JPH01304182A - Coal liquefaction technique - Google Patents
Coal liquefaction techniqueInfo
- Publication number
- JPH01304182A JPH01304182A JP13485988A JP13485988A JPH01304182A JP H01304182 A JPH01304182 A JP H01304182A JP 13485988 A JP13485988 A JP 13485988A JP 13485988 A JP13485988 A JP 13485988A JP H01304182 A JPH01304182 A JP H01304182A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- solution
- heavy oil
- slurry
- oil fraction
- 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.)
- Granted
Links
- 239000003245 coal Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 37
- 239000002904 solvent Substances 0.000 claims abstract description 51
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 43
- 238000004821 distillation Methods 0.000 claims abstract description 41
- 239000000295 fuel oil Substances 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000003921 oil Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 7
- 235000002918 Fraxinus excelsior Nutrition 0.000 abstract 1
- 239000002956 ash Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 13
- 239000012528 membrane Substances 0.000 description 12
- 238000007796 conventional method Methods 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 231100000572 poisoning Toxicity 0.000 description 9
- 230000000607 poisoning effect Effects 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003077 lignite Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、石炭の液化方法に関し、詳細には褐炭等石炭
粉末を所謂２段水添法で水素添加してナフサ等の油分を
得る方法において、１次水添工程で得られる蒸留残渣を
存効に利用し、油分の回収率を高める石炭の液化方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for liquefying coal, and more specifically, a method for obtaining oil such as naphtha by hydrogenating coal powder such as lignite by a so-called two-stage hydrogenation method. The present invention relates to a coal liquefaction method that effectively utilizes the distillation residue obtained in the primary hydrogenation step and increases the oil recovery rate.
（従来の技術）
従来の２段水添法による石炭ｌａ化方法は、原料石炭、
触媒及び溶剤を含む混合体を、先ず高温・高圧下で１次
水添し、得られた１次水冷生成物を薄留してナフサ、中
質油及び蒸留残渣に分離するそして、得られたナフサは
回収されると共に、石炭液化プロセスの溶剤として再利
用される。中質油は２次水添の原料として混合され、最
終的にはナフサへと転換される。(Conventional technology) The conventional two-stage hydrogenation method for converting coal to la
A mixture containing a catalyst and a solvent is first subjected to primary hydrogenation under high temperature and high pressure, and the obtained primary water-cooled product is diluted and separated into naphtha, medium oil and distillation residue. The naphtha is recovered and reused as a solvent in the coal liquefaction process. The medium oil is mixed as a feedstock for secondary hydrogenation and ultimately converted to naphtha.
また、蒸留残渣は、溶剤による脱灰処理、２次水添及び
蒸留される工程、或いは、溶剤による脱灰膜製処理、２
次水添及び蒸留される工程のいづれかの工程に付され、
蒸留残渣からナフサ及び中質油が得られる。尚、ここで
得られたナフサも回収されると共に、溶剤として再利用
され、また、中質油は１次水添の原料として混合され、
最終的にはナフサへと転換される。In addition, the distillation residue may be subjected to deashing treatment using a solvent, secondary hydrogenation and distillation process, or deashing membrane treatment using a solvent,
Subjected to any of the steps of subsequent hydrogenation and distillation,
Naphtha and medium oil are obtained from the distillation residue. The naphtha obtained here is also recovered and reused as a solvent, and the medium oil is mixed as a raw material for primary hydrogenation.
Eventually it will be converted to naphtha.
上記蒸留残渣の溶剤による脱灰処理とは、蒸留残渣に溶
剤を添加し、蒸留残渣中の重質液化物を溶解させた後、
灰分等の不溶物を沈降させ、不溶物が濃縮されたスラリ
（Ｓ１）と、重質油留分及び万骨（プリアスファルテン
）が溶解した溶液（Ａ１）とに分離するものであり、溶
液（Ａ１）はそれより溶剤を分離した後、２次水添、蒸
留される（以降、この脱灰処理工程を経る場合の方法を
従来法Ａという）。尚、スラリ（Ｓ１）は、蒸留等の方
法により溶剤の分離・回収処理が行われる。The above-mentioned deashing treatment of the distillation residue with a solvent involves adding a solvent to the distillation residue to dissolve heavy liquefied substances in the distillation residue, and then
Insoluble matter such as ash is precipitated and separated into a slurry (S1) in which the insoluble matter is concentrated and a solution (A1) in which heavy oil fraction and preasphaltene are dissolved. After separating the solvent from A1), it is subjected to secondary hydrogenation and distillation (hereinafter, the method that undergoes this deashing process will be referred to as conventional method A). Note that the slurry (S1) is subjected to a solvent separation/recovery process by a method such as distillation.
上記蒸留残渣の溶剤による脱灰膜製処理とは、蒸留残渣
に溶剤を添加し、蒸留残渣中の重質油留分を溶解させた
後、灰分等の不溶物及び万骨（プリアスファルテン）を
沈降させ、不溶物及びプリアスファルテンが濃縮された
スラリ（Ｓｌ１） と、重質油留分が溶解した溶液（Ａ
ｌ１） とに分離するものであり、）容ン夜（Ａｌ１）
はそれより）溶剤を分離した後、２次水添、蒸留され
る（以降、この脱灰膜製処理工程を経る場合の方法を従
来法Ｂという）。尚、スラリ（Ｓｌ１）は、蒸留等の方
法により溶剤の分離・回収処理が行われる。The above-mentioned deashing membrane treatment using a solvent for distillation residue refers to adding a solvent to the distillation residue to dissolve the heavy oil fraction in the distillation residue, and then removing insoluble matter such as ash and preasphaltenes. A slurry (Sl1) in which insoluble matters and puriasphaltenes are concentrated by sedimentation and a solution in which heavy oil fractions are dissolved (A
(Al1)
After separating the solvent, it is subjected to secondary hydrogenation and distillation (hereinafter, the method in which this deashing membrane treatment step is performed will be referred to as conventional method B). Note that the slurry (Sl1) is subjected to a solvent separation and recovery process by a method such as distillation.
（発明が解決しようとする課題）
ところで、従来法Ａは、重質油留分及びプリアスファル
テンが溶解した熔／＆（ＡＩ）から溶剤分離されたもの
が２次水添される。この２次水添の原料中には、多量の
プリアスファルテンが含まれ、これは触媒を毒してその
活性を著しく低下させるものである。故に、従来法Ａは
、２次水添用触媒が被毒され、その活性が著しく低下す
るという問題点を有する。(Problems to be Solved by the Invention) In Conventional Method A, a heavy oil fraction and a melt/& (AI) in which a heavy oil fraction and puriasphaltene are dissolved are subjected to solvent separation and subjected to secondary hydrogenation. The feedstock for this secondary hydrogenation contains a large amount of puriasphaltenes, which poison the catalyst and significantly reduce its activity. Therefore, conventional method A has the problem that the secondary hydrogenation catalyst is poisoned and its activity is significantly reduced.
一方、従来法Ｂは、不溶物及びプリアスファルテンが濃
縮されたスラリ（Ｓｌ１）と、重質油留分が？８解した
？８液（Ａ１１）とに分離され、？容）夜（Ａｌ１）か
ら溶剤分離されたものが２次水添されるので、従来法Ａ
のように２次水添用触媒が被毒されるという問題点はな
い、しかし、不溶物及びプリアスファルテンが濃縮され
たスラリ（Ｓｌ１）は石炭液化の系外へ排出される。こ
のスラリ（Ｓｌ１）中のプリアスファルテンは、水添さ
れれば油分となり得るものである。故に、従来法Ｂは、
油分の回収率が低下するという問題点を有する。On the other hand, in conventional method B, a slurry (Sl1) in which insoluble matters and puriasphaltenes are concentrated, and a heavy oil fraction? Did you solve 8? It is separated into 8 liquids (A11) and ? Conventional method A
There is no problem that the secondary hydrogenation catalyst is poisoned as in the above method, but the slurry (S11) in which insoluble matter and preasphaltenes are concentrated is discharged outside the coal liquefaction system. The puriasphaltenes in this slurry (Sl1) can become oil if hydrogenated. Therefore, conventional method B is
This has the problem that the oil recovery rate decreases.
また、従来法Ｂは、前述の如く、脱灰膜製処理により不
溶物及びプリアスファルテンが濃縮されたスラリ（Ｓｌ
１）が得られる。この脱灰膜製処理において、この処理
が高温下で行われるため、プリアスファルテンは、軟化
溶融状態で析出し、灰分等の不溶物と合体して著しく粘
調な付着性物質となる。この付着性物質は、温度が僅か
でも低下すると急激に粘度が増大し、最終的には固化す
る。In addition, as mentioned above, conventional method B uses slurry (Sl
1) is obtained. In this deashing membrane treatment, since this treatment is carried out at high temperatures, the puriasphaltenes precipitate in a softened and molten state, and combine with insoluble matter such as ash to form an extremely viscous adhesive substance. This adhesive substance rapidly increases in viscosity when the temperature decreases even slightly, and eventually solidifies.
故に、従来法Ｂは、脱灰膜製処理に使用される沈降槽の
底部、及びスラリ（Ｓｌ１）排出のための配管に付着性
物質が付着し、閉塞が生じ、石炭液化装置の正常な運転
ができなくなるという問題点を有する。Therefore, in conventional method B, adhesive substances adhere to the bottom of the sedimentation tank used for deashing membrane processing and the piping for discharging slurry (Sl1), causing blockage and disrupting the normal operation of the coal liquefaction equipment. The problem is that it becomes impossible to do so.
本発明はこの様な事情に着目してなされたものであって
、その目的は従来のものがもつ以上のような問題点を解
消し、プリアスファルテンによる２次水添用触媒の被毒
、活性低下、及び、付着性物質の付着による配管等の閉
塞を生じることなく、プリアスファルテンを油分に転換
して油分の回収率を向上し得る石炭の液化方法を提供し
ようとするものである。The present invention has been made in view of these circumstances, and its purpose is to solve the above-mentioned problems of the conventional methods, and to prevent the poisoning and activation of secondary hydrogenation catalysts by preasphaltenes. The purpose of the present invention is to provide a coal liquefaction method that can improve the oil recovery rate by converting puriasphaltenes into oil without causing deterioration or clogging of piping due to adhesion of adhesive substances.
（課題を解決するための手段）
上記の目的を達成するために、本発明は次のような構成
の石炭の液化方法としている。(Means for Solving the Problems) In order to achieve the above object, the present invention provides a coal liquefaction method having the following configuration.
即ち、第１請求項記載の石炭の液化方法は、原料石炭、
触媒及び溶剤を含む混合体を、１次水添し、１留してナ
フサ、中質油及び蒸留残渣とに分＾ｕが溶解した蒸留残
渣を溶剤で脱灰処理して灰分等の不溶物を含むスラリ（
Ｓ１）と、重質油留分及びプリアスファルテンが）容解
した７容７夜（八１）とに分離し、該溶液（Ａ１）を溶
剤で膜製処理してプリアスファルテンが’ｂ？４４ｍさ
れたスラリ（Ｓ２）と、プリアスファルテンが残留して
共有する重質油留分溶解液（Ａ２）とに分離が溶解した
重質油留分溶解液（Ａ２）を、その溶解液（Ａ２）から
溶剤を分離した後、２次水添し、蒸留し、ナフサ及び中
質油を得、一方前記プリアスファルテン′ａ縮スラリ（
Ｓ２）を前記１次水添の原料として混合することを特徴
とする石炭の液化方法である。That is, the method for liquefying coal according to the first claim includes raw material coal,
A mixture containing a catalyst and a solvent is subjected to primary hydrogenation, and the mixture is divided into naphtha, medium oil, and distillation residue in one distillation.The distillation residue in which a portion of the distillation residue has been dissolved is deashed with a solvent to remove insoluble matter such as ash. Slurry containing (
S1) and 7 volumes (81) in which heavy oil fraction and puriasphaltenes were dissolved, and the solution (A1) was treated with a solvent to form a membrane, and puriasphaltenes were dissolved in 'b? The heavy oil fraction solution (A2) in which the separation is dissolved is divided into the slurry (S2) that has been separated by 44 m and the heavy oil fraction solution (A2) in which puriasphaltenes remain and are shared. ), followed by secondary hydrogenation and distillation to obtain naphtha and medium oil, while the preasphaltene'a condensed slurry (
This is a coal liquefaction method characterized in that S2) is mixed as a raw material for the primary hydrogenation.
第２請求項記載の石炭の液化方法は、前記脱灰処理の溶
剤が、１６０〜２２０℃の平均沸点を有する溶剤であり
、且つ前記膜製処理の溶剤が、１５０８Ｃ以下の平均沸
点を有する溶剤である第１請求項記載の石炭の液化方法
である。The coal liquefaction method according to claim 2, wherein the solvent for the deashing treatment is a solvent having an average boiling point of 160 to 220°C, and the solvent for the membrane forming treatment is a solvent having an average boiling point of 1508C or less. A method for liquefying coal according to claim 1.
第３請求項記載の石炭の液化方法は、前記重質油留分溶
解液（Ａ２）中に残留・共有するプリアスファルテンを
、重質油留分に対して１０重世％以下にする第１請求項
および第２請求項に記載の石炭の液化方法である。The method for liquefying coal according to claim 3 provides a first method for reducing the residual/shared puriasphaltenes in the heavy oil fraction solution (A2) to 10% or less based on the heavy oil fraction. A coal liquefaction method according to claims and second claims.
（作 用）
本発明に係る石炭の液化方法は、以上説明したように、
１次水添により得られる蒸留残渣を、溶剤で脱灰処理し
て重質油留分及びプリアスファルテンが／容解したン容
ン夜（Ａ１）を得、二亥？容？夜（Ａ１）を？８剤で膜
製処理してプリアスファルテンが濃縮されたスラリ（Ｓ
２）と、プリアスファルテンが残留して共有する重質油
留分溶解液（Ａ２）とに分離するようにしている。(Function) As explained above, the coal liquefaction method according to the present invention
The distillation residue obtained by the primary hydrogenation was decalcified with a solvent to obtain a mixture (A1) in which the heavy oil fraction and puriasphaltenes were dissolved. Yong? Night (A1)? Slurry (S
2) and a heavy oil fraction solution (A2) in which puriasphaltenes remain and are shared.
そして、該重質油留分溶解液（Ａ２）を、その熔解液（
Ａ２）から溶剤を分離した後、２次水添するようにして
いる。この２次水添の原料中には、触媒被毒物質のプリ
アスファルテンが残留して共有するが、その盟は掻めで
少なく、また膜製処理が良好になされる場合は皆無に等
しい。故に、２次水添用肚媒の被毒、活性低下の程度は
極めて小さく、膜製処理の具合によっては全く触媒の被
毒、活性低下を生じることなく、２次水添することがで
きる。従って、２次水添を長期間安定して行えるように
なる。Then, the heavy oil fraction solution (A2) is added to the solution (A2).
After separating the solvent from A2), secondary hydrogenation is performed. In the raw material for this secondary hydrogenation, puriasphaltene, which is a catalyst poisoning substance, remains and shares the raw material, but its presence is very small, and in cases where the membrane forming process is well carried out, it is almost nonexistent. Therefore, the degree of poisoning and reduction in activity of the medium for secondary hydrogenation is extremely small, and depending on the conditions of membrane preparation, secondary hydrogenation can be carried out without poisoning or reduction in activity of the catalyst. Therefore, secondary hydrogenation can be performed stably for a long period of time.
一方、プリアスファルテン濃縮スラリ（Ｓ２）を、１次
水添の原料として混合するようにしている。On the other hand, the preasphaltene concentrated slurry (S2) is mixed as a raw material for primary hydrogenation.
１次水添も触媒が使用されるが、この触媒は１次水添の
原料の石炭粉末等と混合されて消耗品的に使用されるも
のであるので、触媒被毒は問題とならない。故に、プリ
アスファルテンは問題を生しることなく、１次水添され
、重質油留分及び／又は中質油留分へと転換される。そ
して、これら油留分は、蒸留、２次水添及び蒸留され、
最終的にはナフサへと転換される。A catalyst is also used in the primary hydrogenation, but since this catalyst is mixed with the raw material such as coal powder for the primary hydrogenation and used as a consumable item, catalyst poisoning is not a problem. Therefore, the puriasphaltenes can be primary hydrogenated and converted into heavy oil fractions and/or medium oil fractions without causing problems. These oil fractions are then subjected to distillation, secondary hydrogenation and distillation,
Eventually it will be converted to naphtha.
また、膜製処理して得られるプリアスファルテン濃縮ス
ラリ（Ｓ２）は、膜製処理前の脱灰処理により灰分等の
不溶物が除去されているので、付着性物質が生じない。Further, the preasphaltene concentrated slurry (S2) obtained by the membrane-forming treatment does not generate any adhesive substances because insoluble matter such as ash has been removed by the deashing treatment before the membrane-forming treatment.
付着性物質は、前述の如く、軟化溶融状態のプリアスフ
ァルテンと灰分等の不溶物との合体により生じるもので
あるからである。This is because, as described above, the adhesive substance is produced by the combination of softened and molten puriasphaltene and insoluble matter such as ash.
故に、この膜製処理において、付着性物質の付着による
配管等の閉塞という問題は生じない。Therefore, in this membrane processing, the problem of clogging of pipes etc. due to adhesion of adhesive substances does not occur.
更に、この膜製処理において、軟化溶融状態のプリアス
ファルテンは、粒成長して沈降し、沈降槽の底部に堆積
され、流動性ををするので、容易にポンプ移送できる。Furthermore, in this membrane-forming process, the softened and molten puriasphaltene grows into grains, settles out, and is deposited at the bottom of the sedimentation tank, and has fluidity so that it can be easily pumped.
従って、１次水添の原料として問題なく循環使用できる
。Therefore, it can be recycled without any problem as a raw material for primary hydrogenation.
前記蒸留残渣の脱灰処理に使用する溶剤に関し、蒸留残
渣中の重質油留分だけでなく、プリアスファルテンも充
分）容解させることが望ましい。その目的に合う脱灰処
理用溶剤としては、平均沸点１６０〜２２０℃のものを
使用するのがよく、特に平均沸点１６０〜１８０℃のも
のが望ましい。Regarding the solvent used for the deashing treatment of the distillation residue, it is desirable to sufficiently dissolve not only the heavy oil fraction but also the puriasphaltenes in the distillation residue. As a deashing solvent suitable for this purpose, one having an average boiling point of 160 to 220°C is preferably used, and one having an average boiling point of 160 to 180°C is particularly desirable.
この理由は、プリアスファルテン溶解能力に関し、平均
沸点１６０℃未満の場合は不充分であり、１６０℃以上
では充分なものとなり、平均沸点が高くなるに伴ってそ
の溶解能力が高いものとなる事、一方２２０℃を超える
と脱灰能力が急激に低下して脱灰処理ができなくなる事
、また、１８０’Ｃ超え２２０℃以下では脱灰処理可能
であるが、平均沸点が高くなるに伴って脱灰能力が徐々
に低下する事にある。The reason for this is that the ability to dissolve puriasphaltene is insufficient if the average boiling point is less than 160°C, but sufficient if it is 160°C or higher, and as the average boiling point increases, the ability to dissolve priasphaltene increases. On the other hand, when the temperature exceeds 220°C, the deashing ability decreases rapidly and deashing becomes impossible.Also, above 180'C and below 220°C, deashing is possible, but as the average boiling point increases, deashing becomes impossible. The reason is that the ash ability gradually decreases.
上記の如き条件を充たし、目的に適合する脱灰処理用溶
剤としては、例えば１次水添ナフサ、２次水添ナフサ、
もしくはそれらの混合物があり、それらのいづれも使用
できる。Deashing solvents that meet the above conditions and are suitable for the purpose include, for example, primary hydrogenated naphtha, secondary hydrogenated naphtha,
or a mixture thereof, any of which can be used.
前記脱灰処理工程られる重質油留分溶解液（Ａ２）中に
含有されるプリアスファルテンの量に関し、その量が少
ない程２次水添用触媒の被毒、活性低下の程度を小さく
できるが、重質油留分に対してプリアスファルテンの量
を１０重回％以下にすれば、触媒の被毒、活性低下を生
じることなく、長期間安定して２次水添することができ
るので、この範囲の量に調整するのが望ましい。Regarding the amount of puriasphaltene contained in the heavy oil fraction solution (A2) to be subjected to the deashing process, the smaller the amount, the smaller the degree of poisoning and activity reduction of the secondary hydrogenation catalyst. If the amount of preasphaltenes is 10% or less based on the heavy oil fraction, secondary hydrogenation can be carried out stably for a long period of time without poisoning the catalyst or reducing its activity. It is desirable to adjust the amount within this range.
重質油留分溶解液（Ａ２）中のプリアスファルテンの量
を少なくするには、膜製処理において析出するプリアス
ファルテンの量を多くすればよく、そのためには膜製処
理用溶剤として溶解力が低いものを使用するのが良い、
プリアスファルテンの量を１０重量％以下にするための
脱灰処理用溶剤としては、平均沸点１５０’Ｃ以下のも
のが良く、例えば１次水添ナフサ、２次水添ナフサ、も
しくはそれらの混合物が使用できる。In order to reduce the amount of puriasphaltenes in the heavy oil fraction solution (A2), it is sufficient to increase the amount of puriasphaltenes precipitated in the membrane-forming treatment, and for this purpose, a solvent with high dissolving power as a membrane-forming treatment solvent must be used. It is better to use a lower
The solvent for deashing to reduce the amount of puriasphaltenes to 10% by weight or less is preferably one with an average boiling point of 150'C or less, such as primary hydrogenated naphtha, secondary hydrogenated naphtha, or a mixture thereof. Can be used.
尚、脱灰処理で得られる溶液（ＡＩ）への膜製処理用溶
剤の添加は、溶液（ＡＩ）から溶剤を分離した後行って
もよいし、溶液（Ａ１）に直接添加して行ってもよいが
、後者の場合は前者の場合に比較し、低沸点の膜製処理
用溶剤を使用するのが良い。The membrane-forming treatment solvent may be added to the solution (AI) obtained by the deashing treatment after separating the solvent from the solution (AI), or it may be added directly to the solution (A1). However, in the latter case, it is better to use a membrane-forming treatment solvent with a lower boiling point than in the former case.
（実施例） 本発明の実施例を以下に説明する。(Example) Examples of the present invention will be described below.
第土夫隻尉
第１実施例に係る石炭液化工程のフローチャートを第１
図に示す。粉砕及び脱水されたビクトリア褐炭、鉄系触
媒及び溶剤との混合体を、４５０℃３１５０気圧で１次
水添し、蒸留してナフサ、中質油及び蒸留残渣に分離し
、ここで分離された蒸留残渣を脱灰処理工程に送った。The flowchart of the coal liquefaction process according to the first embodiment of the 1st Dobu Captain
As shown in the figure. A mixture of pulverized and dehydrated Victoria lignite, an iron-based catalyst, and a solvent was subjected to primary hydrogenation at 450°C and 3150 atm, and then distilled to separate naphtha, medium oil, and distillation residue. The distillation residue was sent to a deashing process.
尚、この蒸留残渣は、沸点が４２０℃以上であり、ピリ
ジン可溶物８５％、ピリジン不溶物１５％（灰分１３％
）を含むものである。This distillation residue has a boiling point of 420°C or higher, and contains 85% pyridine soluble matter and 15% pyridine insoluble matter (ash content 13%).
).
分離された上記蒸留残渣を脱灰処理工程に送った。そし
てこの蒸留残渣に平均沸点１７０’Ｃの１次水添ナフサ
を４倍量添加し、２５０’Ｃにし、蒸留残渣中の重質液
化物を溶解させた後、灰分等の不溶物を沈降させ、灰分
等の不溶物を含むスラリ（Ｓ１）と、重質油留分及びプ
リアスファルテンが溶解した溶液（Ａ１）とに分離した
。The separated distillation residue was sent to a deashing process. Then, four times the amount of primary hydrogenated naphtha with an average boiling point of 170'C is added to this distillation residue to bring the temperature to 250'C, and after dissolving heavy liquefied substances in the distillation residue, insoluble matters such as ash are precipitated. The slurry was separated into a slurry (S1) containing insoluble matter such as ash, and a solution (A1) in which heavy oil fraction and puriasphaltene were dissolved.
得られた溶液（Ａ１）は、溶剤分離処理をし、重質液化
物を得た。この重質液化物中のグリアスフ１ルチ２回は
３０％であり、また、灰分等の不溶物は５０００ｐｐｍ
であった。これは、薄留残渣中の重質油留分だけでなく
、殆どのプリアスファルテンが熔解されたことを示して
いる。The obtained solution (A1) was subjected to solvent separation treatment to obtain a heavy liquefied product. In this heavy liquefied material, the amount of filtrate is 30%, and the amount of insoluble matter such as ash is 5000 ppm.
Met. This indicates that not only the heavy oil fraction but also most of the puriasphaltenes in the thin distillate residue were dissolved.
溶剤分離処理後、平均沸点１１０’Ｃの１次水添ナフサ
を４倍量添加し、２５０’Ｃにし、膜製処理してプリア
スファルテン濃縮スラリ（Ｓ２）と、重質油留分溶解液
（Ａ２）とに分離した。尚、この膜製処理は、付方性物
質付着による配管等の閉塞という間部を生じることなく
、実施できた。また、得られたスラリ（Ｓ２）は、プリ
アスファルテン以外に、アスファルテン、溶剤及び若干
狙の油留分を含有していた。After the solvent separation treatment, four times the amount of primary hydrogenated naphtha with an average boiling point of 110'C is added to raise the temperature to 250'C, and membrane processing is performed to form a preasphaltene concentrated slurry (S2) and a heavy oil fraction solution ( It was separated into A2). It should be noted that this membrane treatment could be carried out without causing any problems such as clogging of piping etc. due to adhesion of adhesive substances. Moreover, the obtained slurry (S2) contained asphaltenes, a solvent, and a slight oil fraction in addition to puriasphaltenes.
プリアスファルテン濃縮スラリ（Ｓ２）は、１次水添の
原料として循環使用した。このスラリ（Ｓ２）は、２５
０℃で粘度が８００ｃｐであり、活劇な液であったが、
容易にポンプ移送できた。そして、このスラリ（Ｓ２）
は、１次水添され、蒸留されてナフサ、中質油に分離さ
れた後、２次水添及び蒸留され、ｒｆｉ ８％的にはナ
フサへと転換された。The preasphaltene concentrated slurry (S2) was recycled and used as a raw material for primary hydrogenation. This slurry (S2) is 25
It was an active liquid with a viscosity of 800 cp at 0°C, but
It was easy to pump. And this slurry (S2)
was firstly hydrogenated, distilled and separated into naphtha and medium oil, then secondly hydrogenated and distilled and converted to naphtha at an RFI of 8%.
一方、重質油留分溶解液（Ａ２）は、水蒸気蒸留し、溶
剤を分離した。、溶剤分離後のものは、重質油留分以外
に、灰分５００ｐｐｍ以下、プリアスファルテンｆｆ１
６％を含有していた。溶剤分離後、これを２次水添し、
１留し、ナフサ及び中質油を得た。このとき、全く２次
水添用触媒の被毒、活性低下を生じることなく、２次水
添することができた。On the other hand, the heavy oil fraction solution (A2) was subjected to steam distillation to separate the solvent. , After solvent separation, in addition to heavy oil fraction, ash content is 500 ppm or less, and puriasphaltenes ff1
It contained 6%. After solvent separation, this is subjected to secondary hydrogenation,
One distillation was carried out to obtain naphtha and medium oil. At this time, the secondary hydrogenation could be carried out without any poisoning or reduction in activity of the secondary hydrogenation catalyst.
（発明の効果）
本発明に係る石炭の液化方法によれば、プリアスファル
テンによる２次水添用触媒の被毒、活性低下、及び、付
着性物質の付着による配管等の閉塞を生じることなく、
プリアスファルテンを油りに転換して油分の回収率を向
上し得る。(Effects of the Invention) According to the coal liquefaction method of the present invention, there is no poisoning of the secondary hydrogenation catalyst by puriasphaltenes, no reduction in activity, and no clogging of pipes etc. due to adhesion of adhesive substances.
Puriasphaltenes can be converted into oil to improve oil recovery.
第１回は、第１実施例に係る石炭液化工程のフローチャ
ートを示す図である。
特許出願人 日木褐炭液化株式会社
株式会社神戸製鋼所
三菱化成工業株式会社
出光興産株式会社
アジア石油株式会社
代 理 人 弁理士 金丸 章−
ＩＩ図The first time is a diagram showing a flowchart of the coal liquefaction process according to the first example. Patent applicant: Hiki Lignite Liquefaction Co., Ltd. Kobe Steel, Ltd. Mitsubishi Chemical Industries, Ltd. Idemitsu Kosan Co., Ltd. Asia Oil Co., Ltd. Agent Patent attorney Akira Kanamaru - Figure II
Claims (3)
添し、蒸留してナフサ、中質油及び蒸留残渣とに分離し
、該蒸留残渣を溶剤で脱灰処理して灰分等の不溶物を含
むスラリ（Ｓ１）と、重質油留分及びプリアスファルテ
ンが溶解した溶液（Ａ１）とに分離し、該溶液（Ａ１）
を溶剤で脱瀝処理してプリアスファルテンが濃縮された
スラリ（Ｓ２）と、プリアスファルテンが残留して共存
する重質油留分溶解液（Ａ２）とに分離し、該重質油留
分溶解液（Ａ２）を、その溶解液（Ａ２）から溶剤を分
離した後、２次水添し、蒸留し、ナフサ及び中質油を得
、一方前記プリアスファルテン濃縮スラリ（Ｓ２）を前
記１次水添の原料として混合することを特徴とする石炭
の液化方法。(1) A mixture containing raw coal, a catalyst, and a solvent is subjected to primary hydrogenation, distilled, and separated into naphtha, medium oil, and distillation residue, and the distillation residue is deashed with a solvent to remove ash, etc. A slurry (S1) containing insoluble matter and a solution (A1) in which heavy oil fraction and puriasphaltene are dissolved are separated, and the solution (A1)
is separated into a slurry (S2) in which puriasphaltenes are concentrated by deasphalting with a solvent and a heavy oil fraction solution (A2) in which puriasphaltenes remain and coexist, and the heavy oil fraction is dissolved. After separating the solvent from the solution (A2), the solution (A2) is subjected to secondary hydrogenation and distillation to obtain naphtha and medium oil. A method for liquefying coal, characterized by mixing it as an additional raw material.
沸点を有する溶剤であり、且つ前記脱瀝処理の溶剤が、
１５０℃以下の平均沸点を有する溶剤である第１請求項
記載の石炭の液化方法。(2) The solvent for the deashing process is a solvent having an average boiling point of 160 to 220°C, and the solvent for the deashing process is
The method for liquefying coal according to claim 1, wherein the solvent has an average boiling point of 150°C or less.
るプリアスファルテンを、重質油留分に対して１０重量
％以下にする第１請求項および第２請求項に記載の石炭
の液化方法。(3) The method according to the first and second claims, in which the residual/coexisting puriasphaltenes in the heavy oil fraction solution (A2) are reduced to 10% by weight or less based on the heavy oil fraction. Coal liquefaction method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63134859A JPH0717913B2 (en) | 1988-05-31 | 1988-05-31 | Liquefaction method of coal |
| AU35260/89A AU603299B2 (en) | 1988-05-31 | 1989-05-29 | Coal liquefaction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63134859A JPH0717913B2 (en) | 1988-05-31 | 1988-05-31 | Liquefaction method of coal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01304182A true JPH01304182A (en) | 1989-12-07 |
| JPH0717913B2 JPH0717913B2 (en) | 1995-03-01 |
Family
ID=15138142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63134859A Expired - Fee Related JPH0717913B2 (en) | 1988-05-31 | 1988-05-31 | Liquefaction method of coal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717913B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885976A (en) * | 2010-07-02 | 2010-11-17 | 神华集团有限责任公司 | Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof |
| CN101962560A (en) * | 2010-09-29 | 2011-02-02 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN101962561A (en) * | 2010-09-29 | 2011-02-02 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN112029527A (en) * | 2020-08-14 | 2020-12-04 | 中国神华煤制油化工有限公司 | Method for treating coal direct liquefaction residues, coal direct liquefaction method and application thereof |
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|---|---|---|---|---|
| JPS5470303A (en) * | 1977-10-21 | 1979-06-06 | Gulf Research Development Co | Process for increasing yield of synthetic liquid fuel in coal liquefication treatment |
| JPS59204685A (en) * | 1983-05-06 | 1984-11-20 | Mitsubishi Chem Ind Ltd | Coal liquefaction |
| JPS59213792A (en) * | 1983-05-16 | 1984-12-03 | Mitsubishi Chem Ind Ltd | Conversion of coal to oil fraction |
| JPS6051785A (en) * | 1983-08-31 | 1985-03-23 | Kobe Steel Ltd | Method for liquefying brown coal by two-stage hydrogenation |
| JPS6051784A (en) * | 1983-08-30 | 1985-03-23 | Kobe Steel Ltd | Method of liquefying brown coal |
| JPS61276891A (en) * | 1985-06-03 | 1986-12-06 | Kobe Steel Ltd | Method for liquefying coal containing circulation system |
-
1988
- 1988-05-31 JP JP63134859A patent/JPH0717913B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5470303A (en) * | 1977-10-21 | 1979-06-06 | Gulf Research Development Co | Process for increasing yield of synthetic liquid fuel in coal liquefication treatment |
| JPS59204685A (en) * | 1983-05-06 | 1984-11-20 | Mitsubishi Chem Ind Ltd | Coal liquefaction |
| JPS59213792A (en) * | 1983-05-16 | 1984-12-03 | Mitsubishi Chem Ind Ltd | Conversion of coal to oil fraction |
| JPS6051784A (en) * | 1983-08-30 | 1985-03-23 | Kobe Steel Ltd | Method of liquefying brown coal |
| JPS6051785A (en) * | 1983-08-31 | 1985-03-23 | Kobe Steel Ltd | Method for liquefying brown coal by two-stage hydrogenation |
| JPS61276891A (en) * | 1985-06-03 | 1986-12-06 | Kobe Steel Ltd | Method for liquefying coal containing circulation system |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885976A (en) * | 2010-07-02 | 2010-11-17 | 神华集团有限责任公司 | Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof |
| CN101962560A (en) * | 2010-09-29 | 2011-02-02 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN101962561A (en) * | 2010-09-29 | 2011-02-02 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN112029527A (en) * | 2020-08-14 | 2020-12-04 | 中国神华煤制油化工有限公司 | Method for treating coal direct liquefaction residues, coal direct liquefaction method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0717913B2 (en) | 1995-03-01 |
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