CN105567321B - A kind of method for refining production oil product altogether with oil for coal - Google Patents

A kind of method for refining production oil product altogether with oil for coal Download PDF

Info

Publication number
CN105567321B
CN105567321B CN201510950031.8A CN201510950031A CN105567321B CN 105567321 B CN105567321 B CN 105567321B CN 201510950031 A CN201510950031 A CN 201510950031A CN 105567321 B CN105567321 B CN 105567321B
Authority
CN
China
Prior art keywords
oil
coal
hydrogen
product
heavy
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.)
Active
Application number
CN201510950031.8A
Other languages
Chinese (zh)
Other versions
CN105567321A (en
Inventor
韩保平
冯光平
邢宪军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jun Ming Chemical Engineering Design Co. Ltd.
Original Assignee
Shanghai Yingbao Energy Chemical Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Yingbao Energy Chemical Technology Co Ltd filed Critical Shanghai Yingbao Energy Chemical Technology Co Ltd
Priority to CN201510950031.8A priority Critical patent/CN105567321B/en
Publication of CN105567321A publication Critical patent/CN105567321A/en
Application granted granted Critical
Publication of CN105567321B publication Critical patent/CN105567321B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/708—Coking aspect, coke content and composition of deposits
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A kind of method for refining production oil product altogether with oil for coal, is related to Oil Production method.Coal dust, heavy oil and catalyst are mixed and made into coal, after preheating is mixed with hydrogen, into coal, refining reactor is reacted altogether with oil, reaction product isolates hydrogen-rich gas, light oil, water, crude oil, solvent extraction oil and solid residue, hydrogen-rich gas, light oil and crude oil enter back into the oil products such as hydro-upgrading cellular manufacture gasoline, diesel oil, solvent extraction oil is recycled back to coal preparation unit and carries out coal preparation as heavy oil, and solid residue can be used as semicoke to sell, it can also be used to hydrogen making.Have the advantages that process simple, reaction condition mitigations, oil product high income, without circulate hydrogenation solvent, invest it is small.

Description

A kind of method for refining production oil product altogether with oil for coal
Technical field
The present invention relates to Oil Production method, more particularly, to a kind of method for refining production oil product altogether with oil for coal.
Background technology
DCL/Direct coal liquefaction and coal refine two key areas that technology is clean coal technology with oil altogether.Direct coal liquefaction process is Fine coal is mixed with circulation solvent, is reacted under certain temperature, pressure condition with hydrogen, is converted into the organic matter of coal Liquefaction oil.Again by desulfurization, denitrogenation, further improve liquefaction oil quality, product is produced in general oil plant Transport fuel and chemical products.The advantages of DCL/Direct coal liquefaction is that oil yield and the thermal efficiency are high；Major defect is the behaviour of hydrogenation technique It is harsher to make condition.And it is a kind of coal and heavy oil to grow up on the basis of direct coal liquefaction technology that coal refines technology altogether with oil The technology processed jointly, the technology have the characteristics of completing two processes of heavy oil modification and coal liquefaction simultaneously, are effectively to utilize coal With the important means of inferior heavy oil, be in DCL/Direct coal liquefaction third generation technique most economy and industrialization future technique.
Refining is under conditions of high temperature, high pressure to coal altogether with oil, is broken at the weak cross-bond of coal, forms size not Deng coal free radical fragment, coal free radical fragment receives hydrogen in hydrogen supply dissolvent and hydrogen atmosphere, or coal intramolecular hydrogen occurs and resets Transfer, and carry out hydrogenolysis, cracking and the self-stabilizationization reaction of series of parallel order, the relatively low product of generation molecular weight.In coal During oily refining altogether, coal and heavy oil not fully respective independent reaction, and have very strong reciprocation.Heavy oil is both reaction Thing, while hydrocracking reaction is carried out, the solvent as coal liquefaction again, affect the conversion process of coal.If weight used Oil has good hydrogen supply capacity, and coal has good cooperative effect with heavy oil, and coal refines oil tech to a certain extent altogether with oil Better than conventional direct coal liquefaction technology；But if heavy oil used does not have good hydrogen supply capacity, it can not only improve oily production Rate, it can also reduce oily yield.
Compared with direct coal liquefaction technology, refining technology has following advantage to coal altogether with oil：Reactor can be made full use of Dischargeable capacity, improve the disposal ability of process units and the production efficiency of the technical process；The arene of coal and heavy oil Cooperative effect between paraffin class so that coal and the generation oil that oil refines altogether are easier to process as oil products such as qualified gasoline, diesel oil； Protium in residual oil is higher than the protium content of coal, and during coal with oil altogether refining, hydrogen consumption reduces, and hydrogen utilization rate significantly carries Height, it can effectively reduce energy consumption and equipment investment；Minor metallic element (such as iron, nickel) in heavy oil can be used as hydrogenation activity group Point, the progress of hydrogenation reaction is promoted, effectively increases the quality of oil product.
A kind of method that Chinese patent CN104087339A discloses miscellaneous oil, coal and coal tar hydrogenating refine altogether, this method will Miscellaneous oil, coal, coal tar and catalyst enter paste state bed reactor after being mixed and made into coal, 400~455 DEG C of reaction temperature, 8~19MPa of reaction pressure and hydrogen to oil volume ratio react under conditions of being 800~1200, and product fractionation goes out less than 320 DEG C cuts and entered Enter fixed bed and carry out hydrofinishing, finally fractionate out oil product.Although this method oil product high income, reaction condition is excessively harsh, And producing solid slag can not be handled.
Chinese patent CN1515650A discloses a kind of technique side using thermally dissolving and catalytic preparing liquid fuel from coal Coal dust, lytic agent and catalyst are mixed and made into coal slurry and carry out thermally dissolving and catalytic reaction by method, this method, then by thermally dissolving and catalytic product Filtering, distillation, will be made liquid oil less than 350 DEG C of fraction hydrogenating modifications.Although this method process is simple, running cost It is low, but liquefaction oil yield is relatively low.
At present, how the research refined altogether with oil coal both at home and abroad mainly improves the conversion ratio and oil product yield of coal.But chase after Ask too high coal conversion ratio and oil product yield must be with the reaction condition (430~470 DEG C, 15~30MPa) of harshness for cost.
The content of the invention
It is an object of the invention to provide on the premise of certain oil product yield is maintained, the reaction bar relatively relaxed is used as far as possible Part, a kind of method for refining production oil product altogether with oil for coal of by-product semicoke.
The present invention comprises the following steps：
1) coal dust, catalyst and heavy oil are mixed and made into coal；
2) after coal being mixed to preheating with hydrogen, unit is refined altogether into coal and oil, is obtained coal and is refined reaction product altogether with oil；
3) refining reaction product isolates high temperature gaseous phase materials and high-temperature liquid-phase material to coal through high pressure hot separator altogether with oil；
4) will enter cold high pressure separator after the cooling of high temperature gaseous phase materials that step 3) obtains, isolate hydrogen-rich gas, gently Oil and water；
5) enter vacuum distillation tower after the high-temperature liquid-phase material decompression obtained step 3) and carry out separation of solid and liquid, isolate thick Oil and vacuum tower bottom of towe contain solid Residual oil；
6) vacuum tower bottom of towe is contained into solid Residual oil again through solvent extraction, isolates solvent extraction oil, solvent and solid residue；
7) the isolated solvent extraction oil of step 6) is recycled back in step 1) and coal, solvent warp is made as heavy oil Posterior circle is reclaimed to use；
8) solid residue isolated in step 6) is sold directly as semicoke, or into Hydrogen Unit, through gasification, Hydrogen is produced in Water gas shift/WGS, gas purification, for step 2) and 9) use；
9) crude oil isolated in the hydrogen-rich gas obtained in step 4), light oil and step 5) is mixed, changed into hydrogenation Matter unit；
10) product of hydro-upgrading unit is fractionated into tower and fractionates out the products such as gasoline, diesel oil and fractionating column bottom of tower heavy oil；
11) the fractionating column bottom of tower heavy oil in step 10) is recycled back into Hydrocracking unit to continue to react, can also be recycled back to Prepared in step 1) with heavy oil, solvent extraction oil together as heavy oil for coal.
In step 1), the coal dust is the low mud coal of degree of coalification, bituminous coal, lignite etc., preferably high-volatile bituminous coal and Old lignite, the high volatile refer to volatile matter Vdaf＞ 35%, preferably less than 150 μm of the particle diameter of the coal dust；
The catalyst can use red mud, Natural pyrite, metallurgical flying dust, high ferro gangue, Ni-W bases to be hydrocracked and urge At least one of agent, Ni-Mo base oil dissolubilities hydrogenation catalyst, ultra-fine high dispersive ferrum-based catalyst etc.；
The heavy oil can use reduced crude, decompression residuum, catalytic cracked oil pulp, Aromatics Extractive Project oil, visbreaker tar, coking At least one of heavy oil, coal tar, converting plastic waste to oil, waste rubber tire oil etc.；The boiling range of the heavy oil can be 200~550 DEG C, It is preferred that 360~500 DEG C；
In the coal preparation process, the mass ratio of coal dust and heavy oil can be (1: 9)~(5.5: 4.5), preferably (4.5: 5.5)~(5.5: 4.5).
In step 2), the reactor that the coal refines unit with oil altogether can use suspended-bed reactor or paste state bed reactor Deng；The coal with oil altogether refine unit reaction temperature can be 380~470 DEG C, reaction pressure can be 6~20MPa, hydrogen to oil volume ratio Can be 600~1500；Preferable reaction temperature is 400~455 DEG C, reaction pressure is 8~19MPa, hydrogen to oil volume ratio be 800~ 1200。
In step 5), the stripping section of the vacuum distillation tower does not set column plate；The vacuum distillation tower, crude oil and vacuum tower Cutting temperature of the bottom of towe containing solid Residual oil can be 360~520 DEG C, preferably 420~500 DEG C.
Described to contain solid Residual oil progress solvent extraction to vacuum tower bottom of towe in step 6), its extraction solvent is light petrol, slightly The low boiling point hydrocarbons such as benzene, preferred steps 4) in light oil.
In step 7), the solvent extraction oil can be recycled back to the preparation for being used for coal in step 1) as heavy oil.
In step 8), the solid residue has the characteristics that high-carbon, golf calorific value, can be sold directly as semicoke, uses In boiler combustion, power plants generating electricity etc.；Hydrogen Unit is can also pass through, hydrogen is produced through gasification, water-gas change, gas purification, For being used in step 2) and step 8).
In step 9), the hydro-upgrading unit is refined using fixed bed hydrogenation, hydrocracking unit combination, or is only adopted With fixed bed hydrogenation refining plant.
In step 10), the fractionating column bottom of tower heavy oil can be recycled back to Hydrocracking unit and continue to react, and can also follow Prepared in loopback step 1) with heavy oil, solvent extraction oil together as heavy oil for coal.
The present invention proposes on the premise of certain oil product yield is maintained, to carry out using the reaction condition relatively relaxed as far as possible Coal with oil react altogether by refining, is so advantageous to reduce equipment investment, reduces running cost, can also by-product have the half of economic value Jiao, substantially increase the economic benefit that whole coal refines project with oil altogether.
The advantage of the invention is that：
1. coal and heavy oil are organically combined, refine technology altogether with oil by coal produces oil product, and by-product semicoke simultaneously, has Effect reduces the difficulty of reaction, improves the economic benefit of whole project.
2. pair vacuum tower bottom of towe improves the yield of oil product containing solid Residual oil to greatest extent using the method for solvent extraction, and Solid residue portion after extracting is sold directly as semicoke, partly for hydrogen making.
3. using the reaction condition relatively relaxed, the severity of reaction is reduced, significantly reduces the investment and operation of device Expense.
4. without circulating hydrogenation solvent, the hydrogenation depth that coal refines unit with oil altogether is reduced, improves the utilization rate of hydrogen, Simplify technological process.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention.
In figure each mark for：1 is coal dust；2 be heavy oil；3 be catalyst；4 be coal preparation tank；5 be hydrogen；6 be coal Oil refines unit altogether；7 be vacuum distillation tower；8 be that vacuum tower bottom of towe contains solid Residual oil；9 be hydrofinishing unit；10 be to be hydrocracked list Member；11 be fractionating column；12 be fractionating column bottom of tower heavy oil；13 be solvent extraction unit；14 be solvent extraction oil；15 be that solid is residual Slag；16 be naphtha；17 be diesel oil.
Embodiment
The present invention is described further for the following examples, but not thereby limiting the invention.
Embodiment 1
(1) coal dust below catalytic cracked oil pulp, 100 mesh and catalyst are hybridly prepared into coal, cycle oil Slurry and coal dust are mixed in 1: 1 ratio, and the addition of catalyst is the 7.5% of quality of pc；
(2) step (1) described coal is mixed with hydrogen, after preheated device preheating, into suspended-bed reactor, anti- Answer 400 DEG C of temperature, reaction pressure 6.5MPa, volume space velocity 0.5h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1200；
(3) step (2) described reaction product is isolated into high temperature gaseous phase materials and high-temperature liquid-phase thing through high pressure hot separator Material；After the cooling of high temperature gaseous phase materials, hydrogen-rich gas, light oil and water are isolated；Enter decompression after the decompression of high-temperature liquid-phase material to steam Evaporate tower to be fractionated, isolate crude oil and vacuum tower bottom of towe contains solid heavy still bottoms；
(4) temperature of step (3) described high pressure hot separator is 390 DEG C；The operation bar of step (3) described vacuum distillation tower Part is：385 DEG C of column bottom temperature, tower top residual voltage 40mmHg；
(5) solvent is made using light oil described in step (3), solid heavy still bottoms progress solvent is contained to vacuum tower bottom of towe and is taken out Carry, after solvent recovery, the light oil as solvent recycles；Solvent extraction oil is recycled back in step (1) as heavy oil to be used for The preparation of coal；Solid residue portion after solvent extraction sells as semicoke, partly through gasification, Water gas shift/WGS and After gas purification, for hydrogen making；
(6) crude oil in step (3) and remaining light oil are mixed, into fixed bed hydrogenation finishing reactor；It is described to add Hydrogen refining reaction uses Ni-Mo-W series Hydrobon catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1000；
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracker, it is described to be hydrocracked Reaction uses Ni-W series hydrocracking catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, hydrogen Oil volume than 1000 under conditions of carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated into tower and fractionates out gasoline, diesel oil and fractionating column bottom of tower heavy oil, Fractionating column bottom of tower heavy oil is recycled back in step (7) again, entered together with the hydrotreated product into hydrocracking reactor Row hydrocracking reaction, the fractionating column bottom of tower heavy oil account for the 3% of isocrackate gross mass.
Embodiment 2
(1) coal dust below catalytic cracked oil pulp, 100 mesh and catalyst are hybridly prepared into coal, cycle oil Slurry and coal dust are mixed in 2: 1 ratio, and the addition of catalyst is the 15% of quality of pc；
(2) step (1) described coal is mixed with hydrogen, after preheated device preheating, into suspended-bed reactor, anti- Answer 400 DEG C of temperature, reaction pressure 11MPa, volume space velocity 0.5h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1200；
(3) step (2) described reaction product is isolated into high temperature gaseous phase materials and high-temperature liquid-phase thing through high pressure hot separator Material；After the cooling of high temperature gaseous phase materials, hydrogen-rich gas, light oil and water are isolated；Enter decompression after the decompression of high-temperature liquid-phase material to steam Evaporate tower to be fractionated, isolate crude oil and vacuum tower bottom of towe contains solid heavy still bottoms；
(4) temperature of step (3) described high pressure hot separator is 385 DEG C；The operation bar of step (3) described vacuum distillation tower Part is：380 DEG C of column bottom temperature, tower top residual voltage 30mmHg；
(5) solvent is made using light oil described in step (3), solid heavy still bottoms progress solvent is contained to vacuum tower bottom of towe and is taken out Carry, after solvent recovery, the light oil as solvent recycles；Solvent extraction oil is recycled back in step (1) as heavy oil to be used for The preparation of coal；Solid residue portion after solvent extraction sells as semicoke, partly through gasification, Water gas shift/WGS and After gas purification, for hydrogen making；
(6) crude oil in step (3) and remaining light oil are mixed, into fixed bed hydrogenation finishing reactor；It is described to add Hydrogen refining reaction uses Ni-Mo-W series Hydrobon catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1000；
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracker, it is described to be hydrocracked Reaction uses Ni-W series hydrocracking catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, hydrogen Oil volume than 1000 under conditions of carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated into tower and fractionates out gasoline, diesel oil and fractionating column bottom of tower heavy oil, Fractionating column bottom of tower heavy oil is recycled back in step (1) again, coal is carried out together as heavy oil with the heavy oil, solvent extraction oil Preparation.
Embodiment 3
(1) coal dust below coal tar, 100 mesh and catalyst are hybridly prepared into coal, coal tar and coal dust press 2:1 Ratio mixed, the addition of catalyst is the 15% of quality of pc；
(2) step (1) described coal is mixed with hydrogen, after preheated device preheating, into suspended-bed reactor, anti- Answer 400 DEG C of temperature, reaction pressure 8MPa, volume space velocity 0.5h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1200；
(3) step (2) described reaction product is isolated into high temperature gaseous phase materials and high-temperature liquid-phase thing through high pressure hot separator Material；After the cooling of high temperature gaseous phase materials, hydrogen-rich gas, light oil and water are isolated；Enter decompression after the decompression of high-temperature liquid-phase material to steam Evaporate tower to be fractionated, isolate crude oil and vacuum tower bottom of towe contains solid heavy still bottoms；
(4) temperature of step (3) described high pressure hot separator is 385 DEG C；The operation bar of step (3) described vacuum distillation tower Part is：380 DEG C of column bottom temperature, tower top residual voltage 30mmHg；
(5) solvent is made using light oil described in step (3), solid heavy still bottoms progress solvent is contained to vacuum tower bottom of towe and is taken out Carry, after solvent recovery, the light oil as solvent recycles；Solvent extraction oil is recycled back in step (1) as heavy oil to be used for The preparation of coal；Solid residue portion after solvent extraction sells as semicoke, partly through gasification, Water gas shift/WGS and After gas purification, for hydrogen making；
(6) crude oil in step (3) and remaining light oil are mixed, into fixed bed hydrogenation finishing reactor；It is described to add Hydrogen refining reaction uses Ni-Mo-W series Hydrobon catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1000；
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracker, it is described to be hydrocracked Reaction uses Ni-W series hydrocracking catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, hydrogen Oil volume than 1000 under conditions of carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated into tower and fractionates out gasoline, diesel oil and fractionating column bottom of tower heavy oil, Fractionating column bottom of tower heavy oil is recycled back in step (1) again, coal is carried out together as heavy oil with the heavy oil, solvent extraction oil Preparation.
Embodiment 4
(1) coal dust below coal tar, 100 mesh and Ni-Mo base oil dissolubility hydrogenation catalysts are hybridly prepared into coal, Coal tar and coal dust are mixed in 2: 1 ratio, and the addition of catalyst is the 0.5% of coal quality；
(2) step (1) described coal is mixed with hydrogen, after preheated device preheating, into suspended-bed reactor, anti- Answer 400 DEG C of temperature, reaction pressure 9MPa, volume space velocity 0.5h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1200；
(3) step (2) described reaction product is isolated into high temperature gaseous phase materials and high-temperature liquid-phase thing through high pressure hot separator Material；After the cooling of high temperature gaseous phase materials, hydrogen-rich gas, light oil and water are isolated；Enter decompression after the decompression of high-temperature liquid-phase material to steam Evaporate tower to be fractionated, isolate crude oil and vacuum tower bottom of towe contains solid heavy still bottoms；
(4) temperature of step (3) described high pressure hot separator is 385 DEG C；The operation bar of step (3) described vacuum distillation tower Part is：380 DEG C of column bottom temperature, tower top residual voltage 30mmHg；
(5) solvent is made using light oil described in step (3), solid heavy still bottoms progress solvent is contained to vacuum tower bottom of towe and is taken out Carry, after solvent recovery, the light oil as solvent recycles；Solvent extraction oil is recycled back in step (1) as heavy oil to be used for The preparation of coal；Solid residue portion after solvent extraction sells as semicoke, partly through gasification, Water gas shift/WGS and After gas purification, for hydrogen making；
(6) crude oil in step (3) and remaining light oil are mixed, into fixed bed hydrogenation finishing reactor；It is described to add Hydrogen refining reaction uses Ni-Mo-W series Hydrobon catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1000；
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracker, it is described to be hydrocracked Reaction uses Ni-W series hydrocracking catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, hydrogen Oil volume than 1000 under conditions of carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated into tower and fractionates out gasoline, diesel oil and fractionating column bottom of tower heavy oil, Fractionating column bottom of tower heavy oil is recycled back in step (1) again, coal is carried out together as heavy oil with the heavy oil, solvent extraction oil Preparation.
Embodiment 5
(1) coal dust below catalytic cracked oil pulp, 100 mesh and catalyst are hybridly prepared into coal, cycle oil Slurry and coal dust are mixed in 2: 1 ratio, and the addition of catalyst is the 15% of quality of pc；
(2) step (1) described coal is mixed with hydrogen, after preheated device preheating, into suspended-bed reactor, anti- Answer 380 DEG C of temperature, reaction pressure 8MPa, volume space velocity 0.5h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1200；
(3) step (2) described reaction product is isolated into high temperature gaseous phase materials and high-temperature liquid-phase thing through high pressure hot separator Material；After the cooling of high temperature gaseous phase materials, hydrogen-rich gas, light oil and water are isolated；Enter decompression after the decompression of high-temperature liquid-phase material to steam Evaporate tower to be fractionated, isolate crude oil and vacuum tower bottom of towe contains solid heavy still bottoms；
(4) temperature of step (3) described high pressure hot separator is 385 DEG C；The operation bar of step (3) described vacuum distillation tower Part is：380 DEG C of column bottom temperature, tower top residual voltage 30mmHg；
(5) solvent is made using light oil described in step (3), solid heavy still bottoms progress solvent is contained to vacuum tower bottom of towe and is taken out Carry, after solvent recovery, the light oil as solvent recycles；Solvent extraction oil is recycled back in step (1) as heavy oil to be used for The preparation of coal；Solid residue portion after solvent extraction sells as semicoke, partly through gasification, Water gas shift/WGS and After gas purification, for hydrogen making；
(6) crude oil in step (3) and remaining light oil are mixed, into fixed bed hydrogenation finishing reactor；It is described to add Hydrogen refining reaction uses Ni-Mo-W series Hydrobon catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, carry out hydrogenation reaction under conditions of hydrogen to oil volume ratio 1000；
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracker, it is described to be hydrocracked Reaction uses Ni-W series hydrocracking catalysts, 360 DEG C of reaction temperature, reaction pressure 16MPa, volume space velocity 0.35h-1, hydrogen Oil volume than 1000 under conditions of carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated into tower and fractionates out gasoline, diesel oil and fractionating column bottom of tower heavy oil, Fractionating column bottom of tower heavy oil is recycled back in step (1) again, coal is carried out together as heavy oil with the heavy oil, solvent extraction oil Preparation.
In order to prove the technique effect of coal of the present invention and oil refining production oil product technique altogether, it is special to above-described embodiment 1, it is real Apply example 2, embodiment 3, embodiment 4 and embodiment 5 and carry out measuring.
Conversion ratio=1- (moisture, ash content quality in solid residue quality-coal dust, catalyst)/(dry ash free basis coal of coal Silty amount+dry ash free basis catalyst carrier quality) × 100%；
Gasoline, diesel oil distillate quality/(heavy oil quality+dry ash free basis coal dust matter are generated in oil product yield=whole technique Amount+dry ash free basis catalyst carrier quality) × 100%.
Wherein, the catalyst carrier quality refers both to use catalyst of the coal dust for carrier.
It is as shown in table 1 that the coal of embodiment 1~5 refines result with oil altogether.
Table 1
The invention provides one kind to be used for coal and oil refining production oil product, and the method for by-product semicoke altogether, its key step bag Include：Coal dust, heavy oil and catalyst are mixed and made into coal, after preheating is mixed with hydrogen, refining reactor enters altogether with oil into coal Row reaction, reaction product isolate hydrogen-rich gas, light oil, water, crude oil, solvent extraction oil and solid residue, hydrogen-rich gas, light oil The oil products such as hydro-upgrading cellular manufacture gasoline, diesel oil are entered back into crude oil, solvent extraction oil is recycled back to coal preparation unit work Coal preparation is carried out for heavy oil, solid residue can be used as semicoke to sell, it can also be used to hydrogen making.The present invention has technique side Method is simple, reaction condition mitigations, oil product high income, without circulating hydrogenation solvent, investing the advantages that small.

Claims (11)

  1. A kind of 1. method for refining production oil product altogether with oil for coal, it is characterised in that comprise the following steps：
    1) coal dust, catalyst and heavy oil are mixed and made into coal；
    In the coal preparation process, the mass ratio of coal dust and heavy oil is (1: 9)~(5.5: 4.5)；
    The catalyst using red mud, Natural pyrite, metallurgical flying dust, high ferro gangue, Ni-W bases hydrocracking catalyst, At least one of Ni-Mo base oil dissolubilities hydrogenation catalyst, ultra-fine high dispersive ferrum-based catalyst；
    The heavy oil using reduced crude, decompression residuum, catalytic cracked oil pulp, Aromatics Extractive Project oil, visbreaker tar, coking heavy oil, At least one of converting plastic waste to oil, waste rubber tire oil；The boiling range of the heavy oil is 200~550 DEG C；
    2) after coal being mixed to preheating with hydrogen, unit is refined altogether into coal and oil, is obtained coal and is refined reaction product altogether with oil；
    The reaction temperature that the coal refines unit with oil altogether is 380~470 DEG C, reaction pressure is 6~20MPa, hydrogen to oil volume ratio is 600~1500；
    The reactor that the coal refines unit with oil altogether uses suspended-bed reactor or paste state bed reactor；
    3) refining reaction product isolates high temperature gaseous phase materials and high-temperature liquid-phase material to coal through high pressure hot separator altogether with oil；
    4) cold high pressure separator will be entered after the cooling of high temperature gaseous phase materials that step 3) obtains, isolate hydrogen-rich gas, light oil and Water；
    5) enter vacuum distillation tower after the high-temperature liquid-phase material decompression obtained step 3) and carry out separation of solid and liquid, isolate crude oil and Vacuum tower bottom of towe contains solid Residual oil；
    The stripping section of the vacuum distillation tower does not set column plate；The vacuum distillation tower, crude oil is with vacuum tower bottom of towe containing solid Residual oil Cutting temperature is 360~520 DEG C；
    6) vacuum tower bottom of towe is contained into solid Residual oil again through solvent extraction, isolates solvent extraction oil, solvent and solid residue；
    7) the isolated solvent extraction oil of step 6) is recycled back in step 1) and coal is made as heavy oil, solvent is recovered Posterior circle uses；
    8) solid residue isolated in step 6) is sold directly as semicoke, or into Hydrogen Unit, through gasification, water coal Hydrogen is produced in gas conversion, gas purification, for step 2) and 9) use；
    9) crude oil isolated in the hydrogen-rich gas obtained in step 4), light oil and step 5) is mixed, into hydro-upgrading list Member；
    10) product of hydro-upgrading unit is fractionated into tower and fractionates out gasoline, diesel oil and fractionation column bottom heavy oil product；
    11) the fractionating column bottom of tower heavy oil in step 10) is recycled back into Hydrocracking unit to continue to react, or be recycled back in step 1) Prepared with heavy oil, solvent extraction oil together as heavy oil for coal.
  2. A kind of 2. method for coal and the common refining production oil product of oil as claimed in claim 1, it is characterised in that in step 1), institute Coal dust is stated as at least one of mud coal, bituminous coal, lignite.
  3. 3. a kind of method for coal and the common refining production oil product of oil as claimed in claim 2, it is characterised in that the coal dust is height Volatile matter bituminous coal and old lignite, the high volatile refer to volatile matter Vdaf＞ 35%, the particle diameter of the coal dust for 150 μm with Under.
  4. 4. a kind of method for coal and the common refining production oil product of oil as claimed in claim 1, it is characterised in that the heavy oil evaporates Journey is 360~500 DEG C.
  5. A kind of 5. method for coal and the common refining production oil product of oil as claimed in claim 1, it is characterised in that the vacuum distillation Tower, crude oil are 420~500 DEG C with cutting temperature of the vacuum tower bottom of towe containing solid Residual oil.
  6. 6. a kind of method for coal and the common refining production oil product of oil as claimed in claim 1, it is characterised in that right in step 6) Vacuum tower bottom of towe contains solid Residual oil and carries out solvent extraction, and its extraction solvent is light petrol or crude benzol.
  7. 7. a kind of method for coal and the common refining production oil product of oil as claimed in claim 6, it is characterised in that described to vacuum tower Bottom of towe contains solid Residual oil and carries out solvent extraction, and its extraction solvent is the light petrol in step 4).
  8. A kind of 8. method for coal and the common refining production oil product of oil as claimed in claim 1, it is characterised in that in step 7), institute State solvent extraction oil and be recycled back to the preparation for being used for coal in step 1) as heavy oil.
  9. A kind of 9. method for coal and the common refining production oil product of oil as claimed in claim 1, it is characterised in that in step 8), institute State solid residue to sell directly as semicoke, for boiler combustion, power plants generating electricity；Or into Hydrogen Unit, through gasification, water-gas Hydrogen is produced in change, gas purification, for being used in step 2) and step 8).
  10. A kind of 10. method for coal and the common refining production oil product of oil as claimed in claim 1, it is characterised in that in step 9), The hydro-upgrading unit is refined using fixed bed hydrogenation, hydrocracking unit combination, or only with the refined dress of fixed bed hydrogenation Put.
  11. A kind of 11. method for coal and the common refining production oil product of oil as claimed in claim 1, it is characterised in that in step 10), The fractionating column bottom of tower heavy oil is recycled back to Hydrocracking unit and continues to react, or is recycled back in step 1) and heavy oil, solvent extraction Oil is prepared together as heavy oil for coal.
CN201510950031.8A 2015-12-16 2015-12-16 A kind of method for refining production oil product altogether with oil for coal Active CN105567321B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510950031.8A CN105567321B (en) 2015-12-16 2015-12-16 A kind of method for refining production oil product altogether with oil for coal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510950031.8A CN105567321B (en) 2015-12-16 2015-12-16 A kind of method for refining production oil product altogether with oil for coal

Publications (2)

Publication Number Publication Date
CN105567321A CN105567321A (en) 2016-05-11
CN105567321B true CN105567321B (en) 2017-12-29

Family

ID=55877963

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510950031.8A Active CN105567321B (en) 2015-12-16 2015-12-16 A kind of method for refining production oil product altogether with oil for coal

Country Status (1)

Country Link
CN (1) CN105567321B (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9777235B2 (en) 2016-04-04 2017-10-03 Allard Services Limited Fuel oil compositions and processes
KR102417784B1 (en) 2016-04-04 2022-07-06 에이알큐 아이피 리미티드 Solid-liquid crude oil compositions and fractionation processes thereof
CN108531218A (en) * 2017-03-01 2018-09-14 何巨堂 Hydrogen-consuming process produces the combined method of the hydrogen manufacturing of the hydrogen rich gas hydrocarbon gas and the gasification of carbonaceous solids material
CN107057756A (en) * 2017-06-23 2017-08-18 北京中科诚毅科技发展有限公司 A kind of all-round bed hydroprocessing technique
CN109207183A (en) * 2017-06-30 2019-01-15 昆山超优清洁能源有限公司 A kind of composite oil-soluble catalyst is total to the application method in sweetening process in oily coal
CN109181770B (en) * 2018-07-11 2019-09-27 上海英保能源化工科技有限公司 A method of refining production oil product and chemicals altogether for inferior heavy oil, coal
CN109233890A (en) * 2018-09-04 2019-01-18 新奥科技发展有限公司 A kind of oil gas coproduction gasification process and device
CN111909719A (en) * 2020-06-19 2020-11-10 张家港保税区慧鑫化工科技有限公司 Production system and production method for heavy oil to produce naphtha in large quantity
CN111849554A (en) * 2020-07-03 2020-10-30 张家港保税区慧鑫化工科技有限公司 Garbage liquid-phase suspension bed hydrotreatment system and technology
CN111808636A (en) * 2020-07-17 2020-10-23 张家港保税区慧鑫化工科技有限公司 Sludge heavy oil treatment method
CN111808632A (en) * 2020-07-17 2020-10-23 张家港保税区慧鑫化工科技有限公司 Method for processing mixture of oil and organic waste
CN111849555A (en) * 2020-07-21 2020-10-30 张家港保税区慧鑫化工科技有限公司 System and method for hydrotreating halogen-containing waste oil
CN113214874A (en) * 2021-05-26 2021-08-06 西京学院 Method for kerosene co-catalytic pyrolysis-semicoke catalytic gasification

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220286B (en) * 2007-12-13 2011-10-05 神华集团有限责任公司 Joint processing technique for coal and stone oil
CN101712889B (en) * 2009-11-26 2013-01-09 湖南长岭石化科技开发有限公司 Method for preparing light aromatics from coal tar
CN104178197B (en) * 2013-05-22 2016-06-29 任相坤 The method that coal tar and coal coreaction prepare liquid fuel

Also Published As

Publication number Publication date
CN105567321A (en) 2016-05-11

Similar Documents

Publication Publication Date Title
CN105567321B (en) A kind of method for refining production oil product altogether with oil for coal
CN102191072B (en) Comprise coal method for transformation and the product of fixed bed hydrogenation cleavage stages and two direct ebullated bed liquefaction stages
CN103146413B (en) The method in the presence of coming from the hydrogen of non-fossil sources, carbon-based material being converted by the hydridization approach that direct liquefaction and indirect liquefaction combine
CN101885976B (en) Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof
CN102115674B (en) Coal liquefaction and petroleum refining combined method
CN101580728B (en) Process technology for non-caking coal or weak caking coal
CN1876767B (en) Coal tar hydrocracking method
CN103146411A (en) Process for coal conversion comprising at least one step of liquefaction for the manufacture of aromatics
CN103992823B (en) Low-order coal and the method and system that biomass are Material synthesis methane and petrol and diesel oil
CN106433775B (en) A kind of kerosene is total to smelting method and its device
CN101333448A (en) Direct liquefaction process of coal by replacing circling solvent with petroleum or petroleum refining byproduct
CN104962307B (en) Method for producing light oil through coal liquefaction
CN100412168C (en) Coal tar hydrogenation process and catalyst therefor
CN104087339A (en) Hydrogenation co-processing method for mixed oil, coal and coal tar
CN102031154B (en) Method for comprehensively utilizing lignite
CN107267186A (en) The method that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon
CN104004541B (en) A kind of preparation method of coal-based high arene underwater content stock oil
CN102031135A (en) Comprehensive processing and utilizing method for heavy oil
CN106609149B (en) A kind of residual oil and full fraction of coal tar method of hydrotreating
CN112111294B (en) Method and system for preparing oil from coal-based asphalt
CN109111950A (en) The method of full fraction hydrogenation of tar production liquid fuel
CN109355100B (en) Coal tar processing and coal co-refining combined process
CN110643391A (en) Method for converting coal tar/heavy oil into liquefied gas, naphtha and diesel oil
CN104004542A (en) Method for preparing coal-based high aromatic potential content raw oil
CN105001907B (en) A kind of method and system of paraffinic base crude oil with poor quality Poly-generation

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20190424

Address after: 200120 104, room 1, 2555 Xiu Pu Road, Pudong New Area, Shanghai.

Patentee after: Shanghai Jun Ming Chemical Engineering Design Co. Ltd.

Address before: Room 389, Building 3, 2388 Xiupu Road, Pudong New Area, Shanghai, 200120

Patentee before: SHANGHAI YINGBAO ENERGY CHEMICAL TECHNOLOGY CO., LTD.