遷移金属類および錫からなる群から
選ばれた1種以上が用いられる。これらの金属類
のうちCu,Zn,Y,ランタニド,Sn,V,Cr,
Mo,W,Mn,Fe,CoおよびNiから選らばれた
1種以上を担持した触媒は、石炭類の水素化分解
活性が大きく、かつ比較的安価に得られるなどの
理由のために好適である。これらの担持金属類の
種類あるいは組合せは、マグネシウムシリケート
の種類、原料石炭の種類,性状あるいは反応方
法、条件などに応じて適宜選らばれる。また金属
担持量も多くの因子によつて決められ、きわめて
広範囲であるが、通常、金属として合計0.1重量
%、好ましくは0.5〜10重量%の範囲で任意に選
らばれる。これらの金属類は通常、硝酸塩、硫酸
塩、塩化物、金属酸塩、錯塩あるいはその他の溶
媒可溶性化合物の形で使用される。溶媒としては
費用および安全性などの観点から通常、水が用い
られるが、メタノール、アセトンあるいは液体ア
ンモニアなどの非水溶媒を用いることもできる。
金属類の担持方法としては浸漬、スプレー散布
法、混練法などの公知の任意の方法が用いられ
る。また成形触媒では金属類の担持を成形工程前
の段階で行つてもよく又分割して行つてもよい。
発明者らはセピオライトなどのマグネシウムシリ
ケート担体にイオン交換法によつて担持された金
属がきわめて高度にかつ均一に分散しており、担
持量がきわめて少ない場合においても石炭類の水
素化分解反応に対して高活性を示すことを見出し
ている。担体にイオン交換法によつて担持できる
金属類としては周期律表b,b,aおよび
鉄族金属の他に、V,Cr,Snなどが挙げられ
る。これらの金属は塩化物,硫酸塩,硝酸塩など
の金属鉱酸塩,蟻酸塩,酢酸塩などの有機酸塩あ
るいはアンミン錯塩などの水溶液として用いられ
るが、必要に応じて任意の塩類あるいは酸を加え
てPHを1〜7に調整して使用する。
この方法による担持金属は担体を構成するマグ
ネシウム等と交換、担持されることが要件であ
り、担体中のマグネシウム等と置換されることな
く、単に付着あるいは吸着している金属は、置換
されている金属に比べて金属重量当り活性が低
い。従つてかかる付着あるいは吸着している金属
類は洗浄等によつて回収し、再使用して効果的に
置換せしめるのが望ましい。
イオン交換法によつて担持することができる金
属と、担持できない金属とを同一の担体に担持す
る場合には、多段工程によつて担持状態を変えて
担持することも可能である。例えばイオン交換法
によつて第1の金属群を担持したのち、第2の金
属群をアンモニアあるいはアミン水溶液などの塩
基性ないし、中性溶液として担持する方法であ
る。
発明者らの検討によると、多孔質マグネシウム
シリケート担体のうち、特にセピオライトは上記
のイオン交換法を用いて金属類を担持するのに最
も望ましい。これはセピオライトの比表面積およ
び細孔容積が大きいことの他に、パリゴスカイト
あるいはアタパルジヤイトなどの多孔質マグネシ
ウムシリケートに比べて、活性金属によつてイオ
ン交換されやすく、イオン交換によつて担持され
る金属量が多いことなどによると推測される。イ
オン交換によつてセピオライトに担持される金属
のうち、Fe,Ni,Co,Cu,Zn,V,Cr,Sn,
は、高活性触媒が得られるので特に好適である。
これらの金属類をイオン交換によつて担持したの
ち、Mo,Wなどをさらに担持してもよい。
本発明方法においては金属担持マグネシウムシ
リケート触媒を反応方法などに応じて任意の形態
で用いることができる。例えば天然に得られる多
孔質マグネシウムシリケートを充分に粉砕し、水
などの液体の存在下で混練したものをさらに任意
の形状に成形してから用いてもよくあるいは金属
類を担持した多孔質マグネシウムシリケートを適
当な粒度に粉砕した後、直接、石炭粉末に添加し
て用いてもよい。マグネシウムシリケート触媒を
微粉末として用いる場合には、原料石炭に対する
触媒の添加比率は反応方法、殊に使用触媒の循環
方式によつて大巾に異るが通常1〜20重量%でよ
い。反応工程において添加した触媒の1部を反応
生成物から回収し、再び水素化分解反応系に循環
せしめる場合には、原料石炭に対する微粉末触媒
の添加比率は微かな量で十分目的を達することが
できる。
本発明方法によると実質的にあらゆる固体有機
物、就中、石炭類を液状油に転換せしめることが
できる。しかし一般に、亜炭のように炭素含有率
の著しく少ないものでは液状油の収率が低く、か
つ液化油あたりの化学水素消費量が多くなるため
に必ずしも好適な液化原料とはされない。また、
逆に炭素含有率のきわめて多い、例えば無煙炭な
どは、これから液状油を得ることも不可能ではな
いが、一般に水素化反応性が著しく低いために好
ましい原料とはならない。本発明方法において処
理しうる好ましい石炭類としては、無水・無灰基
準での炭素含有率が60〜90%である瀝青炭,亜瀝
青炭および褐炭などである。これらの石炭類は、
いずれも相当量の水分および灰分を含み液化生成
物の固液分離操作を困難にし、あるいは水素化分
解工程において水素分圧を低下せしめるので、予
め乾燥および選炭処理などによつてこれら灰分な
らびに水分を除去しておくのが望ましい。予備処
理された石炭類は、通常100メツシユ篩通過ま
で、あるいは平均単粒子直径が150μ以下、好ま
しくは、30〜100μに微粉砕して水素化分解工程
に供給する。従つて触媒を粉末状態において使用
する場合には、石炭粉末と同様に150μ以下、好
ましくは30〜100μに微粉砕して用いる。石炭類
の粉砕処理は酸化あるいは粉塵爆発を避けるため
に、不活性気体雰囲気、あるいは水、又は油中で
行なう。最終微粉砕工程は特に危険であり、媒体
油と混合しながら混練・微粉砕するのが好まし
い。通常、石炭粉末は媒体油の存在下において水
素化分解・液化される。媒体油としては石炭液化
油、分解油、石油残渣油、コールタール、アント
ラセン油、アルキルナフタレン,テトラリンな
ど、公知の任意のものが選らばれるが、本発明の
方法で生成する石炭液化油、あるいはこれから分
離された留分は、同一系内の成分のみによつて処
理が行われるという面において特に好適である。
媒体油と石炭粉末との混合比率は、該混合物ス
ラリーの取扱いが可能である範囲内において任意
に決められる。しかし石炭の混合比率が小さいと
液化効率が低下し、大きな反応器容積を要するの
で必ずしも好ましくない。逆に石炭混合比率が高
いと液化効率も高くなるが、スラリーの流動性、
就中、予備加熱管内での流動性が低下し、さらに
反応器内部をコーキングなどによつて汚染するの
で必ずしも好ましい結果が得られない。従つて石
炭粉末と媒体油との重量混合比率は、無水・無灰
基準において通常0.05〜2:1、好ましくは0.2
〜0.6:1の範囲がよい。
反応条件は石炭の種類および反応方法などに応
じて広範囲に選ぶことができる。通常、水素圧50
〜500Kg/cm2、好ましくは100〜250Kg/cm2、温度400
〜500℃、好ましくは420〜470℃である。これら
の反応条件のうち、石炭転化率を向上させるため
には一般に、水素圧および温度が高いことが好ま
しいが、化学水素消費量の増加ならびに、メタン
などの軽質炭化水素収率が増加することから、工
業的には好ましくない。また水素圧が低いと反応
器内のコーキングを起しやすく、反応温度が低い
場合には軽質油の収率が小さく、あるいは大きな
反応器を要するなどの点から必ずしも好適とは言
えない。
反応方法も制限的でなく、粉末触媒を用いた懸
濁触媒法、H―石炭法と同様に流動触媒層に石炭
粉末と媒体油からなるスラリーを供給する法、シ
ンソイル法と同様にマグネシウムシリケート触媒
層に高度の乱流条件下で、石炭粉末と媒体油との
混合物を通じる法等を、任意に採用できる。また
液化生成物の処理についても特に制限はない。液
化生成物は固液分離工程で、固形分濃度の大きい
部分と少ない部分に分離し、少ない部分を更に水
素化処理により精製し、固形分濃度の大きい部分
を循環する方法;生成油を水素化処理により精製
した後媒体油を分離し、媒体油を循環する方法;
生成油から媒体油を分離して循環する法等生成油
の性状に応じた任意の方法によつて媒体油、固形
分の分離を行ない、液状分を回収することができ
る。
本発明の方法では、反応の苛酷度あるいは石炭
から液化油の転化率に応じた多量の水素が消費さ
れるが、これら水素源は、副生するメタン等の軽
質炭化水素を常法により水蒸気改良する方法、固
形分が濃縮した残渣分を部分酸化する方法、ある
いは原料石炭の選炭工程で派生するいわゆる2号
炭を部分酸化する方法等によつて製造してもよ
い。
次に本発明方法を実施例によりさらに詳しく説
明する。ここで特に断らない限り、%および
ppmは重量基準による。
実施例 1,2
下記表―1に性状を示した石炭を表―2に性状
を示した触媒を用い水素化分解した。触媒は特開
昭52―95598および52―113901号などに開示した
方法によつて、スペイン産セピオライトを原料と
して調整した。尚、実施例―1においては直径、
約0.8mmの成形触媒をそのまま用い、実施例―2
においてはこれを粉砕し石炭と同じく100メツシ
ユ篩を通過した粉末触媒として用いた。
反応は高圧オートクレーブを用い、媒体油にα
―メチルナフタレンを、石炭粉末に対して29:71
となるように加えた。反応中、水素は封じ込みで
行ない、烈しく撹拌を続けた。反応方法は実施例
―1においては撹拌プロペラの周辺にステンレス
製カゴを取付け、これに触媒粒子を詰めて反応を
行ない、また実施例―2においてはカゴを使用せ
ず石炭スラリー油に対して触媒粉末を約4%加え
て行なつた。表―3の反応条件を示す。
表―1
原料石炭性状
元素分析*
炭 素 81.2%
水 素 5.8%
窒 素 1.6%
硫 黄 0.62%
酸 素 10.8%
水素/炭素原子比 0.86
水 分 2.75%
灰 分 7.53%
*無灰・無水基準による。
表―2
セピオライト触媒性状
比表面積 171m2/g
細孔容積(水銀圧入法) 0.79c.c./g
分析結果
MoO3 6.6 %
CoO 1.9 %
SiO2 48.8 %
MgO 18.6 %
反応終了後、生成油を5μフイルターを用いて
固液分離し、石炭粉末仕込み量(および触媒量)
と、反応後のトルエン不溶固形分量から石炭転化
率を求めた。それによると無水・無灰基準での石
炭転化率は実施例―1においては78.3%、実施例
―2では90.6%であつた。
表―3
反応条件
水素圧(初圧) 200Kg/cm2
反応温度 430℃
反応時間 3時間
実施例 3〜7
実施例―1,2で用いたものと同一の原料石炭
を、各種のマグネシウムシリケート担体触媒の存
在下において水素化分解した。反応は実施例―1
と同一オートクレーブを用い、また石炭および各
触媒は100メツシユ篩を通過する微粉末状とし
た。石炭粉末を分散させるための媒体油としては
初留点164℃,50%留出点321℃,終点391℃で窒
素を0.68%,硫黄を0.44%含むクレオソート油を
石炭粉末に対して4倍加えた。また反応条件はい
ずれも水素圧160Kg/cm2,反応温度440℃,反応時
間2時間,スラリー油に対する触媒添加率1%と
し、又石炭転化率は実施例―1,2と同様にして
求めた。
本実施例に用いた触媒性状を表―4に示す。実
施例―3において用いた触媒は、硫酸バナジルを
0.5モル%含む水溶液にセピオライトを約1昼夜
浸漬することによつてセピオライト中のマグネシ
ウムの1部をバナジウム(バナジル)によつて置
換し、蒸留水によつて充分に洗浄したのち、各々
200℃および500℃にて1時間づつ乾燥および焼成
して調整した。また実施例―4,5おいては、硫
酸ニツケルを0.5モル%含む、水溶液を用い実施
例―3と同様にして、イオン交換法によつてニツ
ケルを担持した。実施例―5においてはニツケル
を担持したものに、過剰のアンモニアを含むパラ
モリブデン酸アンモン水溶液をスプレーすること
によつて調製した。実施例6―6,7において
は、常法に従つて各担体に硫酸ニツケルおよびパ
ラモリブデン酸アンモンを含むアンモニア水溶液
を含浸させたのち、実施例―3と同様に乾燥・焼
成して調製した。
表―4に各触媒を用いた場合における石炭液化
率を示したが、特にセピオライト担体触媒が石炭
の水素化分解反応に対して高活性を示すことが認
められる。
The present invention relates to a method for converting coal into liquid hydrocarbon oil by hydrocracking using a novel catalyst.
More specifically, coal is heated under high temperature and high hydrogen pressure, and transition metals and tin are supported on a carrier consisting of minerals whose main component is yagnesium silicate, especially one or more selected from sepiolite, palygorskite, and attapulgite. The present invention relates to a method for liquefying coal, which is characterized by bringing the coal into contact with a catalyst consisting of: In recent years, while the demand for oil has increased significantly, the discovery and development of new oil fields has plateaued, resulting in a global energy shortage. In response, research and development on new or alternative energies are being actively conducted, and in particular, a number of processes are being considered for the production of alternative fuels through gasification and liquefaction of coal, which has the largest reserves of fossil energy. has been done. The production of natural gas alternative fuels through the gasification of coal is possible because coal with a high ash content and a wide range of properties can be used as a raw material, and it is also possible to apply coal gasification technology that has been developed for a long time. It is said to be the most technically complete and highly reliable. However, the large-scale production of alternative fuels from coal by or through the gasification process (1) consumes a large amount of expensive oxygen in the gasification process, and the consumed oxygen is reused as an energy source; (2) Coals contain large amounts of heteroelements such as N, O, and S, and therefore, extremely complicated and technically demanding processes are required to remove these compounds contained in the generated gas and obtain purified gas. requires a difficult process; (3) liquefaction via gasification requires an even more complicated process and yields very low liquefied oil; (4) storage if the product is a gas; It is not necessarily considered to be technically or economically advantageous because it is not suitable for long-distance transportation. On the other hand, the direct liquefaction method using hydrocracking of coal is
(1) It consumes a large amount of hydrogen; (2) The hydrogenation reactivity of coal is low and varies widely depending on the type and production area; (3) The ash content in liquefied oil is extremely fine (a few (μ to several tens of μ), making solid-liquid separation technically difficult; (4) The reaction conditions are harsh;
It has been pointed out that this method has many drawbacks, such as the need to simultaneously process raw materials and products consisting of solids. However, (1) it is possible to obtain a liquid fuel that is most similar in composition and properties to petroleum, whose resources are currently being depleted; It can be used almost as is. The social and economic benefits of this are thought to be enormous; (2) Coal contains a considerable amount of hydrogen (H/C atomic ratio = 0.5 to 1.0), but the hydrogen consumed in the hydrogenation and liquefaction process At the same time, since a considerable portion of these is transferred to liquefied oil, it can be effectively used as an energy source; (3) Compared to the indirect liquefaction method via the coal gasification process, the collection of liquefied oil is Excellent features include: (4) Hetero elements in coal are easily desorbed as H 2 S, NH 3 , H 2 O, etc., and refined oil can be obtained directly. Therefore, the direct liquefaction method is considered to be superior to the gasification method, at least in terms of overall economic efficiency. For this reason, many processes for direct liquefaction of coal have been proposed for a long time, and some of them have already been implemented industrially. Liquefaction methods based on direct hydrotreatment of coal are broadly classified into non-catalytic methods and catalytic methods. Although the former has the advantages of not using a catalyst and having low hydrogen consumption, (1) the product (oil) contains a lot of nitrogen, sulfur, oxygen, asphaltenes, etc., and the residual carbon is also extremely large. It is very difficult to refine into high-quality oil; (2) the product has many drawbacks mainly related to the properties of the product, such as a high proportion of pitch-like high boilers and a low distillate yield. In order to compensate for these drawbacks, for example, in the SRC method, the catalytic action of coal ash is utilized by recycling at least one part of the ash-rich residue separated from the liquefied product to the hydrocracking process.
The desulfurization and denitrification rates are increased to improve the yield of liquefied oil. In addition, in the EDS method, coal is extracted and liquefied using a so-called hydrogen donor solvent such as tetralin under hydrogen pressure, and then the ash and unreacted coal are separated into solid and liquid, and the liquefied oil thus obtained is transferred to a fixed catalyst. The layer is used for hydrogenation treatment.
In this two-stage hydrotreating method, the hydrogen donor solvent is separated from the hydrotreated oil and can be recycled and used as it is in the extraction and liquefaction process, and the catalyst is used indirectly in the liquefaction process. This method has the advantage that the problem of catalyst deterioration due to ash in the coal does not occur at all, and relatively high quality liquefied oil can be obtained. However, none of these non-catalytic methods can be said to be sufficient in terms of the yield of liquefied oil and the properties of liquefied oil. In contrast, many proposals have been made for the catalytic method of directly hydrotreating coal in the presence of a catalyst, as it is expected to have a high yield of liquefied oil and produce high-quality oil. There is. In the H-coal process, a coal powder-media oil slurry is hydrocracked using a boiling catalyst bed and converted to synthetic crude oil or heavy fuel oil, depending on the severity of the reaction conditions. In the Synthoil process, a coal-media oil slurry is hydrocracked using a fixed catalyst bed under highly turbulent conditions. All of these methods use expensive desulfurization catalysts made of ordinary activated alumina supported with Mo, Co, Ni, etc., so while good quality oil can be obtained, on the other hand, carbon, iron, titanium, etc. are deposited on the catalyst. Deteriorated catalysts must be frequently replaced with new catalysts due to a decrease in activity due to deterioration or wear due to collisions with fine coal powder, etc., resulting in a significant increase in the cost of catalysts. For this reason, a method of using an extremely inexpensive fine powder catalyst such as red mud in place of such an expensive catalyst has been proposed for a long time. However, these conventionally known inexpensive catalysts have drawbacks such as low activity, the need to add a large amount to coal, and the inability to obtain high quality oil. In other words, although red mud has a low catalyst cost, various mechanical problems are expected due to the need to add it to coal in a high proportion.
Furthermore, inconveniences such as the inability to obtain high-quality oil are considered problems. On the other hand, the inventors have been engaged for many years in the development of methods for hydrotreating heavy oil, particularly demetallization and asphaltene decomposition catalysts, and have published their results in numerous patent applications. In particular, regarding demetalization catalysts, we discovered a new catalyst using porous magnesium silicate as a carrier.
68033, 52-68890, 52-71403, 52-
92891, 52-95598, 53-7592, 53-
30996, 53-34691, 53-102888, 54-
31099 and patent application No. 108122
16859) and other publications. Natural and synthetic porous magnesium silicate minerals are used as supports for the catalysts disclosed herein;
Among these, it has been recognized that fibrous magnesium silicate clay minerals (Clay Handbook, Clay Society of Japan, 1967), in which silicon bonds are composed of so-called double-chain bonds, are particularly preferable. As specific minerals,
For example, in addition to the amphibole asbestos minerals shown in Japanese Patent Application No. 108122, especially anthophyllite, porous clay minerals such as sepiolite, attapulgite, or palygorskite. Catalysts using these minerals and their modified products as carriers (hereinafter referred to as magnesium silicate carriers) have high activity and long life as catalysts for hydrogenation of heavy oil, especially for demetalization, although they have low desulfurization activity. This fact is also stated in detail in the specifications of each of the above-mentioned patent applications. Based on the results of a series of experiments conducted on magnesium silicate carrier catalysts, the inventors noticed that this catalyst had completely unique properties not found in conventional catalysts, and decided to use it for coal liquefaction. As a result, a catalyst using magnesium silicate as a carrier and supporting one or more components selected from transition metals and tin was found to have extremely high activity and a long life, compared to any conventional catalyst method. , it has been found that high quality liquefied oil can be obtained in extremely high yield. The coal liquefaction reaction is a solid decomposition reaction, which is completely different from the heavy oil hydrogenation process.Moreover, the catalyst used must have a high hydrogenation ability. It is surprising that a magnesium silicate supported catalyst, which has become common knowledge in the art and has a low hydrogenation ability represented by desulfurization activity, has shown such high activity in coal liquefaction. . A feature of the hydrocracking of coals according to the method of the present invention is that a porous magnesium silicate catalyst supporting a metal is used. Here, porous magnesium silicate refers to porous clay minerals such as sepiolite, palygorskite, and attapulgite, and products modified by chemical or physical processing such as crushing, kneading, or acid extraction, or hydroxide. It includes all products formed by adding additives such as aluminum sol, alumina silica sol, titania sol, and other clay minerals. Amphibole asbestos mineral is a magnesium silicate mineral with an extremely small pore volume as it is, but it can be easily made porous by a known method, and is one of the carriers that satisfies the purpose of the present invention.
It is one. The most desirable porous magnesium silicates are sepiolite, palygorskite, and attapulgite, considering the performance of the resulting catalyst or the ease of catalyst preparation. All of these are known as fibrous clay minerals with a so-called double-chain structure in which silicon is bonded.
Sepiolite is mainly composed of magnesia and silica, although it is known that some of the magnesium or earth elements have been replaced by other metals, and palygorskite and attapulgite are both porous clay minerals. A part of the silica is replaced with alumina, resulting in magnesium silicate with a high alumina content. Furthermore,
Among these, sepiolite is particularly desirable as it has excellent characteristics as a carrier. That is, (1) the resulting catalyst has a large specific surface area and pore volume;
It is highly active and does not easily deteriorate due to the accumulation of metals such as iron and titanium; (2) A part of the magnesium in sepiolite is easily exchanged with other metals, and the supported metals are The dispersion is extremely good, and highly active catalysts can be obtained at low cost. As the metal supported on the porous magnesium silicate catalyst, one or more selected from the group consisting of transition metals and tin is used. Among these metals, Cu, Zn, Y, lanthanide, Sn, V, Cr,
Catalysts supporting one or more selected from Mo, W, Mn, Fe, Co, and Ni are suitable because they have high hydrocracking activity for coal and can be obtained at relatively low cost. . The type or combination of these supported metals is appropriately selected depending on the type of magnesium silicate, the type of raw coal, properties, reaction method, conditions, etc. Further, the amount of metal supported is determined by many factors and varies over a very wide range, but is usually arbitrarily selected within the range of 0.1% by weight in total, preferably 0.5 to 10% by weight. These metals are usually used in the form of nitrates, sulfates, chlorides, metal salts, complex salts or other solvent-soluble compounds. Water is usually used as the solvent from the viewpoint of cost and safety, but nonaqueous solvents such as methanol, acetone, or liquid ammonia can also be used.
As a method for supporting metals, any known method such as dipping, spraying, kneading, etc. can be used. Further, in the case of a shaped catalyst, the metals may be supported at a stage before the shaping process, or may be carried out in parts.
The inventors discovered that the metal supported on a magnesium silicate support such as sepiolite by ion exchange is extremely highly and uniformly dispersed, and even when the supported amount is extremely small, it is effective against the hydrocracking reaction of coal. It has been found that it exhibits high activity. Examples of metals that can be supported on the carrier by the ion exchange method include V, Cr, and Sn, in addition to the periodic table b, b, and a metals and iron group metals. These metals are used in the form of aqueous solutions such as metal mineral salts such as chlorides, sulfates, and nitrates, organic acid salts such as formates and acetates, or ammine complex salts, but optional salts or acids may be added as necessary. Adjust the pH to 1 to 7 before use. The metal supported by this method is required to be exchanged with and supported by the magnesium etc. constituting the carrier, and the metal that is simply attached or adsorbed without being replaced with the magnesium etc. in the carrier is replaced. Low activity per metal weight compared to metals. Therefore, it is desirable to recover such attached or adsorbed metals by cleaning or the like and reuse them to effectively replace them. When a metal that can be supported by an ion exchange method and a metal that cannot be supported are supported on the same carrier, it is also possible to support the metals in different supported states through a multi-stage process. For example, after the first metal group is supported by an ion exchange method, the second metal group is supported as a basic or neutral solution such as an ammonia or amine aqueous solution. According to the inventors' studies, among porous magnesium silicate carriers, sepiolite is particularly the most desirable for supporting metals using the above-mentioned ion exchange method. This is because, in addition to the large specific surface area and pore volume of sepiolite, it is more easily ion-exchanged by active metals than porous magnesium silicate such as palygoskite or attapulgite, and the amount of metal supported by ion exchange is higher. It is assumed that this is due to the fact that there are many Among the metals supported on sepiolite by ion exchange, Fe, Ni, Co, Cu, Zn, V, Cr, Sn,
is particularly suitable since a highly active catalyst can be obtained.
After supporting these metals by ion exchange, Mo, W, etc. may be further supported. In the method of the present invention, the metal-supported magnesium silicate catalyst can be used in any form depending on the reaction method. For example, naturally-obtained porous magnesium silicate may be thoroughly ground, kneaded in the presence of a liquid such as water, and then molded into an arbitrary shape before use, or porous magnesium silicate supported with metals may be used. After pulverizing to a suitable particle size, it may be used by directly adding it to coal powder. When the magnesium silicate catalyst is used as a fine powder, the ratio of the catalyst added to the raw coal varies widely depending on the reaction method, particularly the circulation method of the catalyst used, but is usually 1 to 20% by weight. When a part of the catalyst added in the reaction process is recovered from the reaction product and recycled to the hydrocracking reaction system, a small amount of finely powdered catalyst to the raw coal is sufficient to achieve the purpose. can. According to the process of the invention, virtually any solid organic matter, especially coal, can be converted into liquid oil. However, in general, lignite, which has a significantly low carbon content, has a low yield of liquid oil and consumes a large amount of chemical hydrogen per liquefied oil, so it is not necessarily considered a suitable raw material for liquefaction. Also,
On the other hand, it is not impossible to obtain liquid oil from anthracite coal, which has a very high carbon content, but it is generally not a preferred raw material because of its extremely low hydrogenation reactivity. Preferred coals that can be treated in the method of the present invention include bituminous coal, subbituminous coal, and lignite having a carbon content of 60 to 90% on an anhydrous and ashless basis. These coals are
Both contain a considerable amount of water and ash, which makes solid-liquid separation of the liquefied product difficult or reduces the hydrogen partial pressure in the hydrocracking process. It is desirable to remove it. The pretreated coal is usually pulverized until it passes through a 100-mesh sieve or has an average single particle diameter of 150 μm or less, preferably 30 to 100 μm, and then supplied to the hydrocracking process. Therefore, when the catalyst is used in powder form, it is finely ground to 150 microns or less, preferably 30 to 100 microns, like coal powder. The pulverization of coal is carried out in an inert gas atmosphere, water, or oil to avoid oxidation or dust explosions. The final pulverization step is particularly dangerous, and it is preferable to knead and pulverize while mixing with a medium oil. Usually, coal powder is hydrocracked and liquefied in the presence of medium oil. Any known medium oil can be selected as the medium oil, such as coal liquefied oil, cracked oil, petroleum residue oil, coal tar, anthracene oil, alkylnaphthalene, and tetralin. The separated fraction is particularly suitable in that the treatment is carried out using only the components within the same system. The mixing ratio of the medium oil and the coal powder can be arbitrarily determined within a range that allows handling of the mixture slurry. However, if the mixing ratio of coal is small, the liquefaction efficiency decreases and a large reactor volume is required, which is not necessarily preferable. Conversely, when the coal mixing ratio is high, the liquefaction efficiency increases, but the fluidity of the slurry
Particularly, the fluidity within the preheating tube decreases, and furthermore, the inside of the reactor is contaminated by coking, etc., so that favorable results are not necessarily obtained. Therefore, the weight mixing ratio of coal powder and medium oil is usually 0.05 to 2:1, preferably 0.2 on an anhydrous and ashless basis.
A range of ~0.6:1 is preferable. Reaction conditions can be selected from a wide range depending on the type of coal, reaction method, etc. Usually hydrogen pressure 50
~500Kg/cm 2 , preferably 100-250Kg/cm 2 , temperature 400
-500°C, preferably 420-470°C. Among these reaction conditions, high hydrogen pressure and temperature are generally preferred in order to improve the coal conversion rate, but they are not recommended because they increase chemical hydrogen consumption and increase the yield of light hydrocarbons such as methane. , industrially unfavorable. Furthermore, if the hydrogen pressure is low, coking in the reactor is likely to occur, and if the reaction temperature is low, the yield of light oil is low or a large reactor is required, which is not necessarily suitable. The reaction method is also not limited, and there is a suspension catalyst method using a powdered catalyst, a method of supplying a slurry consisting of coal powder and medium oil to a fluidized catalyst bed like the H-coal method, and a method using a magnesium silicate catalyst like the thin soil method. Optionally, methods such as passing a mixture of coal powder and media oil through the formation under highly turbulent conditions can be employed. There are also no particular restrictions on the treatment of the liquefied product. A method in which the liquefied product is separated into a part with a high solid content and a part with a low solid content in a solid-liquid separation process, the part with a low solid content is further refined by hydrotreating, and the part with a high solid content is recycled; the produced oil is hydrogenated. A method of separating the medium oil after refining it by treatment and circulating the medium oil;
The medium oil and solid content can be separated and the liquid content can be recovered by any method depending on the properties of the produced oil, such as a method of separating and circulating the medium oil from the produced oil. In the method of the present invention, a large amount of hydrogen is consumed depending on the severity of the reaction or the conversion rate of coal to liquefied oil, but these hydrogen sources are produced by converting light hydrocarbons such as by-product methane into steam by conventional methods. It may be produced by a method of partially oxidizing a residue with concentrated solid content, or a method of partially oxidizing so-called No. 2 coal derived from a coal preparation process of raw coal. Next, the method of the present invention will be explained in more detail with reference to Examples. Unless otherwise specified here, % and
ppm is based on weight. Examples 1 and 2 Coal whose properties are shown in Table 1 below was hydrocracked using a catalyst whose properties are shown in Table 2. The catalyst was prepared using Spanish sepiolite as a raw material by the method disclosed in JP-A-52-95598 and JP-A-52-113901. In addition, in Example-1, the diameter,
Using a shaped catalyst of about 0.8 mm as it is, Example-2
This was pulverized and passed through a 100-mesh sieve in the same way as coal and used as a powder catalyst. The reaction was carried out using a high-pressure autoclave, and the medium oil was
- Methylnaphthalene to coal powder 29:71
I added it so that During the reaction, hydrogen was confined and vigorous stirring was continued. In Example 1, a stainless steel cage was attached around the stirring propeller and catalyst particles were packed in the cage to carry out the reaction, and in Example 2, a cage was not used and the catalyst was applied to coal slurry oil. Approximately 4% powder was added. Table 3 shows the reaction conditions. Table-1 Raw coal properties Elemental analysis * Carbon 81.2% Hydrogen 5.8% Nitrogen 1.6% Sulfur 0.62% Oxygen 10.8% Hydrogen/carbon atomic ratio 0.86 Moisture 2.75% Ash 7.53% *Based on ashless and anhydrous standards . Table-2 Sepiolite catalyst properties Specific surface area 171m 2 /g Pore volume (mercury porosimetry) 0.79cc/g Analysis results MoO 3 6.6% CoO 1.9% SiO 2 48.8% MgO 18.6% After the reaction, the produced oil was filtered through a 5μ filter. The amount of coal powder (and amount of catalyst)
The coal conversion rate was determined from the toluene-insoluble solid content after the reaction. According to this, the coal conversion rate on an anhydrous and ashless basis was 78.3% in Example-1 and 90.6% in Example-2. Table 3 Reaction conditions Hydrogen pressure (initial pressure) 200 Kg/cm 2 Reaction temperature 430°C Reaction time 3 hours Examples 3 to 7 The same raw coal used in Examples 1 and 2 was mixed with various magnesium silicate carriers. Hydrocracking was carried out in the presence of a catalyst. The reaction is Example-1
The same autoclave was used, and the coal and each catalyst were made into fine powders that could pass through a 100-mesh sieve. As a medium oil for dispersing coal powder, creosote oil containing 0.68% nitrogen and 0.44% sulfur at an initial boiling point of 164°C, a 50% distillation point of 321°C, and a final point of 391°C is 4 times the amount of coal powder. added. The reaction conditions were hydrogen pressure of 160 kg/cm 2 , reaction temperature of 440°C, reaction time of 2 hours, and catalyst addition rate to slurry oil of 1%, and the coal conversion rate was determined in the same manner as in Examples 1 and 2. . Table 4 shows the properties of the catalyst used in this example. The catalyst used in Example 3 was vanadyl sulfate.
By immersing sepiolite in an aqueous solution containing 0.5 mol% for about one day and night, a part of the magnesium in sepiolite was replaced with vanadium (vanadyl), and after thoroughly washing with distilled water, each
Conditions were prepared by drying and firing at 200°C and 500°C for 1 hour each. In Examples 4 and 5, nickel was supported by the ion exchange method in the same manner as in Example 3 using an aqueous solution containing 0.5 mol% of nickel sulfate. Example 5 was prepared by spraying an aqueous ammonium paramolybdate solution containing excess ammonia onto the nickel-supported material. In Examples 6-6 and 7, each carrier was impregnated with an ammonia aqueous solution containing nickel sulfate and ammonium paramolybdate according to a conventional method, and then dried and calcined in the same manner as in Example-3. Table 4 shows the coal liquefaction rate when using each catalyst, and it is observed that the sepiolite carrier catalyst exhibits particularly high activity for the hydrocracking reaction of coal.
【表】【table】
【表】
番 号 担 体 金属担持量 石炭液化率
[Table] No. Support Metal supported amount Coal liquefaction rate
Claims (1)
質担体に遷移金属および錫からなる群から選ばれ
た1種以上の金属の化合物を担持してなる触媒の
存在下に、媒体油中の石炭類を水素圧50〜500Kg/
cm2,温度400〜500℃で水素化処理することを特徴
とする石炭類の水素化分解法。 2 触媒および石炭類が共に100メツシユ通過の
微粉砕物である特許請求の範囲第1項記載の方
法。 3 触媒担体がセピオライト,パリゴルスカイト
およびアタパルジヤイトから選ばれた1種以上か
らなり、金属類がCu,Zn,Y,ランタニド,
V,Cr,Mo,W,Mn,Sn,Fe,Co,Niから選
らばれた1種以上である特許請求の範囲第1ある
いは2項記載の方法。 4 担体がセピオライトからなり、金属類が
Fe,Ni,Co,Cu,Zn,V,Cr,Snから選らば
れる1種以上である特許請求の範囲第3項記載の
方法。 5 媒体油が石炭液化油,分解油,石油残渣油,
コールタール,アントラセン油,アルキルナフタ
レンあるいはテトラリンである特許請求の範囲第
1,2,3あるいは4項記載の方法。[Scope of Claims] 1. In the presence of a catalyst comprising a porous carrier mainly composed of magnesium silicate supporting a compound of one or more metals selected from the group consisting of transition metals and tin, in a medium oil. of coal at hydrogen pressure of 50 to 500Kg/
cm 2 and a temperature of 400 to 500°C. 2. The method according to claim 1, wherein both the catalyst and the coal are finely pulverized products that have passed through 100 meshes. 3 The catalyst carrier consists of one or more selected from sepiolite, palygorskite and attapulgite, and the metals include Cu, Zn, Y, lanthanide,
The method according to claim 1 or 2, wherein the material is one or more selected from V, Cr, Mo, W, Mn, Sn, Fe, Co, and Ni. 4 The carrier is made of sepiolite, and the metals are
The method according to claim 3, wherein the material is one or more selected from Fe, Ni, Co, Cu, Zn, V, Cr, and Sn. 5 The medium oil is coal liquefied oil, cracked oil, petroleum residue oil,
The method according to claim 1, 2, 3 or 4, wherein coal tar, anthracene oil, alkylnaphthalene or tetralin is used.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14915079A JPS5672079A (en) | 1979-11-17 | 1979-11-17 | Hydrocracking of coal |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14915079A JPS5672079A (en) | 1979-11-17 | 1979-11-17 | Hydrocracking of coal |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5672079A JPS5672079A (en) | 1981-06-16 |
JPS6126836B2 true JPS6126836B2 (en) | 1986-06-23 |
Family
ID=15468865
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14915079A Granted JPS5672079A (en) | 1979-11-17 | 1979-11-17 | Hydrocracking of coal |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5672079A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02137425U (en) * | 1989-04-18 | 1990-11-16 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6037295A (en) * | 1998-03-25 | 2000-03-14 | Council Of Scientific & Industrial Research | Process for the preparation of a new catalyst useful for producing alkylated aromatic amines |
US8226816B2 (en) | 2006-05-24 | 2012-07-24 | West Virginia University | Method of producing synthetic pitch |
US8882862B2 (en) | 2007-05-24 | 2014-11-11 | West Virginia University | Method of forming a mesophase pitch from a coal extract suitable for processing to a high value coke |
US8449632B2 (en) | 2007-05-24 | 2013-05-28 | West Virginia University | Sewage material in coal liquefaction |
US8597382B2 (en) | 2007-05-24 | 2013-12-03 | West Virginia University | Rubber material in coal liquefaction |
US8465561B2 (en) | 2007-05-24 | 2013-06-18 | West Virginia University | Hydrogenated vegetable oil in coal liquefaction |
JP2013533343A (en) * | 2010-06-22 | 2013-08-22 | ウエストバージニア ユニバーシティ | A novel hydrogenation solvent for coal liquefaction. |
CN105016794B (en) * | 2015-07-06 | 2018-07-27 | 内蒙古蒙肥生物科技有限公司 | A kind of preparation method producing fulvic acid liquid fertilizer |
CN106824204B (en) * | 2017-02-28 | 2019-07-23 | 山西大学 | A kind of attapulgite loaded Raney nickel and preparation method and application |
-
1979
- 1979-11-17 JP JP14915079A patent/JPS5672079A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02137425U (en) * | 1989-04-18 | 1990-11-16 |
Also Published As
Publication number | Publication date |
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