CN104087339B - A kind of method that assorted oil, coal and coal tar hydrogenating refine altogether - Google Patents
A kind of method that assorted oil, coal and coal tar hydrogenating refine altogether Download PDFInfo
- Publication number
- CN104087339B CN104087339B CN201410276047.0A CN201410276047A CN104087339B CN 104087339 B CN104087339 B CN 104087339B CN 201410276047 A CN201410276047 A CN 201410276047A CN 104087339 B CN104087339 B CN 104087339B
- Authority
- CN
- China
- Prior art keywords
- coal
- oil
- bed reactor
- assorted
- altogether
- 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
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a kind of assorted oil, coal and coal tar hydrogenating smelting method altogether, achieve and oily coal is total to sweetening process and coal tar hydrogenation process, organically combines, efficiently solve coal in prior art, the coal of assorted oil in kerosene refines altogether and the oily problem preparing the intermiscibility difference of coal oil mixture, the inventive method raising kerosene refine altogether in coal with oil prepare the intermiscibility of coal oil mixture while, generate vapour after can making coal tar hydrogenating, diesel yield improves 10%-30%, and improve the oil quality of product oil, thus greatly improve the economic benefit of kerosene Gong Lian 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 are more and more obvious, but along with the quick growth of economy, society grows with each passing day to the demand of petroleum products.Heavy Oil Processing Technology not only effectively can utilize petroleum resources, and can improve the economic benefit of oil-processing enterprises.Meanwhile, China is the country of a rich coal resources, how rich reserves and cheap coal resources is changed into the important development direction that liquid product becomes coal resources clean utilization.
Kerosene (hydrogenation) has refined one of major progress since technology is the eighties acquired by coal direct liquefaction research field altogether.Its principal feature replaces classical solvent oil by the heavy such as black petroleum products, residual oil oils, and once by hydrogenation reaction device, coal becomes light, middle matter oil and a small amount of hydrocarbon gas with residual oil hydrocracking simultaneously.The advantage that kerosene refines technology is altogether the circulating solvent originally needing to add in coal slurry preparation, and replace with a part of residual oil, make the internal circulating load of oil product less, treatment capacity can become large; Synergistic effect between the aromatics of coal and the paraffin class of heavy oil, makes to generate oil during coal-residual coprocessing and does not need upgrading hydrogenation technique, 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 when reacting as catalyzer, also may after the reaction time be adsorbed on unreacted coal, be conducive to removing, be conducive to improving the quality of oil product; Because the protium in residual oil is higher than the protium content of coal, when reacting, hydrogen consumption reduces, and hydrogen utilization ratio (consuming the product oil kg number that every kg hydrogen obtains) increases substantially, 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. just began one's study in 1974 coal-residual coprocessing technique, the end of the year 1985, under USDOE and Institute of Electric Power, peace great strategy synthol company of Russia, the graduate subsidy of Transport Model for Alberta, developed two sections of coal-residual coprocessing techniques cooperatively.German gelatin liquefaction companies in 1987 and Mitsui Ship-building Company also take part in the technological development of HRI, and experimental size reaches the scale of t/d level.HRI kerosene altogether sweetening process is the hydrogen-oil process of the assorted oily catalytic cracking of developing before hydrocarbon polymer research company, on the hydrogen-coal method of DCL/Direct coal liquefaction and catalysis two-stage liquification Process ba-sis, again through the DCL/Direct coal liquefaction novel method of packaged unit and process exploitation apparatus experimental study for many years development.It is two-stage catalytic hydrogenation cracking technology that the kerosene of HRI is total to sweetening process, is characterized in adopting unique ebullated bed catalyticreactor, high reactivity CoMo/Al
2o
3and NiMo/Al
2o
3carried catalyst, and the activity keeping catalyst in reactor in the mode added continuously and discharge.Kerosene coal slurry is once by reactor, and when high coal concentration, circulate with a small amount of mink cell focus, its recycle ratio is also only 0.5.
The Pyrosol coal-residual coprocessing technique that coal liquefaction company of Germany transforms 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 remaining dregs of fat utilize abandoning property Fe-series catalyst 450-475 DEG C, hydrotreatment under 20.0Mp, and the oil after hydrogenation first reclaims through fractionation and heats up in a steamer oil content, and the fractionation dregs of fat are as the solvent of coal-residual coprocessing.Coal is made into coal slurry with higher ratio and solvent, and the concentration of coal is more than 30%.Entering second segment reactor, temperature of reaction is 450-475 DEG C, hydrogen pressure 20.0Mp.Second segment reaction product goes fractionation again, and the residue steaming distillate goes hydrogenation coking again, and make it be converted into oil and coke, tar returns again second segment reactor.
The coal-residual coprocessing technique that Canadian Minerals energy centre (CANMET) is developed grows up on the basis of oil hydrocracking process.Utilize to be loaded with FeSO at first
4coal as residual hydrocracking catalyzer, the add-on of coal only has 5% of residual oil, the little coking of residual oil under relatively exacting terms.Added the coal of 30% afterwards, and made residual oil and coal hydrocracking simultaneously, have received good effect.
In the above-described techniques, in slurry bed system hydrogenation reaction unit, the problem of the intermiscibility that coal, the coal oil mixture of assorted oil in kerosene refines altogether usually exist due to the coal of aromatics and the assorted oil of straight chain hydrocarbon, is easy to the sedimentation causing coal, the blocking of pipeline, makes kerosene refine altogether and is all in development phase or demonstration program; Solid-liquid separation all takes 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 about 90%, the content of asphaltene class material is about 15%, there is the asphaltene molecules that aromaticity is high, also the asphaltene molecules of straight chain is had, have and polymerization or crosslinked feature easily occur, particularly bitumen is after carrying out a hydrogenation reaction, and the micromolecular fracture on pitch and the reduction of nitrogen and sulphur content, be particularly suitable as the raw material of needle coke, carbon fibre mesophase spherule.
Summary of the invention
For this reason, technical problem to be solved by this invention is the problem of the intermiscibility that coal, the coal oil mixture of assorted oil in kerosene refines altogether usually exist due to the coal of aromatics and the assorted oil of straight chain hydrocarbon, be easy to the sedimentation causing coal, the blocking of pipeline, kerosene is refined altogether and is all in development phase or demonstration program, thus 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) distillation process is carried out to coal tar raw material, be divided into≤the heavy distillate of the light ends of 320 DEG C oil and > 320 DEG C;
(2) step (1) distillation is processed the described heavy distillate obtained to mix with coal, assorted oil, add catalyzer and promotor, make coal oil mixture; Wherein, the mass ratio of described heavy distillate, coal, assorted oil is 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 that step (2) obtains is sent into hydrogenator after preheating, carry out hydrogenation reaction;
(4) high-temperature high-pressure separator is adopted 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) obtained and step (1) obtain≤and the light ends of 320 DEG C is oily after preheating, sends into the first fixed-bed reactor successively and the second fixed-bed reactor carry out hydrofining together with the gaseous phase materials that step (4) gas-liquid separation obtains;
(7) product after hydrofining step (6) obtained obtains gasoline, diesel oil and 350 DEG C of-500 DEG C of mink cell focuses through fractionation, wherein, the mink cell focus of described 350 DEG C-500 DEG C is recycled in step (2) as circulation hydrogen supply dissolvent, 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 DEG C-500 DEG C 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 counts the 1-3wt% of described heavy distillate with active metal.
The temperature of carrying out hydrogenation reaction in step (3) is 420-455 DEG C, 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 first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, double-layer separate fabric swatch is provided with in described bubbling bed reactor, wherein lower floor's grid distributor is provided with guard catalyst, upper strata grid distributor is provided with hydrogenation catalyst, the bottom of described bubbling bed reactor is provided with reducing valve; Described second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge.
Described guard catalyst in described first fixed-bed reactor is special nickel-molybdenum system guard catalyst, and described hydrogenation catalyst is nickel-molybdenum series catalyst; The temperature of reaction of described first fixed-bed reactor is 300-380 DEG C, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-2500NL/kg; The catalyzer used in described second fixed-bed reactor is nickel-molybdenum-W-Sn deposits; The temperature of reaction of described second fixed-bed reactor is 300-380 DEG C, 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, achieve oily coal sweetening process and coal tar hydrogenation process altogether, organically combine, efficiently solve coal in prior art, the problem of the intermiscibility difference of coal oil mixture prepared by the coal of assorted oil in kerosene refines altogether and oil, the sedimentation of coal is avoided easily to cause the blocking of pipeline, the inventive method raising kerosene refine altogether in coal with oil prepare the intermiscibility of coal oil mixture while, vapour is generated after can making coal tar hydrogenating, diesel yield improves 10%-30%, and improve the oil quality of product oil, thus greatly improve the economic benefit of kerosene Gong Lian factory.
(2) assorted oil of the present invention, coal, coal tar hydrogenating smelting method altogether, different fixed-bed reactor are adopted: hydrogenation protecting reactor and upgrading hydrogenator in described online hydrogenation technique, 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) distillation process is carried out to coal tar raw material, be divided into≤the heavy distillate of the light ends of 320 DEG C oil and > 320 DEG C;
(2) step (1) distillation is processed the described heavy distillate obtained and become coal oil mixture with coal, normal pressure petroleum residual oil, γ-FeOOH with sulfur catalyst mixture, the addition of wherein said γ-FeOOH counts the 1wt% of described heavy distillate with Fe, in S and the γ-FeOOH in described sulphur, the mol ratio of Fe is 1:3; Send into slurry bed system hydrogenator after being mixed with hydrogen by described coal oil mixture, at 455 DEG C, 19MPa, vapour-liquid ratio is carry out hydrogenation reaction under the condition of 1500NL/kg; Wherein, the mass ratio of described heavy distillate, coal, normal pressure petroleum residual oil is 2:1:3;
(3) coal oil mixture step (2) prepared is pumped into the material after coal slurry preheater preheats by high-pressure coal slurry and sends into paste state bed reactor, carries out hydrogenation reaction.
(4) step (3) is carried out gas-liquid separation through the material of reaction at high-temperature high-pressure separator, wherein the temperature of high-temperature high-pressure separator is 400 DEG C;
(5) high-temperature high-pressure separator of step (4) is separated the solid heavy still bottoms that contains obtained and carries out underpressure distillation;
(6) decompression oil step (5) obtained and from (1) obtain≤after the lightweight oil of 320 DEG C delivers to oil product preheater preheats by injection pump, the High Temperature Gas phase materials obtained with step (4) gas-liquid separation converges, then oil product upgrading hydrogenation protecting reactor (the first fixed-bed reactor are sent into together successively, 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) carry out hydrofining and obtain material,
Wherein said first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, double-layer separate fabric swatch is provided with in described bubbling bed reactor, lower floor's grid distributor is provided with guard catalyst, and guard catalyst described in the present embodiment is Ni-Mo series catalysts; Upper strata grid distributor is provided with hydrogenation catalyst, and the hydrogenation catalyst on the grid distributor of upper strata described in the present embodiment is Ni-Mo series catalysts; The bottom of described bubbling bed reactor is provided with reducing valve; The temperature of reaction of described bubbling bed reactor is 300 DEG C, and pressure is 15Mpa, and vapour-liquid ratio is 500NL/kg; Described second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge, are provided with particulate solid catalyst bed in described trickle-bed reactor, and the particulate solid catalyst described in the present embodiment is Ni-Mo-W series catalysts; The temperature of reaction of described trickle-bed reactor is 300 DEG C, and pressure is 15Mpa, and vapour-liquid ratio is 500NL/kg;
(7) product after hydrofining step (6) obtained obtains gasoline, diesel oil and 350 DEG C of-500 DEG C of mink cell focuses through fractionation, wherein, the mink cell focus of described 350 DEG C-500 DEG C is recycled in step (2) as circulation hydrogen supply dissolvent, 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 DEG C-500 DEG C are 1:1.
Embodiment 2
The present embodiment provides a kind of oil, coal, coal tar hydrogenating smelting method altogether, comprises the steps:
(1) distillation process is carried out to coal tar raw material, be divided into≤the heavy distillate of the light ends of 320 DEG C oil and > 320 DEG C;
(2) step (1) distillation is processed the described heavy distillate obtained and become coal oil mixture with coal, high viscous oil, γ-FeOOH, Ni series catalysts with sulfur catalyst mixture, the addition of wherein said γ-FeOOH counts the 1wt% of described heavy distillate with Fe, in S and γ-FeOOH in described sulphur, the mol ratio of Fe is 1:1, and described Ni series catalysts is based on nickelous sulfide and nickeliferous quality is 3% of Fe interpolation quality; Wherein, the mass ratio of described heavy distillate, coal, high viscous oil is 1:3:1;
(3) be pumped into the material after coal slurry preheater preheats by high-pressure coal slurry after being mixed with hydrogen by coal oil mixture prepared by step (2) and send into paste state bed reactor, at 420 DEG C, 15MPa, vapour-liquid ratio is carry out hydrogenation reaction under the condition of 500NL/kg;
(4) step (3) is carried out gas-liquid separation through the material of reaction at high-temperature high-pressure separator, wherein the temperature of high-temperature high-pressure separator is 400 DEG C;
(5) high-temperature high-pressure separator of step (4) is separated the solid heavy still bottoms that contains obtained and carries out underpressure distillation;
(6) by the decompression of step (5) oil and from (1) obtain≤320 DEG C of lightweight oils pass through injection pump, after delivering to oil product preheater preheats, with step (4) in gas-liquid separation obtain High Temperature Gas phase materials converge, then oil product upgrading hydrogenation protecting reactor (the first fixed-bed reactor are sent into together successively, 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) carry out hydrofining and obtain material,
Wherein said first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, double-layer separate fabric swatch is provided with in described bubbling bed reactor, lower floor's grid distributor is provided with guard catalyst, and guard catalyst described in the present embodiment is Ni-Mo series catalysts; Upper strata grid distributor is provided with hydrogenation catalyst, and the hydrogenation catalyst on the grid distributor of upper strata described in the present embodiment is Ni-Mo series catalysts; The bottom of described bubbling bed reactor is provided with reducing valve; The temperature of reaction of described bubbling bed reactor is 380 DEG C, and pressure is 25Mpa, and vapour-liquid ratio is 2500NL/kg; Described second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge, are provided with particulate solid catalyst bed in described trickle-bed reactor, and the particulate solid catalyst described in the present embodiment is Ni-Mo-W series catalysts; The temperature of reaction of described trickle-bed reactor is 380 DEG C, and pressure is 25Mpa, and vapour-liquid ratio is 2500NL/kg;
(7) product after hydrofining step (6) obtained obtains gasoline, diesel oil and 350 DEG C of-500 DEG C of mink cell focuses through fractionation, wherein, the mink cell focus of described 350 DEG C-500 DEG C is recycled in step (2) as circulation hydrogen supply dissolvent, 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 DEG C-500 DEG C are 1:3.
Embodiment 3
The present embodiment provides a kind of oil, coal, coal tar hydrogenating smelting method altogether, comprises the steps:
(1) distillation process is carried out to coal tar raw material, be divided into≤the heavy distillate of the light ends of 320 DEG C oil and > 320 DEG C;
(2) step (1) distillation is processed the described heavy distillate obtained and become coal oil mixture with coal, normal pressure petroleum residual oil, γ-FeOOH, Mo series catalysts with sulfur catalyst mixture, the addition of wherein said γ-FeOOH counts the 3wt% of described heavy distillate with Fe, in S and γ-FeOOH in described sulphur, the mol ratio of Fe is 1:3, and described Mo series catalysts is based on ammonium molybdate and containing molybdenum quality for Fe adds 1% of quality; Wherein, the mass ratio of described heavy distillate, coal, normal pressure petroleum residual oil is 4:1:4;
(3) paste state bed reactor is sent into again after being pumped into coal slurry preheater preheats by high-pressure coal slurry after being mixed with hydrogen by described coal oil mixture prepared by step (2), at 455 DEG C, 25MPa, vapour-liquid ratio is carry out hydrogenation reaction under the condition of 1500NL/kg;
(4) step (3) is carried out gas-liquid separation through the material of reaction at high-temperature high-pressure separator, wherein the temperature of high-temperature high-pressure separator is 400 DEG C;
(5) high-temperature high-pressure separator of step (4) is separated the solid heavy still bottoms that contains obtained and carries out underpressure distillation;
(6) by the decompression of step (5) oil and from step (1) obtain≤after the lightweight oil of 320 DEG C delivers to oil product preheater preheats by injection pump, the High Temperature Gas phase materials obtained with step (4) gas-liquid separation converges, then oil product upgrading hydrogenation protecting reactor (the first fixed-bed reactor are sent into together successively, 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) carry out hydrofining and obtain material,
Wherein said first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, double-layer separate fabric swatch is provided with in described bubbling bed reactor, lower floor's grid distributor is provided with guard catalyst, and guard catalyst described in the present embodiment is Ni-Mo series catalysts; Upper strata grid distributor is provided with hydrogenation catalyst, and the hydrogenation catalyst on the grid distributor of upper strata described in the present embodiment is Ni-Mo series catalysts; The bottom of described bubbling bed reactor is provided with reducing valve; The temperature of reaction of described bubbling bed reactor is 350 DEG C, and pressure is 20Mpa, and vapour-liquid ratio is 2000NL/kg; Described second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge, are provided with particulate solid catalyst bed in described trickle-bed reactor, and the particulate solid catalyst described in the present embodiment is Ni-Mo-W series catalysts; The temperature of reaction of described trickle-bed reactor is 350 DEG C, and pressure is 20Mpa, and vapour-liquid ratio is 2000NL/kg;
(7) product after hydrofining step (6) obtained through fractionation obtain gasoline, diesel oil and and 350 DEG C of-500 DEG C of mink cell focuses, wherein, the mink cell focus of described 350 DEG C-500 DEG C is recycled in step (2) as circulation hydrogen supply dissolvent, 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 DEG C-500 DEG C are 4:1.
Experimental example
In order to prove the technique effect of coal tar hydrogenation process of the present invention, this experimental example measures 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 DEG C;
The gas fraction generated in the whole hydrogenation process of gas productive rate %=/(coal+coal tar+assorted oil) × 100%;
The moisture (coal+coal tar+assorted oil)/× 100% generated in the whole hydrogenation process of aquatic products rate %=;
The hydrogen expended 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 using 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 used in step (2), except FeO, 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, achieve oily coal sweetening process and coal tar hydrogenation process altogether, organically combine, efficiently solve coal in prior art, the problem of the intermiscibility difference of coal oil mixture prepared by the coal of assorted oil in kerosene refines altogether and oil, the sedimentation of coal is avoided easily to cause the blocking of pipeline, the inventive method raising kerosene refine altogether in coal with oil prepare the intermiscibility of coal oil mixture while, vapour is generated after can making coal tar hydrogenating, diesel yield improves 10%-30%, and improve the oil quality of product oil, thus greatly improve the economic benefit of kerosene Gong Lian factory.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not 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 the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (8)
1. assorted oil, a coal and coal tar hydrogenating method of refining altogether, comprises the steps:
(1) distillation process is carried out to coal tar raw material, be divided into≤the heavy distillate of the light ends of 320 DEG C oil and > 320 DEG C;
(2) step (1) distillation is processed the described heavy distillate obtained to mix with coal, assorted oil, add hydrogenation catalyst, make coal oil mixture; Wherein, the mass ratio of described heavy distillate, coal, assorted oil is 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 that step (2) obtains is sent into hydrogenator after preheating, carry out hydrogenation reaction;
(4) high-temperature high-pressure separator is adopted 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) obtained and step (1) obtain≤and the light ends of 320 DEG C is oily after preheating, sends into the first fixed-bed reactor successively and the second fixed-bed reactor carry out hydrofining together with the gaseous phase materials that step (4) gas-liquid separation obtains;
(7) product after hydrofining step (6) obtained obtains gasoline, diesel oil and 350 DEG C of-500 DEG C of mink cell focuses through fractionation, wherein, the mink cell focus of described 350 DEG C-500 DEG C is recycled in step (2) as circulation hydrogen supply dissolvent, 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 DEG C-500 DEG C are 1:3-4:1.
2. assorted oil according to claim 1, coal and the coal tar hydrogenating method of refining altogether, it is characterized in that, the described hydrogenator in step (3) is paste state bed reactor.
3. assorted oil according to claim 1 and 2, coal and the coal tar hydrogenating method of refining 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 counts the 1-3wt% of described heavy distillate with active metal.
4. assorted oil according to claim 3, coal and the coal tar hydrogenating method of refining altogether, it is characterized in that, the temperature of carrying out hydrogenation reaction in step (3) is 420-455 DEG C, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-1500NL/kg.
5. assorted oil according to claim 3, coal and the coal tar hydrogenating method of refining altogether, it is characterized in that, described Fe series catalysts is γ-FeOOH.
6. assorted oil according to claim 5, coal and the coal tar hydrogenating method of refining altogether, 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 that assorted oil, coal and coal tar hydrogenating according to claim 1 or 2 or 4 or 5 or 6 refine altogether, it is characterized in that, described first fixed-bed reactor are the bubbling bed reactor of lower charging, top discharge, double-layer separate fabric swatch is provided with in described bubbling bed reactor, wherein lower floor's grid distributor is provided with guard catalyst, upper strata grid distributor is provided with hydrogenation catalyst, the bottom of described bubbling bed reactor is provided with reducing valve; Described second fixed-bed reactor are the trickle-bed reactor of upper feeding, bottom discharge.
8. assorted oil according to claim 7, coal and the coal tar hydrogenating method of refining altogether, it is characterized in that, the described guard catalyst in described first fixed-bed reactor is nickel-molybdenum series catalyst, and described hydrogenation catalyst is nickel-molybdenum series catalyst; The temperature of reaction of described first fixed-bed reactor is 300-380 DEG C, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-2500NL/kg; The catalyzer used in described second fixed-bed reactor is nickel-molybdenum-W-Sn deposits; The temperature of reaction of described second fixed-bed reactor is 300-380 DEG C, and pressure is 15-25Mpa, and vapour-liquid ratio is 500-2500NL/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410276047.0A CN104087339B (en) | 2014-06-19 | 2014-06-19 | A kind of method that assorted oil, coal and coal tar hydrogenating refine altogether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410276047.0A CN104087339B (en) | 2014-06-19 | 2014-06-19 | A kind of method that assorted oil, coal and coal tar hydrogenating refine altogether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104087339A CN104087339A (en) | 2014-10-08 |
| CN104087339B true CN104087339B (en) | 2015-11-18 |
Family
ID=51635104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410276047.0A Active CN104087339B (en) | 2014-06-19 | 2014-06-19 | A kind of method that assorted oil, coal and coal tar hydrogenating refine altogether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104087339B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017109014A1 (en) * | 2015-12-22 | 2017-06-29 | Rhodia Operations | Positive active material for rechargeable lithium-sulfur battery |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106693975B (en) * | 2016-11-24 | 2020-03-27 | 中国石油大学(华东) | Oil-soluble Fe-Ni bimetallic catalyst and preparation method and application thereof |
| CN106433775B (en) * | 2016-12-20 | 2018-07-10 | 煤炭科学技术研究院有限公司 | A kind of kerosene is total to smelting method and its device |
| CN106732672B (en) * | 2017-02-23 | 2020-05-01 | 中国石油大学(华东) | Coal-loaded molybdenum-based catalyst for coal-oil suspension bed hydrogenation co-refining |
| 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 |
| CN111359547A (en) * | 2019-03-15 | 2020-07-03 | 南京延长反应技术研究院有限公司 | Oil-coal co-hydrogenation micro-interface reinforced emulsion bed reaction system |
| CN111686654A (en) * | 2019-03-15 | 2020-09-22 | 南京延长反应技术研究院有限公司 | Coal tar hydrogenation micro-interface emulsion bed enhanced reaction system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1546808A (en) * | 1976-01-05 | 1979-05-31 | Us Energy | Coal liquefaction process |
| CN1351130A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Hydrogenation process for preparing diesel oil from coal-tar oil |
| CN103540351A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Combined process method for treating coal tar whole fraction |
| CN103773477A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Coal tar and residuum hydrocracking-delayed coking combination processing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA828311B (en) * | 1981-11-18 | 1983-09-28 | Hydrocarbon Research Inc | Coal hydrogenation process using petroleum derived slurryiing oil |
-
2014
- 2014-06-19 CN CN201410276047.0A patent/CN104087339B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1546808A (en) * | 1976-01-05 | 1979-05-31 | Us Energy | Coal liquefaction process |
| CN1351130A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Hydrogenation process for preparing diesel oil from coal-tar oil |
| CN103540351A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Combined process method for treating coal tar whole fraction |
| CN103773477A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Coal tar and residuum hydrocracking-delayed coking combination processing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017109014A1 (en) * | 2015-12-22 | 2017-06-29 | Rhodia Operations | Positive active material for rechargeable lithium-sulfur battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104087339A (en) | 2014-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104087339B (en) | A kind of method that assorted oil, coal and coal tar hydrogenating refine altogether | |
| CN103289740B (en) | Method for preparing clean fuel oil from coal tar | |
| CN102796559B (en) | Method and the device of oil fuel are produced in hydrocracking | |
| CN1876767B (en) | Coal tar hydrocracking method | |
| CN105694966B (en) | A kind of method that naphtha and clean gasoline are produced by catalytic cracking diesel oil | |
| CN101067089A (en) | Shale oil producing process | |
| CN104862004A (en) | Combined coal tar whole fraction hydroprocessing system and application thereof | |
| CN101899326B (en) | Shale oil catalytic upgrading method | |
| CN102465018B (en) | Technological method for hydrogenation of coker full-range distillate | |
| CN105154134A (en) | Method for preparing catalytic thermal cracking raw materials from full-fraction shale oil | |
| CN100389179C (en) | Hydrogenation cracking method of mass production of chemical materials | |
| CN103102980A (en) | Combined process for in-depth conversion of residual oil | |
| CN104277879B (en) | A kind of two-stage slurry bed system hydrogenation technique of middle coalite tar | |
| CN108048121B (en) | Direct coal liquefaction method and direct coal liquefaction device | |
| CN105400537B (en) | A kind of method using mixed refining technique processing oil and coal | |
| CN103102982A (en) | Combined process for conversion of residual oil | |
| CN100569925C (en) | A kind of heavy, residual oil combinational processing method | |
| CN100404646C (en) | Method for modifying poor-quality diesel-oil by cut fraction | |
| CN107033955A (en) | A kind of full plant process flow using all-round bed hydroprocessing technique | |
| CN104109558B (en) | A kind of poor quality oil two-part hydrogenation method for refining | |
| CN106221797B (en) | Deep processing of shale oil method | |
| CN102585898A (en) | High-nitrogen high-aromatic-oil two-stage method hydrocarbon hydrogenation method | |
| CN104178209A (en) | Joint hydrogenation method for different fractions of high aromatic hydrocarbons | |
| CN105087061A (en) | Hydrocracking method in pre-upgrading region of high aromatic hydrocarbon hydrogenation refined heavy oil | |
| CN102311782A (en) | Method for producing diesel oil by purifying coal tar through hydrogenating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100029 Beijing City, Chaoyang District Hui New Street No. 11 Ziguang building A block 12 layer Patentee after: BEIJING BAOJU ENERGY SCIENCE AND TECHNOLOGY CO.,LTD. Address before: 100029 Beijing City, Chaoyang District Hui New Street No. 11 Ziguang building A block 12 layer Patentee before: BEIJING BAOTASANJU ENERGY TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201019 Address after: 100080, Beijing, Haidian District North Road, No. 33, building 1, foundation building, 9 floor Patentee after: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. Address before: 100029, Beijing, Chaoyang District Xin Tung Street, No. 11 violet development building, block A, 12 Patentee before: BEIJING BAOJU ENERGY SCIENCE AND TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Address before: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |