CN104087339A - Hydrogenation co-processing method for mixed oil, coal and coal tar - Google Patents
Hydrogenation co-processing method for mixed oil, coal and coal tar Download PDFInfo
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Abstract
The invention provides a hydrogenation co-processing method for mixed oil, coal and coal tar. The method realizes organic combination of oil-coal co-processing technology and coal tar hydrogenation technology, effectively overcomes the problem of poor intermiscibility of oil-coal slurry prepared from coal and mixed oil in oil-coal co-processing in the prior art, improves the intermiscibility of oil-coal slurry prepared from coal and oil in oil-coal co-processing, enables the yield of gasoline and diesel oil produced after hydrogenation of coal tar to be increased by 10 to 30% and enhances the quality of product oil, thereby greatly improving economic benefits of a coal-oil co-processing factory.
Description
Technical field
The present invention relates to a kind of assorted oil, coal, coal tar hydrogenating smelting method altogether, belong to the technical field that oily coal hydrogenation refines altogether.
Background technology
In recent years, world petroleum resource worsening shortages, and the heaviness of petroleum resources and in poor quality problem more and more obvious, but along with economic rapid growth, society the demand of petroleum products is grown with each passing day.Heavy Oil Processing Technology not only can effectively be utilized petroleum resources, and can improve the economic benefit of refining of petroleum enterprise.Meanwhile, China is the country of a rich coal resources, and how reserves are abundant and cheap coal resources change into the important development direction that liquid product becomes coal resources clean utilization.
Kerosene (hydrogenation) refining technology has altogether been one of obtained major progress of coal direct liquefaction research field since the eighties.Its principal feature is to replace classical solvent oil by heavy oils such as black petroleum products, residual oil, and once by hydrogenation reaction device, hydrocracking simultaneously becomes light, middle matter oil and a small amount of hydrocarbon gas to coal with residual oil.The advantage that kerosene refines technology is altogether the circulating solvent that originally needs to add in coal slurry preparation, with a part of residual oil, replaces, and makes the internal circulating load of oil product less, and it is large that treatment capacity can become; Synergistic effect between the aromatics of coal and the paraffin class of heavy oil, generates oil and does not need upgrading hydrogenation technique while making kerosene co-processing, be more easily processed into the oil products such as qualified gasoline, diesel oil; Micro-metals in residual oil, such as nickel, iron etc., both can be in when reaction as catalyzer, in the time of also may be after reaction, be adsorbed on unreacted coal, was conducive to remove, and was conducive to improve the quality of oil product; Because the protium in residual oil is higher than the protium content of coal, when reaction, hydrogen consumption reduces, and hydrogen utilization ratio (consuming the resulting product oil of every kg hydrogen kg number) increases substantially, and favourable minimizing energy consumption, reduces the investment of equipment.The same with the direct liquefaction of coal, the research that the direct liquefaction of coal and kerosene refine technology is altogether a chief component in the research of clean coal technology project.
The hydrocarbon polymer research company (HRI) of the U.S. kerosene co-processing technique that just began one's study in 1974, under USDOE and Institute of Electric Power, Russia peace great strategy synthol company, the graduate subsidy of Transport Model for Alberta, develop two sections of kerosene co-processing techniques cooperatively the end of the year 1985.German gelatin liquefaction company in 1987 and Mitsui Ship-building Company have also participated in the technological development of HRI, and experimental size has reached the scale of t/d level.Hydrogen-the oil process of the HRI kerosene assorted oily catalytic cracking that sweetening process Shi hydrocarbon polymer research company developed in the past altogether, on hydrogen-coal method of DCL/Direct coal liquefaction and catalysis two-stage liquification technique basis, the DCL/Direct coal liquefaction novel method that process packaged unit and process exploitation apparatus experimental study for many years develop again.The kerosene of HRI altogether sweetening process is two-stage catalytic hydrogenation cracking technology, is characterized in adopting unique ebullated bed catalyticreactor, high reactivity CoMo/Al
2o
3and NiMo/Al
2o
3carried catalyst, and in the mode adding continuously and discharge, keep the activity of catalyst in reactor.Kerosene coal slurry is once by reactor, and when high coal concentration, with a small amount of mink cell focus circulation, its recycle ratio is only also 0.5.
Germany coal liquefaction company transforms the Pyrosol kerosene co-processing technique forming on Pyrosol technique DCL/Direct coal liquefaction basis.First this technique carry out fractionation to mink cell focus, reclaims the mink cell focus in raw material.The hydrotreatment under 450-475 ℃, 20.0Mp of remaining abandoning property of dregs of fat utilization Fe-series catalyst, the oil after hydrogenation first reclaims and heats up in a steamer oil content through fractionation, and the fractionation dregs of fat are as the solvent of kerosene co-processing.Coal is made into coal slurry with higher ratio and solvent, and the concentration of coal surpasses 30%.Entering second segment reactor, temperature of reaction is 450-475 ℃, hydrogen pressure 20.0Mp.Second segment reaction product is gone fractionation again, and the residue that steams distillate goes hydrogenation coking again, makes it be converted into oil and coke, and tar returns to again second segment reactor.
The kerosene co-processing technique of Canadian Minerals energy centre (CANMET) exploitation is to grow up on the basis of oil hydrocracking process.To utilize to be loaded with FeSO at first
4coal as residual hydrocracking catalyzer, the add-on of coal only has 5% of residual oil, seldom coking of residual oil under exacting terms relatively.Add afterwards 30% coal, made the hydrocracking simultaneously of residual oil and coal, received good effect.
In above-mentioned technology, in slurry state bed hydroprocessing reaction member, coal, the coal oil mixture of assorted oil in kerosene refines altogether usually, due to the problem of the coal of aromatics and the assorted oily intermiscibility existing of straight chain hydrocarbon, are easy to cause the sedimentation of coal, the obstruction of pipeline, refines altogether all in development phase or demonstration program kerosene; Solid-liquid separation has all been taked air distillation and underpressure distillation, and VACUUM TOWER BOTTOM Residual oil is usually as fuel combustion.In Residual oil after kerosene refines altogether, the massfraction of carbon is in 90% left and right, the content of asphaltene class material is 15% left and right, there is the asphaltene molecule that aromaticity is high, also the asphaltene molecule that has straight chain, there is easy generation polymerization or crosslinked feature, particularly bitumen is after carrying out a hydrogenation reaction, and the micromolecular fracture on pitch and the reduction of nitrogen and sulphur content are particularly suitable as the raw material of phase in the middle of needle coke, carbon fibre.
Summary of the invention
For this reason, technical problem to be solved by this invention is that coal, the coal oil mixture of assorted oil in kerosene refines are altogether usually due to the problem of the intermiscibility of the coal of aromatics and the assorted oil existence of straight chain hydrocarbon, be easy to cause the sedimentation of coal, the obstruction of pipeline, kerosene is refined all altogether in development phase or demonstration program, thereby propose a kind of coal and the good assorted oil of assorted oil phase dissolubility, coal, coal tar hydrogenating smelting method altogether.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
The method that assorted oil, coal and coal tar hydrogenating refine altogether, comprises the steps:
(1) coal tar raw material is distilled to processing, the heavy distillate that the be divided into≤light ends of 320 ℃ oil and > are 320 ℃;
(2) step (1) distillation is processed to the described heavy distillate obtaining and mixed with coal, assorted oil, add catalyzer and promotor, make coal oil mixture; Wherein, described heavy distillate, coal, assorted oily mass ratio are 1-4:1-3:1-4; Described assorted oil is a kind of in petroleum residual oil, high viscous oil or both mixtures;
(3) coal oil mixture step (2) being obtained is sent into hydrogenator after preheating, carries out hydrogenation reaction;
(4) adopt high-temperature high-pressure separator to carry out gas-liquid separation on the resultant of step (3) hydrogenation reaction;
(5) what will obtain through step (4) gas-liquid separation carries out underpressure distillation containing solid heavy still bottoms, obtains decompression oil;
(6) described decompression oil step (5) being obtained and step (1) obtain≤the light ends oil of 320 ℃ after preheating, send into successively the first fixed-bed reactor together with the gaseous phase materials obtaining with step (4) gas-liquid separation and the second fixed-bed reactor carry out hydrofining;
(7) product after hydrofining step (6) being obtained obtains gasoline, diesel oil and 350 ℃ of-500 ℃ of mink cell focuses through fractionation, wherein, using the mink cell focus of described 350 ℃-500 ℃ as circulation hydrogen supply dissolvent, be recycled in step (2), send into hydrogenator with described heavy distillate, coal together with assorted oil and carry out hydrogenation reaction, mink cell focus and the described heavy distillate mass ratio of described 350 ℃-500 ℃ are 1:3-4:1.
Described hydrogenator in step (3) is in paste state bed reactor.
Hydrogenation catalyst in step (2) is one or more in Fe series catalysts, Mo series catalysts, Ni series catalysts, and the addition of described hydrogenation catalyst is counted the 1-3wt% of described heavy distillate with active metal.
The temperature of carrying out hydrogenation reaction in step (3) is 420-455 ℃, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-1500NL/kg.
Described Fe series catalysts is γ-FeOOH.
Described hydrogenation catalyst is also added with sulphur or organic sulfide, and in the S in described sulphur or organic sulfide and described hydrogenation catalyst, the mol ratio of active metal Fe is 1:1-3:1.
Described the first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, in described bubbling bed reactor, be provided with double-layer separate fabric swatch, wherein on lower floor's grid distributor, be provided with guard catalyst, on the grid distributor of upper strata, be provided with hydrogenation catalyst, in the bottom of described bubbling bed reactor, be provided with reducing valve; Described the second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge.
Described guard catalyst in described the first fixed-bed reactor is that special nickel-molybdenum is guard catalyst, and described hydrogenation catalyst is nickel-molybdenum series catalyst; The temperature of reaction of described the first fixed-bed reactor is 300-380 ℃, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-2500NL/kg; The catalyzer using in described the second fixed-bed reactor is nickel-molybdenum-tungsten series catalysts; The temperature of reaction of described the second fixed-bed reactor is 300-380 ℃, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-2500NL/kg.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) assorted oil of the present invention, coal, coal tar hydrogenating is smelting method altogether, realized oily coal has been total to sweetening process and coal tar hydrogenation process, organically combine, efficiently solve coal in prior art, the problem that the coal of assorted oil in kerosene refines is altogether poor with the intermiscibility of oil preparation coal oil mixture, avoid the sedimentation of coal easily to cause the obstruction of pipeline, the inventive method improve kerosene refine altogether in the intermiscibility of coal and oil preparation coal oil mixture, can make to generate vapour after coal tar hydrogenating, diesel yield improves 10%-30%, and improved the oil quality of product oil, thereby greatly improved the economic benefit of kerosene Gong Lian factory.
(2) assorted oil of the present invention, coal, coal tar hydrogenating are total to smelting method, in described online hydrogenation technique, adopt different fixed-bed reactor: hydrogenation protecting reactor and upgrading hydrogenator, wherein said hydrogenation protecting reactor, i.e. the first fixed-bed reactor, adopt the fixed-bed reactor of bubbling bed form, lower charging, top discharge, reactor lower part is empty tubbiness, on grid distributor, the first layer is guard catalyst, the second layer is hydrogenation catalyst, and reactor bottom has the sedimental reducing valve of discharge; Described upgrading hydrogenator, i.e. the second fixed-bed reactor, adopt the fixed-bed reactor of trickle bed form, upper feeding, bottom discharge), effectively prevent poisoning of catalyst, extend the life-span of hydrogenator catalyzer.
Embodiment
Embodiment 1
The present embodiment provides a kind of assorted oil, coal, coal tar hydrogenating smelting method altogether, comprises the steps:
(1) coal tar raw material is distilled to processing, the heavy distillate that the be divided into≤light ends of 320 ℃ oil and > are 320 ℃;
(2) step (1) distillation is processed to the described heavy distillate obtaining and be mixed into coal oil mixture with coal, normal pressure petroleum residual oil, γ-FeOOH with sulfur catalyst, the addition of wherein said γ-FeOOH is counted the 1wt% of described heavy distillate with Fe, in the S in described sulphur and γ-FeOOH, the mol ratio of Fe is 1:3; After described coal oil mixture is mixed with hydrogen, send into slurry state bed hydroprocessing reactor, at 455 ℃, 19MPa, under the condition that vapour-liquid ratio is 1500NL/kg, carry out hydrogenation reaction; Wherein, the mass ratio of described heavy distillate, coal, normal pressure petroleum residual oil is 2:1:3;
(3) material that the coal oil mixture of being prepared by step (2) is pumped into after the preheating of coal slurry preheater by high-pressure coal slurry is sent into paste state bed reactor, carries out hydrogenation reaction.
(4) step (3) is carried out to gas-liquid separation through the material reacting at high-temperature high-pressure separator, wherein the temperature of high-temperature high-pressure separator is 400 ℃;
(5) what the high-temperature high-pressure separator separation of step (4) is obtained carries out underpressure distillation containing solid heavy still bottoms;
(6) decompression oil step (5) being obtained and from (1), obtain≤lightweight oil of 320 ℃ delivers to the preheating of oil product preheater by injection pump, the High Temperature Gas phase materials obtaining with step (4) gas-liquid separation converges, then send into successively together oil product upgrading hydrogenation protecting reactor (the first fixed-bed reactor, adopt bubbling bed form in fixed bed, lower charging, top discharge, the sedimental reducing valve of discharge is arranged at bottom) and oil product upgrading hydrogenator (the second fixed-bed reactor, adopt trickle bed form in fixed bed, upper feeding, bottom discharge) carrying out hydrofining obtains material;
Wherein said the first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, in described bubbling bed reactor, be provided with double-layer separate fabric swatch, on lower floor's grid distributor, be provided with guard catalyst, guard catalyst described in the present embodiment is Ni-Mo series catalysts; On the grid distributor of upper strata, be provided with hydrogenation catalyst, the hydrogenation catalyst on the grid distributor of upper strata described in the present embodiment is Ni-Mo series catalysts; Bottom at described bubbling bed reactor is provided with reducing valve; The temperature of reaction of described bubbling bed reactor is 300 ℃, and pressure is 15Mpa, and vapour-liquid ratio is 500NL/kg; Described the second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge, are provided with particulate solid beds in described trickle-bed reactor, and the particulate solid catalyzer described in the present embodiment is Ni-Mo-W series catalysts; The temperature of reaction of described trickle-bed reactor is 300 ℃, and pressure is 15Mpa, and vapour-liquid ratio is 500NL/kg;
(7) product after hydrofining step (6) being obtained obtains gasoline, diesel oil and 350 ℃ of-500 ℃ of mink cell focuses through fractionation, wherein, using the mink cell focus of described 350 ℃-500 ℃ as circulation hydrogen supply dissolvent, be recycled in step (2), send into hydrogenator with described heavy distillate, coal together with assorted oil and carry out hydrogenation reaction, mink cell focus and the described heavy distillate mass ratio of described 350 ℃-500 ℃ are 1:1.
Embodiment 2
The present embodiment provides a kind of oil, coal, coal tar hydrogenating smelting method altogether, comprises the steps:
(1) coal tar raw material is distilled to processing, the heavy distillate that the be divided into≤light ends of 320 ℃ oil and > are 320 ℃;
(2) step (1) distillation is processed to the described heavy distillate obtaining and be mixed into coal oil mixture with coal, high viscous oil, γ-FeOOH, Ni series catalysts with sulfur catalyst, the addition of wherein said γ-FeOOH is counted the 1wt% of described heavy distillate with Fe, in S in described sulphur and γ-FeOOH, the mol ratio of Fe is 1:1, described Ni series catalysts be take nickelous sulfide as main and nickeliferous quality be Fe add quality 3%; Wherein, the mass ratio of described heavy distillate, coal, high viscous oil is 1:3:1;
(3) material being pumped into after the preheating of coal slurry preheater by high-pressure coal slurry after the coal oil mixture of being prepared by step (2) mixes with hydrogen is sent into paste state bed reactor, at 420 ℃, 15MPa, carries out hydrogenation reaction under the condition that vapour-liquid ratio is 500NL/kg;
(4) step (3) is carried out to gas-liquid separation through the material reacting at high-temperature high-pressure separator, wherein the temperature of high-temperature high-pressure separator is 400 ℃;
(5) what the high-temperature high-pressure separator separation of step (4) is obtained carries out underpressure distillation containing solid heavy still bottoms;
(6) by the decompression oil of step (5) and from (1), obtain≤320 ℃ of lightweight oils pass through injection pump, deliver to after the preheating of oil product preheater, with step (4) in gas-liquid separation obtain High Temperature Gas phase materials converge, then send into successively together oil product upgrading hydrogenation protecting reactor (the first fixed-bed reactor, adopt bubbling bed form in fixed bed, lower charging, top discharge, the sedimental reducing valve of discharge is arranged at bottom) and oil product upgrading hydrogenator (the second fixed-bed reactor, adopt trickle bed form in fixed bed, upper feeding, bottom discharge) carrying out hydrofining obtains material;
Wherein said the first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, in described bubbling bed reactor, be provided with double-layer separate fabric swatch, on lower floor's grid distributor, be provided with guard catalyst, guard catalyst described in the present embodiment is Ni-Mo series catalysts; On the grid distributor of upper strata, be provided with hydrogenation catalyst, the hydrogenation catalyst on the grid distributor of upper strata described in the present embodiment is Ni-Mo series catalysts; Bottom at described bubbling bed reactor is provided with reducing valve; The temperature of reaction of described bubbling bed reactor is 380 ℃, and pressure is 25Mpa, and vapour-liquid ratio is 2500NL/kg; Described the second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge, are provided with particulate solid beds in described trickle-bed reactor, and the particulate solid catalyzer described in the present embodiment is Ni-Mo-W series catalysts; The temperature of reaction of described trickle-bed reactor is 380 ℃, and pressure is 25Mpa, and vapour-liquid ratio is 2500NL/kg;
(7) product after hydrofining step (6) being obtained obtains gasoline, diesel oil and 350 ℃ of-500 ℃ of mink cell focuses through fractionation, wherein, using the mink cell focus of described 350 ℃-500 ℃ as circulation hydrogen supply dissolvent, be recycled in step (2), send into hydrogenator with described heavy distillate, coal together with assorted oil and carry out hydrogenation reaction, mink cell focus and the described heavy distillate mass ratio of described 350 ℃-500 ℃ are 1:3.
Embodiment 3
The present embodiment provides a kind of oil, coal, coal tar hydrogenating smelting method altogether, comprises the steps:
(1) coal tar raw material is distilled to processing, the heavy distillate that the be divided into≤light ends of 320 ℃ oil and > are 320 ℃;
(2) step (1) distillation is processed to the described heavy distillate obtaining and be mixed into coal oil mixture with coal, normal pressure petroleum residual oil, γ-FeOOH, Mo series catalysts with sulfur catalyst, the addition of wherein said γ-FeOOH is counted the 3wt% of described heavy distillate with Fe, in S in described sulphur and γ-FeOOH, the mol ratio of Fe is 1:3, and described Mo series catalysts is to take ammonium molybdate as master and is 1% of Fe interpolation quality containing molybdenum quality; Wherein, the mass ratio of described heavy distillate, coal, normal pressure petroleum residual oil is 4:1:4;
(3) after being pumped into the preheating of coal slurry preheater by high-pressure coal slurry after the described coal oil mixture of being prepared by step (2) mixes with hydrogen, send into again paste state bed reactor, at 455 ℃, 25MPa, under the condition that vapour-liquid ratio is 1500NL/kg, carry out hydrogenation reaction;
(4) step (3) is carried out to gas-liquid separation through the material reacting at high-temperature high-pressure separator, wherein the temperature of high-temperature high-pressure separator is 400 ℃;
(5) what the high-temperature high-pressure separator separation of step (4) is obtained carries out underpressure distillation containing solid heavy still bottoms;
(6) by the decompression oil of step (5) and from step (1), obtain≤lightweight oil of 320 ℃ delivers to the preheating of oil product preheater by injection pump, the High Temperature Gas phase materials obtaining with step (4) gas-liquid separation converges, then send into successively together oil product upgrading hydrogenation protecting reactor (the first fixed-bed reactor, adopt bubbling bed form in fixed bed, lower charging, top discharge, the sedimental reducing valve of discharge is arranged at bottom) and oil product upgrading hydrogenator (the second fixed-bed reactor, adopt trickle bed form in fixed bed, upper feeding, bottom discharge) carrying out hydrofining obtains material;
Wherein said the first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, in described bubbling bed reactor, be provided with double-layer separate fabric swatch, on lower floor's grid distributor, be provided with guard catalyst, guard catalyst described in the present embodiment is Ni-Mo series catalysts; On the grid distributor of upper strata, be provided with hydrogenation catalyst, the hydrogenation catalyst on the grid distributor of upper strata described in the present embodiment is Ni-Mo series catalysts; Bottom at described bubbling bed reactor is provided with reducing valve; The temperature of reaction of described bubbling bed reactor is 350 ℃, and pressure is 20Mpa, and vapour-liquid ratio is 2000NL/kg; Described the second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge, are provided with particulate solid beds in described trickle-bed reactor, and the particulate solid catalyzer described in the present embodiment is Ni-Mo-W series catalysts; The temperature of reaction of described trickle-bed reactor is 350 ℃, and pressure is 20Mpa, and vapour-liquid ratio is 2000NL/kg;
(7) product after hydrofining step (6) being obtained through fractionation obtain gasoline, diesel oil and and 350 ℃ of-500 ℃ of mink cell focuses, wherein, using the mink cell focus of described 350 ℃-500 ℃ as circulation hydrogen supply dissolvent, be recycled in step (2), send into hydrogenator with described heavy distillate, coal together with assorted oil and carry out hydrogenation reaction, mink cell focus and the described heavy distillate mass ratio of described 350 ℃-500 ℃ are 4:1.
Experimental example
In order to prove the technique effect of coal tar hydrogenation process of the present invention, this experimental example is measured the productive rate in the hydrogenation technique described in above-described embodiment 1, embodiment 2 and embodiment 3.Wherein:
Product yield %=step (7) fractionation obtains≤gasoline, diesel oil/(coal+coal tar+assorted oil) * 100% of 350 ℃;
The gas fraction generating in the whole hydrogenation process of gas productive rate %=/(coal+coal tar+assorted oil) * 100%;
The moisture generating in the whole hydrogenation process of aquatic products rate %=(coal+coal tar+assorted oil)/* 100%;
The hydrogen expending in the whole hydrogenation process of hydrogen consumption %=/(coal+coal tar+assorted oil) * 100%;
Above-mentioned productive rate is mass percent, and coal, coal tar, assorted oily raw material are usingd moisture-and-ash-free basis as analysis foundation.
Measurement result is as shown in the table:
| ? | Product yield % | Gas productive rate % | Aquatic products rate % | Hydrogen consumption % |
| Embodiment 1 | 86.15 | 4.56 | 2.34 | 3.15 |
| Embodiment 2 | 82.10 | 3.28 | 1.79 | 2.00 |
| Embodiment 3 | 90.75 | 5.01 | 2.25 | 3.79 |
It should be noted that, in coal tar hydrogenation process described in above-described embodiment, the hydrogenation catalyst using in step (2), except FeO, the γ-FeOOH of above-mentioned use, moly-sulfide, can also be Fe series hydrocatalyst in prior art, one or more in Mo series hydrocatalyst, Ni series hydrocatalyst.Wherein Fe series hydrocatalyst can be Fe
3o
4, pyrite, rhombohedral iron ore, kakoxene, limonite etc.Mo series hydrocatalyst can be moly-sulfide, ammonium molybdate etc., and Ni series hydrocatalyst can be nickelous sulfide etc.
Assorted oil of the present invention, coal, coal tar hydrogenating is smelting method altogether, realized oily coal has been total to sweetening process and coal tar hydrogenation process, organically combine, efficiently solve coal in prior art, the problem that the coal of assorted oil in kerosene refines is altogether poor with the intermiscibility of oil preparation coal oil mixture, avoid the sedimentation of coal easily to cause the obstruction of pipeline, the inventive method improve kerosene refine altogether in the intermiscibility of coal and oil preparation coal oil mixture, can make to generate vapour after coal tar hydrogenating, diesel yield improves 10%-30%, and improved the oil quality of product oil, thereby greatly improved the economic benefit of kerosene Gong Lian factory.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments.And the apparent variation of being extended out thus or change are still among the protection domain in the invention.
Claims (8)
1. the method that assorted oil, coal and coal tar hydrogenating refine altogether, comprises the steps:
(1) coal tar raw material is distilled to processing, the heavy distillate that the be divided into≤light ends of 320 ℃ oil and > are 320 ℃;
(2) step (1) distillation is processed to the described heavy distillate obtaining and mixed with coal, assorted oil, add hydrogenation catalyst, make coal oil mixture; Wherein, described heavy distillate, coal, assorted oily mass ratio are 1-4:1-3:1-4, and described assorted oil is a kind of in petroleum residual oil, high viscous oil or both mixtures;
(3) coal oil mixture step (2) being obtained is sent into hydrogenator after preheating, carries out hydrogenation reaction;
(4) adopt high-temperature high-pressure separator to carry out gas-liquid separation on the resultant of step (3) hydrogenation reaction;
(5) what will obtain through step (4) gas-liquid separation carries out underpressure distillation containing solid heavy still bottoms, obtains decompression oil;
(6) described decompression oil step (5) being obtained and step (1) obtain≤the light ends oil of 320 ℃ after preheating, send into successively the first fixed-bed reactor together with the gaseous phase materials obtaining with step (4) gas-liquid separation and the second fixed-bed reactor carry out hydrofining;
(7) product after hydrofining step (6) being obtained obtains gasoline, diesel oil and 350 ℃ of-500 ℃ of mink cell focuses through fractionation, wherein, using the mink cell focus of described 350 ℃-500 ℃ as circulation hydrogen supply dissolvent, be recycled in step (2), send into hydrogenator with described heavy distillate, coal together with assorted oil and carry out hydrogenation reaction, mink cell focus and the described heavy distillate mass ratio of described 350 ℃-500 ℃ are 1:3-4:1.
2. the method that assorted oil according to claim 1, coal and coal tar hydrogenating refine altogether, is characterized in that, the described hydrogenator in step (3) is in paste state bed reactor.
3. the method that assorted oil according to claim 1 and 2, coal and coal tar hydrogenating refine altogether, it is characterized in that, hydrogenation catalyst in step (2) is one or more in Fe series catalysts, Mo series catalysts, Ni series catalysts, and the addition of described hydrogenation catalyst is counted the 1-3wt% of described heavy distillate with active metal.
4. the method for refining altogether according to claim 1-3 arbitrary described assorted oil, coal and coal tar hydrogenating, is characterized in that, the temperature of carrying out hydrogenation reaction in step (3) is 420-455 ℃, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-1500NL/kg.
5. the method that assorted oil according to claim 3, coal and coal tar hydrogenating refine altogether, is characterized in that, described Fe series catalysts is γ-FeOOH.
6. the method for refining altogether according to claim 1-5 arbitrary described assorted oil, coal and coal tar hydrogenating, it is characterized in that, described hydrogenation catalyst is also added with sulphur or organic sulfide, and in the S in described sulphur or organic sulfide and described hydrogenation catalyst, the mol ratio of active metal Fe is 1:1-1:3.
7. the method for refining altogether according to claim 1-6 arbitrary described assorted oil, coal and coal tar hydrogenating, it is characterized in that, described the first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, in described bubbling bed reactor, be provided with double-layer separate fabric swatch, wherein on lower floor's grid distributor, be provided with guard catalyst, on the grid distributor of upper strata, be provided with hydrogenation catalyst, in the bottom of described bubbling bed reactor, be provided with reducing valve; Described the second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge.
8. the method for refining altogether according to claim 1-7 arbitrary described assorted oil, coal and coal tar hydrogenating, is characterized in that, the described guard catalyst in described the first fixed-bed reactor is nickel-molybdenum series catalyst, and described hydrogenation catalyst is nickel-molybdenum series catalyst; The temperature of reaction of described the first fixed-bed reactor is 300-380 ℃, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-2500NL/kg; The catalyzer using in described the second fixed-bed reactor is nickel-molybdenum-tungsten series catalysts; The temperature of reaction of described the second fixed-bed reactor is 300-380 ℃, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-2500NL/kg.
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| CN104785272A (en) * | 2015-04-20 | 2015-07-22 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| CN106433775A (en) * | 2016-12-20 | 2017-02-22 | 煤炭科学技术研究院有限公司 | Coal and oil coprocessing method and device |
| CN106693975A (en) * | 2016-11-24 | 2017-05-24 | 中国石油大学(华东) | Oil-soluble Fe-Ni bimetallic catalyst, and preparation method and application of bimetallic catalyst |
| CN106732672A (en) * | 2017-02-23 | 2017-05-31 | 中国石油大学(华东) | It is a kind of to load catalyst with base of molybdenum for the coal that kerosene floating bed hydrogenation is refined altogether |
| CN109929585A (en) * | 2017-12-19 | 2019-06-25 | 何巨堂 | Condense the hydrocarbon material process for selective hydrogenation of middle matter hydrocarbon in the gas phase of reuse reaction product |
| WO2020186635A1 (en) * | 2019-03-15 | 2020-09-24 | 南京延长反应技术研究院有限公司 | Enhanced emulsion reaction system on oil-coal co-hydrogenation micro-interface |
| WO2020186636A1 (en) * | 2019-03-15 | 2020-09-24 | 南京延长反应技术研究院有限公司 | Micro-interface emulsification bed enhanced reaction system for hydrogenation of coal tar |
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| WO2017109014A1 (en) * | 2015-12-22 | 2017-06-29 | Rhodia Operations | Positive active material for rechargeable lithium-sulfur battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104785272A (en) * | 2015-04-20 | 2015-07-22 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| CN106693975A (en) * | 2016-11-24 | 2017-05-24 | 中国石油大学(华东) | Oil-soluble Fe-Ni bimetallic catalyst, and preparation method and application of bimetallic catalyst |
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| CN109929585A (en) * | 2017-12-19 | 2019-06-25 | 何巨堂 | Condense the hydrocarbon material process for selective hydrogenation of middle matter hydrocarbon in the gas phase of reuse reaction product |
| WO2020186635A1 (en) * | 2019-03-15 | 2020-09-24 | 南京延长反应技术研究院有限公司 | Enhanced emulsion reaction system on oil-coal co-hydrogenation micro-interface |
| WO2020186636A1 (en) * | 2019-03-15 | 2020-09-24 | 南京延长反应技术研究院有限公司 | Micro-interface emulsification bed enhanced reaction system for hydrogenation of coal tar |
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