CN105567321A - Method for producing oil product by corefining coal and oil - Google Patents
Method for producing oil product by corefining coal and oil Download PDFInfo
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- CN105567321A CN105567321A CN201510950031.8A CN201510950031A CN105567321A CN 105567321 A CN105567321 A CN 105567321A CN 201510950031 A CN201510950031 A CN 201510950031A CN 105567321 A CN105567321 A CN 105567321A
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- 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
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- 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
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- 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
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- 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
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to an oil product production method, particularly a method for producing an oil product by corefining coal and oil. The method comprises the following steps: mixing coal powder, heavy oil and a catalyst to prepare an oil coal slurry, mixing with hydrogen gas, preheating, sending into a coal-oil corefining reactor, reacting, separating hydrogen-rich gas, light oil, water, crude oil, solvent extracted oil and solid residues from the reaction products, sending the hydrogen-rich gas, light oil and crude oil into a hydrogenation modification unit to produce gasoline, diesel and other oil products, and circulating the solvent extracted oil back to an oil coal slurry preparation unit as heavy oil to prepare the oil coal slurry, wherein the solid residues can be used sold as semicoke and can also be used for preparing hydrogen gas. The method has the advantages of simple technique, mild reaction conditions, high oil product yield, no need of hydrogenation solvent circulation, low investment and the like.
Description
Technical field
The present invention relates to Oil Production method, especially relate to and a kind ofly refine the method for producing oil product altogether for coal and oil.
Background technology
DCL/Direct coal liquefaction and coal and the oil altogether technology of refining are two key areas of clean coal technology.Direct coal liquefaction process is mixed with circulating solvent by fine coal, with hydrogen reaction under certain temperature, pressure condition, makes the organic matter of coal be converted into liquefaction oil.Again by desulfurization, denitrogenation, improve liquefaction oil quality further, make product can produce transport fuel and Chemicals in general refinery.The advantage of DCL/Direct coal liquefaction is that oily yield and thermo-efficiency are high; Main drawback is that the operational condition of hydrogenation technique is harsher.And coal and oil altogether the technology of refining be the technology that a kind of coal of growing up on the basis of direct coal liquefaction technology and heavy oil are processed jointly, this technology has the advantages that to complete heavy oil modification and gelatin liquefaction two processes simultaneously, being the important means effectively utilizing coal and inferior heavy oil, is the technique of most economy and industrialization future in DCL/Direct coal liquefaction third generation technique.
It is under the condition of high temperature, high pressure that coal and oil refine altogether, rupture at the weak cross-link bond place of coal, form the coal free radical fragment differed in size, coal free radical fragment accepts hydrogen in hydrogen supply dissolvent and hydrogen atmosphere, or there is hydrogen rearrangement transfer in coal molecule, and carry out the hydrogenolysis of series of parallel order, cracking and self stabilizationization reaction, generate the product that molecular weight is lower.In coal and oil refining process altogether, coal and heavy oil is not exclusively respective independent reaction also, and has very strong interaction.Heavy oil is reactant, while carrying out hydrocracking reaction, again as the solvent of gelatin liquefaction, affects the conversion process of coal.If heavy oil used has good hydrogen supply capacity, coal and heavy oil have good synergistic effect, and coal and oil are refined oil tech altogether and is better than conventional direct coal liquefaction technology to a certain extent; If but heavy oil used does not have good hydrogen supply capacity, not only oily productive rate can not be improved, also oily productive rate can be reduced.
Compared with direct coal liquefaction technology, coal and the oil altogether technology of refining have following advantage: the useful volume that can make full use of reactor, improve the processing power of production equipment and the production efficiency of this technological process; Synergistic effect between the arene of coal and the paraffin class of heavy oil, the generation that coal and oil are refined altogether oil is more easily processed into the oil products such as qualified gasoline, diesel oil; Protium in residual oil is higher than the protium content of coal, and in coal and oil refining process altogether, hydrogen consumption reduces, and hydrogen utilization ratio increases substantially, and can effectively reduce energy consumption and facility investment; Micro-metals (as iron, nickel etc.) in heavy oil can be used as hydrogenation active component, facilitates the carrying out of hydrogenation reaction, effectively improves the quality of oil product.
Chinese patent CN104087339A discloses a kind of method that assorted oil, coal and coal tar hydrogenating refine altogether, the method enters paste state bed reactor after assorted oil, coal, coal tar and catalyst mix are made coal oil mixture, react under temperature of reaction 400 ~ 455 DEG C, reaction pressure 8 ~ 19MPa and hydrogen to oil volume ratio are the condition of 800 ~ 1200, product fractionation goes out to be less than 320 DEG C of cuts and enters fixed bed and carry out hydrofining, finally fractionates out oil product.Although the method oil product yield is high, reaction conditions is too harsh, and produces solid slag and cannot process.
Chinese patent CN1515650A discloses a kind of processing method utilizing thermally dissolving and catalytic preparing liquid fuel from coal, coal dust, solvating agent and catalyst mix are made coal slurry and are carried out thermally dissolving and catalytic reaction by the method, again thermally dissolving and catalytic product filtered, distill, 350 DEG C of fraction hydrogenating modifications will be less than and make liquid oil.Although the method processing method is simple, running cost is low, liquefaction oil yield is lower.
At present, how the research of refining altogether coal and oil both at home and abroad mainly improves transformation efficiency and the oil product yield of coal.But pursue too high coal transformation efficiency and oil product yield must with the reaction conditions of harshness (430 ~ 470 DEG C, 15 ~ 30MPa) for cost.
Summary of the invention
The object of this invention is to provide under the prerequisite maintaining certain oil product yield, adopt the reaction conditions comparatively relaxed as far as possible, a kind of of by-product semicoke refines the method for producing oil product altogether for coal and oil.
The present invention includes following steps:
1) coal dust, catalyzer and heavy oil are mixed and made into coal oil mixture;
2) by coal oil mixture with after hydrogen mixing preheating, enter coal and oil refines unit altogether, obtain coal and oil refines reaction product altogether;
3) coal and oil refine reaction product altogether and isolate High Temperature Gas phase materials and high-temperature liquid-phase material through high pressure hot separator;
4) by step 3) enter cold high pressure separator after the cooling of the High Temperature Gas phase materials that obtains, isolate hydrogen-rich gas, light oil and water;
5) by step 3) enter vacuum still after the decompression of the high-temperature liquid-phase material that obtains and carry out solid-liquid separation, isolate at the bottom of thick oil and vacuum distillation tower tower containing Residual oil admittedly;
6) by containing solid Residual oil at the bottom of vacuum distillation tower tower again through solvent extraction, solvent extraction oil, solvent and solid residue is isolated;
7) using step 6) be separated the oil circulation time step 1 of solvent extraction that obtains) in make coal oil mixture as heavy oil, solvent uses through reclaiming Posterior circle;
8) using step 6) in be separated the solid residue that obtains and directly sell as semicoke, or enter Hydrogen Unit, produce hydrogen, for step 2 through gasification, water-gas shift, gas sweetening) and 9);
9) by step 4) in the hydrogen-rich gas, light oil and the step 5 that obtain) in isolated thick oil mixing, enter hydro-upgrading unit;
10) product of hydro-upgrading unit fractionates out the products such as heavy oil at the bottom of gasoline, diesel oil and separation column tower through separation column;
11) by step 10) in separation column tower at the bottom of heavy oil loop back Hydrocracking unit continue reaction, also can loop back step 1) in together with heavy oil, solvent extraction oil as heavy oil be used for coal oil mixture prepare.
In step 1) in, described coal dust is the mud coal, bituminous coal, brown coal etc. that degree of coalification is low, and preferred high-volatile bituminous coal and old brown coal, described high volatile refers to volatile matter V
daf> 35%, the particle diameter of described coal dust preferably less than 150 μm;
Described catalyzer can adopt at least one in red mud, Natural pyrite, metallurgical flying dust, high ferro coal gangue, Ni-W base hydrocracking catalyst, Ni-Mo base oil dissolubility hydrogenation catalyst, ultra-fine high dispersive ferrum-based catalyst etc.;
Described heavy oil can adopt at least one in long residuum, vacuum residuum, catalytically cracked oil, Aromatics Extractive Project oil, visbreaker tar, coking heavy oil, coal tar, converting plastic waste to oil, waste rubber tire wet goods; The boiling range of described heavy oil can be 200 ~ 550 DEG C, preferably 360 ~ 500 DEG C;
In described coal oil mixture 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) in, the reactor that described coal and oil refine unit altogether can adopt suspended-bed reactor or paste state bed reactor etc.; Described coal and oil refine altogether unit temperature of reaction 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 is 800 ~ 1200.
In step 5) in, the stripping section of described vacuum still does not establish column plate; Described vacuum still, thick oil can be 360 ~ 520 DEG C, preferably 420 ~ 500 DEG C with at the bottom of vacuum distillation tower tower containing the cutting temperature of solid Residual oil.
In step 6) in, describedly carry out solvent extraction at the bottom of vacuum distillation tower tower containing solid Residual oil, its extraction solvent is the low boiling point hydrocarbon such as petroleum naphtha, crude benzol, preferred steps 4) in light oil.
In step 7) in, described solvent extraction oil can loop back step 1) in be used for the preparation of coal oil mixture as heavy oil.
In step 8) in, described solid residue has the feature such as high-carbon, golf calorific value, can directly sell, for boiler combustion, power plants generating electricity etc. as semicoke; Also can enter Hydrogen Unit, produce hydrogen, for step 2 through gasification, water-gas change, gas sweetening) and step 8) in.
In step 9) in, described hydro-upgrading unit employing fixed bed hydrogenation is refining, hydroeracking unit coupling, or only adopts fixed bed hydrogenation refining plant.
In step 10) in, heavy oil at the bottom of described separation column tower can loop back Hydrocracking unit continue reaction, also can loop back step 1) in together with heavy oil, solvent extraction oil as heavy oil be used for coal oil mixture prepare.
The present invention proposes under the prerequisite maintaining certain oil product yield, adopt the reaction conditions that comparatively relaxes to carry out coal and oil refines reaction altogether as far as possible, be conducive to like this reducing facility investment, reducing running cost, also can have the semicoke of economic worth by by-product, substantially increase the economic benefit that whole coal and oil refine project altogether.
The invention has the advantages that:
1. coal and heavy oil are organically combined, produce oil product by coal and oil technology of refining altogether simultaneously, and by-product semicoke, effectively reduce the difficulty of reaction, improve the economic benefit of whole project.
2. adopt the method for solvent extraction to improve the yield of oil product to greatest extent containing solid Residual oil at the bottom of pair vacuum distillation tower tower, and directly sold as semicoke by the solid residue portion after extracting, part is used for hydrogen making.
3. adopt the reaction conditions comparatively relaxed, reduce the severity of reaction, significantly reduce investment and the process cost of device.
4., without the need to the hydrogenation solvent that circulates, reduce the hydrogenation depth that coal and oil refine unit altogether, improve the utilization ratio of hydrogen, simplify technical process.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Respectively be labeled as in figure: 1 is coal dust; 2 is heavy oil; 3 is catalyzer; 4 is coal oil mixture preparation tank; 5 is hydrogen; 6 refine unit altogether for kerosene; 7 is vacuum still; 8 is containing solid Residual oil at the bottom of vacuum distillation tower tower; 9 is hydrofining unit; 10 is Hydrocracking unit; 11 is separation column; 12 is heavy oil at the bottom of separation column tower; 13 is solvent extraction unit; 14 is solvent extraction oil; 15 is solid residue; 16 is petroleum naphtha; 17 is 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 catalytically cracked oil, 100 orders and catalyst mix are mixed with coal oil mixture, catalytically cracked oil and coal dust mix in the ratio of 1: 1, and the addition of catalyzer is 7.5% of quality of pc;
(2) step (1) described coal oil mixture is mixed with hydrogen, after preheater preheats, enter suspended-bed reactor, at temperature of reaction 400 DEG C, reaction pressure 6.5MPa, volume space velocity 0.5h
-1, hydrogen to oil volume ratio 1200 condition under carry out hydrogenation reaction;
(3) step (2) described reaction product is isolated High Temperature Gas phase materials and high-temperature liquid-phase material through high pressure hot separator; After the cooling of High Temperature Gas phase materials, isolate hydrogen-rich gas, lightweight oil and water; Enter vacuum still after the decompression of high-temperature liquid-phase material and carry out fractionation, isolate at the bottom of thick oil and vacuum distillation tower tower containing solid heavy still bottoms;
(4) temperature of step (3) described high pressure hot separator is 390 DEG C; The operational condition of step (3) described vacuum still is: column bottom temperature 385 DEG C, tower top residual voltage 40mmHg;
(5) adopt lightweight oil described in step (3) to make solvent, carry out solvent extraction at the bottom of vacuum distillation tower tower containing solid heavy still bottoms, after solvent recuperation, the lightweight oil as solvent recycles; Solvent extraction oil loops back the preparation for coal oil mixture in step (1) as heavy oil; Solid residue portion after solvent extraction sells as semicoke, partly after gasification, water-gas shift and gas sweetening, for hydrogen making;
(6) by the thick oil in step (3) and the mixing of residue lightweight oil, fixed bed hydrogenation refining reaction device is entered; Described hydrofining reaction adopts Ni-Mo-W series Hydrobon catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction;
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracking case, described hydrocracking reaction adopts Ni-W series hydrocracking catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated out heavy oil at the bottom of gasoline, diesel oil and separation column tower through separation column, again heavy oil at the bottom of separation column tower is looped back in step (7), enter hydrocracking reactor and carry out hydrocracking reaction together with described hydrotreated product, at the bottom of described separation column tower, heavy oil accounts for 3% of isocrackate total mass.
Embodiment 2
(1) coal dust below catalytically cracked oil, 100 orders and catalyst mix are mixed with coal oil mixture, catalytically cracked oil and coal dust mix in the ratio of 2: 1, and the addition of catalyzer is 15% of quality of pc;
(2) step (1) described coal oil mixture is mixed with hydrogen, after preheater preheats, enter suspended-bed reactor, at temperature of reaction 400 DEG C, reaction pressure 11MPa, volume space velocity 0.5h
-1, hydrogen to oil volume ratio 1200 condition under carry out hydrogenation reaction;
(3) step (2) described reaction product is isolated High Temperature Gas phase materials and high-temperature liquid-phase material through high pressure hot separator; After the cooling of High Temperature Gas phase materials, isolate hydrogen-rich gas, lightweight oil and water; Enter vacuum still after the decompression of high-temperature liquid-phase material and carry out fractionation, isolate at the bottom of thick oil and vacuum distillation tower tower containing solid heavy still bottoms;
(4) temperature of step (3) described high pressure hot separator is 385 DEG C; The operational condition of step (3) described vacuum still is: column bottom temperature 380 DEG C, tower top residual voltage 30mmHg;
(5) adopt lightweight oil described in step (3) to make solvent, carry out solvent extraction at the bottom of vacuum distillation tower tower containing solid heavy still bottoms, after solvent recuperation, the lightweight oil as solvent recycles; Solvent extraction oil loops back the preparation for coal oil mixture in step (1) as heavy oil; Solid residue portion after solvent extraction sells as semicoke, partly after gasification, water-gas shift and gas sweetening, for hydrogen making;
(6) by the thick oil in step (3) and the mixing of residue lightweight oil, fixed bed hydrogenation refining reaction device is entered; Described hydrofining reaction adopts Ni-Mo-W series Hydrobon catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction;
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracking case, described hydrocracking reaction adopts Ni-W series hydrocracking catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated out heavy oil at the bottom of gasoline, diesel oil and separation column tower through separation column, again heavy oil at the bottom of separation column tower is looped back in step (1), carry out the preparation of coal oil mixture as heavy oil together with described heavy oil, solvent extraction oil.
Embodiment 3
(1) coal dust below coal tar, 100 orders and catalyst mix are mixed with coal oil mixture, coal tar and coal dust mix in the ratio of 2:1, and the addition of catalyzer is 15% of quality of pc;
(2) step (1) described coal oil mixture is mixed with hydrogen, after preheater preheats, enter suspended-bed reactor, at temperature of reaction 400 DEG C, reaction pressure 8MPa, volume space velocity 0.5h
-1, hydrogen to oil volume ratio 1200 condition under carry out hydrogenation reaction;
(3) step (2) described reaction product is isolated High Temperature Gas phase materials and high-temperature liquid-phase material through high pressure hot separator; After the cooling of High Temperature Gas phase materials, isolate hydrogen-rich gas, lightweight oil and water; Enter vacuum still after the decompression of high-temperature liquid-phase material and carry out fractionation, isolate at the bottom of thick oil and vacuum distillation tower tower containing solid heavy still bottoms;
(4) temperature of step (3) described high pressure hot separator is 385 DEG C; The operational condition of step (3) described vacuum still is: column bottom temperature 380 DEG C, tower top residual voltage 30mmHg;
(5) adopt lightweight oil described in step (3) to make solvent, carry out solvent extraction at the bottom of vacuum distillation tower tower containing solid heavy still bottoms, after solvent recuperation, the lightweight oil as solvent recycles; Solvent extraction oil loops back the preparation for coal oil mixture in step (1) as heavy oil; Solid residue portion after solvent extraction sells as semicoke, partly after gasification, water-gas shift and gas sweetening, for hydrogen making;
(6) by the thick oil in step (3) and the mixing of residue lightweight oil, fixed bed hydrogenation refining reaction device is entered; Described hydrofining reaction adopts Ni-Mo-W series Hydrobon catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction;
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracking case, described hydrocracking reaction adopts Ni-W series hydrocracking catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated out heavy oil at the bottom of gasoline, diesel oil and separation column tower through separation column, again heavy oil at the bottom of separation column tower is looped back in step (1), carry out the preparation of coal oil mixture as heavy oil together with described heavy oil, solvent extraction oil.
Embodiment 4
(1) coal dust below coal tar, 100 orders and Ni-Mo base oil dissolubility hydrogenation catalyst are hybridly prepared into coal oil mixture, coal tar and coal dust mix in the ratio of 2: 1, and the addition of catalyzer is 0.5% of coal oil mixture quality;
(2) step (1) described coal oil mixture is mixed with hydrogen, after preheater preheats, enter suspended-bed reactor, at temperature of reaction 400 DEG C, reaction pressure 9MPa, volume space velocity 0.5h
-1, hydrogen to oil volume ratio 1200 condition under carry out hydrogenation reaction;
(3) step (2) described reaction product is isolated High Temperature Gas phase materials and high-temperature liquid-phase material through high pressure hot separator; After the cooling of High Temperature Gas phase materials, isolate hydrogen-rich gas, lightweight oil and water; Enter vacuum still after the decompression of high-temperature liquid-phase material and carry out fractionation, isolate at the bottom of thick oil and vacuum distillation tower tower containing solid heavy still bottoms;
(4) temperature of step (3) described high pressure hot separator is 385 DEG C; The operational condition of step (3) described vacuum still is: column bottom temperature 380 DEG C, tower top residual voltage 30mmHg;
(5) adopt lightweight oil described in step (3) to make solvent, carry out solvent extraction at the bottom of vacuum distillation tower tower containing solid heavy still bottoms, after solvent recuperation, the lightweight oil as solvent recycles; Solvent extraction oil loops back the preparation for coal oil mixture in step (1) as heavy oil; Solid residue portion after solvent extraction sells as semicoke, partly after gasification, water-gas shift and gas sweetening, for hydrogen making;
(6) by the thick oil in step (3) and the mixing of residue lightweight oil, fixed bed hydrogenation refining reaction device is entered; Described hydrofining reaction adopts Ni-Mo-W series Hydrobon catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction;
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracking case, described hydrocracking reaction adopts Ni-W series hydrocracking catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated out heavy oil at the bottom of gasoline, diesel oil and separation column tower through separation column, again heavy oil at the bottom of separation column tower is looped back in step (1), carry out the preparation of coal oil mixture as heavy oil together with described heavy oil, solvent extraction oil.
Embodiment 5
(1) coal dust below catalytically cracked oil, 100 orders and catalyst mix are mixed with coal oil mixture, catalytically cracked oil and coal dust mix in the ratio of 2: 1, and the addition of catalyzer is 15% of quality of pc;
(2) step (1) described coal oil mixture is mixed with hydrogen, after preheater preheats, enter suspended-bed reactor, at temperature of reaction 380 DEG C, reaction pressure 8MPa, volume space velocity 0.5h
-1, hydrogen to oil volume ratio 1200 condition under carry out hydrogenation reaction;
(3) step (2) described reaction product is isolated High Temperature Gas phase materials and high-temperature liquid-phase material through high pressure hot separator; After the cooling of High Temperature Gas phase materials, isolate hydrogen-rich gas, lightweight oil and water; Enter vacuum still after the decompression of high-temperature liquid-phase material and carry out fractionation, isolate at the bottom of thick oil and vacuum distillation tower tower containing solid heavy still bottoms;
(4) temperature of step (3) described high pressure hot separator is 385 DEG C; The operational condition of step (3) described vacuum still is: column bottom temperature 380 DEG C, tower top residual voltage 30mmHg;
(5) adopt lightweight oil described in step (3) to make solvent, carry out solvent extraction at the bottom of vacuum distillation tower tower containing solid heavy still bottoms, after solvent recuperation, the lightweight oil as solvent recycles; Solvent extraction oil loops back the preparation for coal oil mixture in step (1) as heavy oil; Solid residue portion after solvent extraction sells as semicoke, partly after gasification, water-gas shift and gas sweetening, for hydrogen making;
(6) by the thick oil in step (3) and the mixing of residue lightweight oil, fixed bed hydrogenation refining reaction device is entered; Described hydrofining reaction adopts Ni-Mo-W series Hydrobon catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction;
(7) hydrotreated product in step (6) is directly entered fixed bed hydrogenation cracking case, described hydrocracking reaction adopts Ni-W series hydrocracking catalyst, temperature of reaction 360 DEG C, reaction pressure 16MPa, volume space velocity 0.35h
-1, hydrogen to oil volume ratio 1000 condition under carry out hydrogenation reaction.
(8) isocrackate in step (7) is fractionated out heavy oil at the bottom of gasoline, diesel oil and separation column tower through separation column, again heavy oil at the bottom of separation column tower is looped back in step (1), carry out the preparation of coal oil mixture as heavy oil together with described heavy oil, solvent extraction oil.
In order to prove that coal of the present invention and oil refine the technique effect producing oil product technique altogether, spy has carried out measuring to above-described embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5.
Transformation efficiency=1-(in solid residue quality-coal dust, catalyzer moisture, ash content quality)/(dry ash-free basis quality of pc+dry ash-free basis support of the catalyst quality) × 100% of coal;
Gasoline, diesel oil distillate quality/(heavy oil quality+dry ash-free basis quality of pc+dry ash-free basis support of the catalyst quality) × 100% is generated in oil product productive rate=whole technique.
Wherein, described support of the catalyst quality all refers to adopt coal dust to be the catalyzer of carrier.
It is as shown in table 1 that embodiment 1 ~ 5 coal and oil refine result altogether.
Table 1
The invention provides one and refine production oil product altogether for coal and oil, and the method for by-product semicoke, its key step comprises: by coal dust, heavy oil and catalyst mix make coal oil mixture, after hydrogen mixing preheating, enter coal and oil to refine reactor altogether and react, reaction product isolates hydrogen-rich gas, light oil, water, thick oil, solvent extraction oil and solid residue, hydrogen-rich gas, light oil and thick oil enter hydro-upgrading cellular manufacture gasoline again, the oil products such as diesel oil, the oil circulation oil return coal slurry of solvent extraction is prepared unit and is carried out coal oil mixture preparation as heavy oil, solid residue can be used as semicoke and sells, also can be used for hydrogen making.The present invention has that processing method is simple, reaction conditions relaxes, oil product yield is high, without the need to the hydrogenation solvent that circulates, invest the advantages such as little.
Claims (10)
1. refine a method of producing oil product altogether for coal and oil, it is characterized in that comprising the steps:
1) coal dust, catalyzer and heavy oil are mixed and made into coal oil mixture;
2) by coal oil mixture with after hydrogen mixing preheating, enter coal and oil refines unit altogether, obtain coal and oil refines reaction product altogether;
3) coal and oil refine reaction product altogether and isolate High Temperature Gas phase materials and high-temperature liquid-phase material through high pressure hot separator;
4) by step 3) enter cold high pressure separator after the cooling of the High Temperature Gas phase materials that obtains, isolate hydrogen-rich gas, light oil and water;
5) by step 3) enter vacuum still after the decompression of the high-temperature liquid-phase material that obtains and carry out solid-liquid separation, isolate at the bottom of thick oil and vacuum distillation tower tower containing Residual oil admittedly;
6) by containing solid Residual oil at the bottom of vacuum distillation tower tower again through solvent extraction, solvent extraction oil, solvent and solid residue is isolated;
7) using step 6) be separated the oil circulation time step 1 of solvent extraction that obtains) in make coal oil mixture as heavy oil, solvent uses through reclaiming Posterior circle;
8) using step 6) in be separated the solid residue that obtains and directly sell as semicoke, or enter Hydrogen Unit, produce hydrogen, for step 2 through gasification, water-gas shift, gas sweetening) and 9);
9) by step 4) in the hydrogen-rich gas, light oil and the step 5 that obtain) in isolated thick oil mixing, enter hydro-upgrading unit;
10) product of hydro-upgrading unit fractionates out the products such as heavy oil at the bottom of gasoline, diesel oil and separation column tower through separation column;
11) by step 10) in separation column tower at the bottom of heavy oil loop back Hydrocracking unit continue reaction, or loop back step 1) in together with heavy oil, solvent extraction oil as heavy oil be used for coal oil mixture prepare.
2. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 1) in, described coal dust is at least one in mud coal, bituminous coal, brown coal, and preferred high-volatile bituminous coal and old brown coal, described high volatile refers to volatile matter V
daf> 35%, the particle diameter of described coal dust preferably less than 150 μm.
3. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 1) in, described catalyzer adopts at least one in red mud, Natural pyrite, metallurgical flying dust, high ferro coal gangue, Ni-W base hydrocracking catalyst, Ni-Mo base oil dissolubility hydrogenation catalyst, ultra-fine high dispersive ferrum-based catalyst;
Described heavy oil can adopt at least one in long residuum, vacuum residuum, catalytically cracked oil, Aromatics Extractive Project oil, visbreaker tar, coking heavy oil, coal tar, converting plastic waste to oil, waste rubber tire oil; The boiling range of described heavy oil can be 200 ~ 550 DEG C, preferably 360 ~ 500 DEG C;
In described coal oil mixture 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).
4. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 2) in, the reactor that described coal and oil refine unit altogether adopts suspended-bed reactor or paste state bed reactor; Described coal and oil refine altogether unit temperature of reaction 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 is 800 ~ 1200.
5. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 5) in, the stripping section of described vacuum still does not establish column plate; Described vacuum still, thick oil can be 360 ~ 520 DEG C, preferably 420 ~ 500 DEG C with at the bottom of vacuum distillation tower tower containing the cutting temperature of solid Residual oil.
6. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 6) in, describedly carry out solvent extraction at the bottom of vacuum distillation tower tower containing solid Residual oil, its extraction solvent is petroleum naphtha or crude benzol, preferred steps 4) in light oil.
7. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 7) in, the oil circulation time step 1 of described solvent extraction) in be used for the preparation of coal oil mixture as heavy oil.
8. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 8) in, described solid residue is directly sold, for boiler combustion, power plants generating electricity as semicoke; Or enter Hydrogen Unit, produce hydrogen, for step 2 through gasification, water-gas change, gas sweetening) and step 8) in.
9. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 9) in, described hydro-upgrading unit adopts that fixed bed hydrogenation is refining, hydroeracking unit coupling, or only adopts fixed bed hydrogenation refining plant.
10. a kind ofly as claimed in claim 1 refine the method for producing oil product altogether for coal and oil, it is characterized in that in step 10) in, heavy oil at the bottom of described separation column tower loop back Hydrocracking unit continue reaction, or loop back step 1) in together with heavy oil, solvent extraction oil as heavy oil be used for coal oil mixture prepare.
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