CN104277879B - A kind of two-stage slurry bed system hydrogenation technique of middle coalite tar - Google Patents
A kind of two-stage slurry bed system hydrogenation technique of middle coalite tar Download PDFInfo
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- CN104277879B CN104277879B CN201310282780.9A CN201310282780A CN104277879B CN 104277879 B CN104277879 B CN 104277879B CN 201310282780 A CN201310282780 A CN 201310282780A CN 104277879 B CN104277879 B CN 104277879B
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- 239000002002 slurry Substances 0.000 title claims abstract description 85
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000003921 oil Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 238000004508 fractional distillation Methods 0.000 claims abstract description 31
- 239000000295 fuel oil Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 239000011269 tar Substances 0.000 claims description 58
- 239000011280 coal tar Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 29
- 239000002283 diesel fuel Substances 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910020515 Co—W Inorganic materials 0.000 claims description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010742 number 1 fuel oil Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides the two-stage slurry bed system hydrogenation technique of a kind of middle coalite tar, comprises the steps: that (1) centering coalite tar carries out purified treatment；(2) carrying out reducing pressure or air-distillation by the middle coalite tar after purified treatment in described step (1), cut into light oil distillate and heavy oil fraction, the temperature range of cut point is 320～380 DEG C；(3) by the heavy oil fraction higher than cut point in described step (2) and hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, the hydrocracked product prepared is carried out fractional distillation process, using the temperature range of cut point described in step (2) that hydrocracked product is carried out fractional distillation, the fraction that will be less than above-mentioned cut point distillates；3～8% ＞ 540 DEG C fraction outside arrange, remaining loops back one-level paste state bed reactor.The liquid fuel using technique of the present invention to prepare has the advantage that hydrogen consumption is low, product yield is high.
Description
Technical field
The present invention relates to the two-stage slurry bed system hydrogenation technique of a kind of middle coalite tar, belong to coalification
Work technical field.
Background technology
Liquid fuel occupies highly important status in the various energy.Various automobiles, boats and ships,
The means of transport such as aircraft, engineering machinery uses liquid fuel the most in a large number.Liquid fuel mainly comes
Come from from underground mining oil out.And in recent years, along with world petroleum resource day by day
Exhausted and the continuous of China's energy crisis is deepened, and finds reasonable, economic alternative energy source, changes
Become energy consumption structure, it has also become the task of top priority that China faces.
Along with China's iron and steel and the fast development of coal chemical industry, the yield of coal tar is increasingly
Greatly, effective utilization of coal tar also becomes more and more important.And with coal tar as raw material,
Under the effect of catalyst, carry out hydrofinishing or be hydrocracked the technology work preparing liquid fuel
Substitute products for petrochemical industry the most just receive much concern, and it can not only be mended by petroleum replacing chemical industry
Fill the deficiency of domestic petroleum resource, and for ensureing energy strategy safety, have reality and
Long-range strategic importance.
According to pyrolysis of coal pyrolysis temperature and the difference of process approach, coal tar is commonly divided into low
Coalite tar in gentleness warm, middle, its composition difference is bigger.At present, coal tar hydrogenating skill
Art can substantially be summarized as according to its technical characterstic: coal tar hydrorefining technology, delayed coking-
It is hydrocracked process integration technology, the fixed bed hydrogenation cracking technology of coal tar and coal tar
Slurry bed system hydrocracking technology.Such as Chinese patent literature CN103059973A discloses one
Planting slurry bed system and the fixed bed coupling process of full fraction of coal tar hydrogenation, the method mainly includes
Following steps: (1) full fraction of coal tar oil through dehydration, udst separation pretreatment after, with
Hydrocracking catalyst mix homogeneously, preheated entrance slurry bed system Hydrocracking unit；(2)
At slurry bed system Hydrocracking unit, described full fraction of coal tar oil is made at hydrocracking catalyst
Being hydrocracked under with, this process is continuous feed, and first hydrogenated products enter fractionation unit；
(3) at fractionation unit, described just hydrogenated products are fractionated into operating wherein light components and enter solid
Fixed bed hydrofinishing unit, midbarrel loops back paste state bed reactor together with catalyst,
Heavy component still loops back after the coke that partial catalyst and cracking process produce is removed by filtration
Step (1)；(4) at fixed bed hydrogenation refined unit, the lightweight group of described just hydrogenated products
Under Hydrobon catalyst effect, point carry out being hydrogenated with saturated, desulfurization, torr folk prescription speech, obtain
Hydrogenated products；(5) at product rectification cell, hydrogenated products enter rectifying column, carry out fraction
Cutting obtains final products vapour, diesel oil.
First full fraction of coal tar after pretreatment is hydrocracked by above-mentioned technology at slurry bed system
Unit is hydrocracked, and the first hydrogenated products obtained are fractionated into again, and light components enters solid
Fixed bed hydrofinishing unit carries out hydrofinishing, and midbarrel is recycled to paste state bed reactor and enters
Row is hydrocracked, and heavy component carries out pretreatment through filtration treatment Posterior circle to pretreatment unit.
The petrol and diesel oil target product prepared through above-mentioned technology is the petrol and diesel oil meeting Standard.
But it is hydrocracked owing to above-mentioned technology directly carries out slurry bed system to full fraction of coal tar, and coal
The full fraction of tar does not contain only heavy end, possibly together with midbarrel and light ends, and
Light ends is when carrying out slurry bed system and being hydrocracked, and light ends forms dilution to heavy end
Effect, reduces reactant concentration, so can cause hydrogen consumption in slurry bed system hydrocracking process
Increasing, cause the wasting of resources, also can affect coal tar hydrogenating prepares the receipts of liquid fuel simultaneously
Rate..
In prior art, also have and first carry out reducing pressure or after air-distillation by full fraction of coal tar,
Cut into light oil distillate and heavy oil fraction, then light oil distillate and heavy oil fraction are urged respectively
Change the Hydrogenation report for liquid fuel.Such as Chinese patent literature CN101864327A is public
Having opened a kind of coal tar hydrogenation modification method, the method mainly comprises the steps: first coal
Tar is cut into the light oil distillate of ＜ 205 DEG C and ＞ 205 DEG C through air-distillation or decompression distillation
Heavy oil fraction；Again the light oil distillate to ＜ 205 DEG C carry out one section of fixed bed hydrogenation refine, to this
Hydrotreated product is alkylated reaction, obtains gasoline products；Mink cell focus to ＞ 205 DEG C
Fraction is solid by weight being mixed into two ends after adding flux oil mix homogeneously for 1:1 with hydrogen
Fixed bed hydrogenation reactor carries out deep hydrofinishing, obtains diesel oil distillate after being fractionated into processing.
Although above-mentioned technology has first carried out decompression or air-distillation to full fraction of coal tar, then to obtaining
Light ends and heavy end carry out hydrofinishing respectively, but in above-mentioned technology, counterweight
When matter distillate carries out catalytic hydrogenation, use again flux oil that heavy distillate is first diluted,
The hydrofinishing again the heavy distillate employing fixed bed after dilution carried out, and flux oil
Exist and also result in hydrogen consumption increase in unifining process, cause the wasting of resources, the most also
Coal tar hydrogenating can be affected and prepare the yield of liquid fuel.
It is to say, in prior art the heavy distillate in coal tar is carried out slurry bed system or
During fixed bed hydrogenation reaction, it is all to use light ends or flux oil that heavy end is diluted
After carry out hydrogenation reaction again, and the present inventor is found by research, and light ends too much exists
In heavy end, when jointly carrying out hydrogenation reaction with heavy end, there is hydrogen consumption height, simultaneously
Also cause coal tar hydrogenating to be prepared the yield of liquid fuel is low, the S of liquid fuel, N content high,
The problem that the Cetane number content of the diesel product especially obtained is low.
Summary of the invention
The technical problem to be solved is in prior art, coal tar to be carried out catalysis to add
During hydrogen, need first to use light ends or diluent to add again after heavy end is diluted
Hydrogen, so can reduce reactant concentration, causes hydrogen consumption in catalytic hydrogenation to increase, and liquid
The yield of fuel is low, S in liquid fuel, N content is high, the diesel product that especially obtains
Cetane number content low, and then provide a kind of by coalite tar is carried out suitable fractional distillation
After, different fractions is fixed respectively the hydrogen consumption that bed hydroprocessing refines and slurry bed system is hydrocracked
Low, liquid fuel yield height, the Unionfining technique of excellent quality.
In order to solve above-mentioned technical problem, the invention provides the two-stage of a kind of middle coalite tar
Slurry bed system hydrogenation technique, comprises the steps:
(1) centering coalite tar carries out purified treatment；
(2) the middle coalite tar after purified treatment in described step (1) is reduced pressure
Or air-distillation, cutting into light oil distillate and heavy oil fraction, the temperature range of cut point is
320～380 DEG C；
(3) heavy oil fraction higher than cut point in described step (2) is urged with being hydrocracked
Agent, H2Mixing, sequentially enters one-level slurry bed system, two grades of slurry bed system are carried out after mix homogeneously
Two-stage hydrocracking reaction, carries out fractional distillation process to the hydrocracked product prepared, and uses
Described in step (2), the temperature range of cut point carries out fractional distillation to hydrocracked product, by low
Fraction in above-mentioned cut point distillates, and obtains Petroleum and bavin after the further fractional distillation of product distillated
Oil product, 3～8% ＞ 540 DEG C fraction outside arrange, remaining loops back one-level paste state bed reactor.
The light oil distillate being less than cut point in described step (2) is carried out phenol removal, the phenol of removing
Device is gone out as product；Light oil distillate after phenol removal is less than described in step (3)
Cut point and the fraction mixing that distillates, as the charging of fixed bed hydrogenation device, are urged in hydrofinishing
Carry out hydrofining reaction under agent effect, hydrorefined product is carried out fractional distillation, obtains stone
Cerebrol and diesel oil.
Described Hydrobon catalyst is any in Co-Mo, Ni-Mo, Co-W, Ni-W
One or more.
The condition of described fixed bed hydrogenation reaction is: temperature be 220～450 DEG C, pressure be
12.0～18.0MPa, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio be 500～3000.
Middle coalite tar in described step (1) adds in high temperature coal-tar, residual oil
One or more, wherein said residual oil select high-sulfur heavy resid, high bitumen content heavy resid,
One or more in high content of beary metal heavy resid.
Described hydrocracking catalyst is containing hydrogenation active component Fe, Co, Ni, Mo, W
In any one or a few nanometer materials.
After described step (3) is higher than the heavy oil fraction first preheated process of cut point, then with
Hydrocracking catalyst, H2Mixing.
Described preheating temperature is 100～250 DEG C.
Described one-level slurry reactor temperature 350～550 DEG C, two grades of slurry reactor temperature are
350～550 DEG C, other reaction conditions of two paste state bed reactors are: pressure is
10.0～18.0MPa, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio be 1200～5000.
The present invention compared with prior art has the advantage that
(1) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, the most right
Middle coalite tar carries out purified treatment, and the purpose of purified treatment is coalite tar in removing
In contain solid impurity, water etc.；The most again to the middle coalite tar after purified process
Carry out reducing pressure or air-distillation, cut into light oil distillate and heavy oil fraction, with 320～380 DEG C
For the temperature range of cut point, it is because meeting in the heavy oil fraction in this cutting temperature scope
Containing the light oil distillate of Sq, and the existence of this part light oil distillate to heavy oil fraction rear
Two grades of continuous slurry bed system have collaborative facilitation in being hydrocracked, and it can be greatly improved this
The hydrogenation conversion of part heavy oil fraction.Use the two-stage of middle coalite tar of the present invention
The liquid fuel that slurry bed system hydrogenation technique prepares has high excellent of hydrogen low, the product yield of consumption
Point, and two-stage slurry bed system be hydrocracked after obtain the light oil distillate less than cut point temperature through entering
S in product Petroleum that one step fractional distillation obtains and diesel oil, N content are far below prior art
In S, N content in the liquid fuel for preparing, and diesel-fuel cetane number is greatly improved.
(2) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, further
Define after the light oil distillate less than cut point is first carried out phenol removal, then starch with through two-stage
The fraction mixing of the cut point less than 320～380 DEG C obtained after state bed hydroprocessing cracking, then
It is fixed bed hydroprocessing to refine, this is because containing a large amount of in middle coalite tar light ends
Phenols, use suitable technology will in phenol therefrom coalite tar light fraction propose, as
Product its there is the highest market value, simultaneously because substantial amounts of phenols is suggested, middle low temperature
It is relatively low that the oxygen content of coal tar light fraction drops, and significantly reduces its hydrogenation hydrogen consumption, and keeps away
Exempt from the phenols of high value is become the hydro carbons such as benzene.Light oil distillate after dephenolize with through two-stage slurry
The described fraction mixing distillated less than cut point that bed hydroprocessing aftercut goes out adds as fixed bed
The charging of hydrogen production device, then be fixed bed hydroprocessing refined after can improve institute of the present invention further
State the conversion ratio of middle coalite tar, and after hydrofinishing, obtain product Petroleum and diesel oil
S, N content reduce further, and diesel-fuel cetane number improves further.
(3) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, further
Ground, it is also possible to add the one or several in high temperature coal-tar, residual oil in middle coalite tar
Plant and form mixture, then use above-mentioned steps to carry out catalytic hydrogenation, due to right in this mixture
This mixture is provided with the cut point of 320～380 DEG C equally, and the mixing on this cut point
Can be containing the light oil distillate of Sq in heavy oil fraction in thing, and the depositing of this part light oil distillate
Heavy oil fraction in mixture is had collaborative in follow-up two-stage slurry bed system is hydrocracked
Facilitation, it can be greatly improved the hydro-conversion of the heavy oil fraction in this part mixes
Rate.Therefore, use the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention,
It is possible not only to centering coalite tar and carries out catalytic hydrogenation, it is also possible to centering coalite tar,
The mixed material that high temperature coal-tar, residual oil are formed carries out catalytic hydrogenation, and the liquid prepared
Fluid fuel has the advantage that hydrogen consumption is low, product yield is high equally.
(4) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, further
Ground, it is also possible to select to carry out the pre-heat treatment to more than the heavy oil fraction of cut point temperature, then with
Hydrocracking catalyst, H2Mixing, so can make this part heavy oil fraction and catalyst,
H2Mix is more uniform, in order to improve its hydrogenation catalyst efficiency further.
(5) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, through slurry
What bed hydroprocessing obtained after processing enters fixed bed hydrogenation device less than the fraction of cut point under hot,
It is greatly enhanced the thermal efficiency；And in using slurry bed system to process in coalite tar more than cutting temperature
Fraction, can avoid owing to coking and metal deposit cause hydrogenation plant pressure drop rapid increase to cause
The short problem of on-stream time；In addition the present invention also controls slurry bed system device conversion per pass, and
Outer row's part high boiling fraction, can be by the metal of removing, Jiao of knot and used catalyst row
Go out device, it is ensured that device long period steady running.
Accompanying drawing explanation
Fig. 1 is the technique of the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention
Flow chart；
Reference is as follows:
1. coalite tar raw material in；2. purified treatment；3. normal pressure or vacuum distillation tower；4. it is higher than
The fraction of cut point；5. less than the fraction of cut point；6.3～the fraction of ＞ 540 DEG C of 8%；7.
One-level slurry reactor device；8. two grades of slurry reactor devices；9. fixed-bed reactor；
10. remaining fraction；11. Petroleums；12. diesel oil.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
Embodiment 1
(1) in purification apparatus centering coalite tar carry out being dehydrated, the purification of remove impurity
Processing, the middle coalite tar water content after dehydration is less than 0.5wt%；
(2) will through the middle coalite tar air-distillation after purified treatment in described step (1),
Cutting into light oil distillate and heavy oil fraction, the temperature range of cut point is 320 DEG C；
(3) by the heavy oil fraction higher than 320 DEG C of cut points in described step (2) and hydrogenation
Cracking catalyst, H2Mixing, wherein, described hydrocracking catalyst is nanometer materials,
Consisting of 50wt% alpha-feooh, surplus is γ-Al2O3, sequentially enter after mix homogeneously
One-level slurry bed system, two grades of slurry bed system carry out two-stage hydrocracking reaction, the bar of hydrocracking reaction
Part is as follows: described one-level slurry reactor temperature is 350 DEG C, and two grades of slurry reactor temperature are
350 DEG C, other reaction condition of one-level slurry bed system and two grades of slurry bed system is: pressure is
18.0MPa, volume space velocity are 0.5h-1, hydrogen to oil volume ratio be 1200；To adding of preparing
Hydrogen cracked product carries out fractional distillation process, uses the temperature range of cut point described in step (2)
Hydrocracked product is carried out fractional distillation, and the fraction that will be less than 320 DEG C distillates, and continues fractional distillation and obtains
Petroleum and diesel product；3～8% ＞ 540 DEG C fraction outside arrange, remaining loop back one-level slurry
State bed reactor.
In in above-described embodiment, the total conversion of coalite tar is 92.4%, diesel oil total recovery
39.7%。
Embodiment 2
(1) in purification apparatus centering coalite tar carry out being dehydrated, the purification of remove impurity
Processing, the middle coalite tar water content after dehydration is less than 0.5wt%；
(2) will distill through the middle coalite tar decompression after purified treatment in described step (1),
Cutting into light oil distillate and heavy oil fraction, cut point is 340 DEG C；
(3) by the heavy oil fraction higher than 340 DEG C of cut points in described step (2) and hydrogenation
Cracking catalyst, H2Mixing, wherein, described hydrocracking catalyst is nanometer materials,
Consisting of 25wt%MoO3, 5wt%NiO, surplus be γ-Al2O3, depend on after mix homogeneously
Secondary entrance one-level slurry bed system, two grades of slurry bed system carry out two-stage hydrocracking reaction, are hydrocracked anti-
The condition answered is as follows: described one-level slurry reactor temperature is 400 DEG C, two grades of slurry reactors
Temperature is 400 DEG C, and other reaction condition of one-level slurry bed system and two grades of slurry bed system is: pressure is
16.0MPa, volume space velocity are 1.0h-1, hydrogen to oil volume ratio be 1600；To adding of preparing
Hydrogen cracked product carries out fractional distillation process, uses the temperature range of cut point described in step (2)
Hydrocracked product is carried out fractional distillation, and the fraction that will be less than 340 DEG C distillates, and continues fractional distillation and obtains
Petroleum and diesel product；3～8% ＞ 540 DEG C fraction outside arrange, remaining loop back one-level slurry
State bed reactor；
(4) light oil distillate being less than 340 DEG C of cut points in described step (2) is carried out dephenolize
Processing, the phenol of removing goes out device as product；Light oil distillate after phenol removal and step (3)
Described in fraction mixing less than 340 DEG C as the charging of fixed bed hydrogenation device, in hydrogenation essence
Carrying out hydrofining reaction under catalyst action processed, the condition of described fixed bed hydrogenation reaction is:
Temperature be 220 DEG C, pressure be 18.0MPa, volume space velocity be 0.5h-1, hydrogen to oil volume ratio
It is 500；Hydrofining reaction, wherein said hydrogenation is carried out under Hydrobon catalyst effect
The composition of catalyst for refining is as follows: 7wt%NiO, 20wt%MoO3, surplus be that ZSM-5 divides
Son sieve, carries out fractional distillation to hydrorefined product, obtains Petroleum and diesel oil；
In in above-described embodiment, the total conversion of coalite tar is 94.7%, diesel oil total recovery
73%, phenol yield 9.7%.
Embodiment 3
(1) in purification apparatus, centering coalite tar, the mixture of residual oil take off
Water, the purified treatment of remove impurity, wherein said residual oil is chosen as high-sulfur heavy resid, high heavy metal contains
The mixture of amount heavy resid, described middle coalite tar, high-sulfur heavy resid, high content of beary metal
The mass ratio of heavy resid is 5:0.5:0.5, and the mixture water content after dehydration is less than 0.5wt%；
(2) will distill through the middle coalite tar decompression after purified treatment in described step (1),
Cutting into light oil distillate and heavy oil fraction, cut point is 360 DEG C；
(3) by the heavy oil fraction higher than 360 DEG C of cut points in described step (2) at 100 DEG C
Under carry out the pre-heat treatment, then with hydrocracking catalyst, H2Mixing, wherein, described hydrogenation
Cracking catalyst is nanometer materials, consisting of 5wt%NiO, 30wt%WO3Surplus is
Natural zeolite molecular sieve, sequentially enters one-level slurry bed system, two grades of slurry bed system are carried out after mix homogeneously
Two-stage hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactor
Temperature is 455 DEG C, and two grades of slurry reactor temperature are 455 DEG C, one-level slurry bed system and two grades of slurries
Other reaction condition of state bed is: pressure is 12.0MPa, volume space velocity is 0.5h-1, hydrogen oil
Volume ratio is 2500；The hydrocracked product prepared is carried out fractional distillation process, uses step
Suddenly described in (2), the temperature range of cut point carries out fractional distillation to hydrocracked product, will be less than
The fraction of 360 DEG C distillates, and continues fractional distillation and obtains Petroleum and diesel product；3～the ＞ 540 DEG C of 8%
Fraction outside arrange, remaining loops back one-level paste state bed reactor；
(4) light oil distillate being less than 360 DEG C of cut points in described step (2) is carried out dephenolize
Processing, the phenol of removing goes out device as product；Light oil distillate after phenol removal and step (3)
Described in fraction mixing less than 360 DEG C as the charging of fixed bed hydrogenation device, in hydrogenation essence
Carrying out hydrofining reaction under catalyst action processed, the condition of described fixed bed hydrogenation reaction is:
Temperature be 360 DEG C, pressure be 14.0MPa, volume space velocity be 1.0h-1, hydrogen to oil volume ratio
It is 900；Hydrofining reaction, wherein said hydrogenation is carried out under Hydrobon catalyst effect
The composition of catalyst for refining is as follows: 7wt%NiO, 35wt%CoO, surplus are that ZSM-5 divides
Son sieve, carries out fractional distillation to hydrorefined product, obtains Petroleum and diesel oil；
In above-described embodiment, the total conversion of coal oil mixture is 95.2%, diesel oil total recovery
78%, phenol yield 9%.
Embodiment 4
(1) centering coalite tar and the mixture of high temperature coal-tar in purification apparatus
Carry out being dehydrated, the purified treatment of remove impurity, wherein, described middle coalite tar and high temperature coal-tar
Mass ratio be 3:1, the mixture water content after dehydration is less than 0.5wt%；
(2) will through the middle coalite tar air-distillation after purified treatment in described step (1),
Cutting into light oil distillate and heavy oil fraction, cut point is 355 DEG C；
(3) by the heavy oil fraction higher than 355 DEG C of cut points in described step (2) at 150 DEG C
Under carry out the pre-heat treatment, then with hydrocracking catalyst, H2Mixing, wherein, described hydrogenation
Cracking catalyst is nanometer materials, consisting of consisting of 5wt%CoO, 35wt%MoO3
Surplus is natural zeolite molecular sieve, sequentially enters one-level slurry bed system, two grades of slurry after mix homogeneously
Bed carries out two-stage hydrocracking reaction, and the condition of hydrocracking reaction is as follows: described one-level slurry
Bed reaction temperature be 500 DEG C, two grades of slurry reactor temperature are 500 DEG C, one-level slurry bed system and
Other reaction condition of two grades of slurry bed system is: pressure is 16.0MPa, volume space velocity is 1.5h-1,
Hydrogen to oil volume ratio is 3500；The hydrocracked product prepared is carried out fractional distillation process, adopts
By the temperature range of cut point described in step (2), hydrocracked product is carried out fractional distillation, will
Fraction less than 355 DEG C distillates, and continues fractional distillation and obtains Petroleum and diesel product；3～the ＞ of 8%
Arranging outside the fraction of 540 DEG C, remaining loops back one-level paste state bed reactor；
(4) light oil distillate being less than 355 DEG C of cut points in described step (2) is carried out dephenolize
Processing, the phenol of removing goes out device as product；Light oil distillate after phenol removal and step (3)
Described in fraction mixing less than 355 DEG C as the charging of fixed bed hydrogenation device, in hydrogenation essence
Carrying out hydrofining reaction under catalyst action processed, the condition of described fixed bed hydrogenation reaction is:
Temperature be 400 DEG C, pressure be 14.0MPa, volume space velocity be 1.5h-1, hydrogen to oil volume ratio
It is 2000；Under Hydrobon catalyst effect, carry out hydrofining reaction, wherein said add
The composition of hydrogen catalyst for refining is as follows: 27wt%WO3, 10wt%CoO, surplus be ZSM-5
Molecular sieve, carries out fractional distillation to hydrorefined product, obtains Petroleum and diesel oil.
In above-described embodiment, the total conversion of coal oil mixture is 98.8%, diesel oil total recovery
79.4%, phenol yield 10.6%.
Embodiment 5
(1) in purification apparatus, centering coalite tar, the mixture of residual oil take off
Water, the purified treatment of remove impurity, wherein said residual oil select high bitumen content heavy resid, described in
Coalite tar, the mass ratio of residual oil are 5:1, the coal oil mixture water content after dehydration
Less than 0.5wt%；
(2) will through the middle coalite tar air-distillation after purified treatment in described step (1),
Cutting into light oil distillate and heavy oil fraction, cut point is 380 DEG C；
(3) by the heavy oil fraction higher than 380 DEG C of cut points in described step (2) at 250 DEG C
Under carry out the pre-heat treatment, then with hydrocracking catalyst, H2Mixing, wherein, described hydrogenation
Cracking catalyst is nanometer materials, consisting of consisting of 5wt%Fe2O3、35wt%WO3
Surplus is natural zeolite molecular sieve, sequentially enters one-level slurry bed system, two grades of slurry after mix homogeneously
Bed carries out two-stage hydrocracking reaction, and the condition of hydrocracking reaction is as follows: described one-level slurry
Bed reaction temperature be 550 DEG C, two grades of slurry reactor temperature are 550 DEG C, one-level slurry bed system and
Other reaction condition of two grades of slurry bed system is: pressure is 10.0MPa, volume space velocity is 2.0h-1、
Hydrogen to oil volume ratio is 5000；The hydrocracked product prepared is carried out fractional distillation process, adopts
By the temperature range of cut point described in step (2), hydrocracked product is carried out fractional distillation, will
Fraction less than 380 DEG C distillates, and distillation obtains Petroleum and diesel product after continuing on through fractional distillation；
3～8% ＞ 540 DEG C fraction outside arrange, remaining loops back one-level paste state bed reactor；
(4) light oil distillate being less than 380 DEG C of cut points in described step (2) is carried out dephenolize
Processing, the phenol of removing goes out device as product；Light oil distillate after phenol removal and step (3)
Described in fraction mixing less than 380 DEG C as the charging of fixed bed hydrogenation device, in hydrogenation essence
Carrying out hydrofining reaction under catalyst action processed, the condition of described fixed bed hydrogenation reaction is:
Temperature be 450 DEG C, pressure be 12.0MPa, volume space velocity be 2.0h-1, hydrogen to oil volume ratio
It is 3000；Under Hydrobon catalyst effect, carry out hydrofining reaction, wherein said add
The composition of hydrogen catalyst for refining is as follows: 7wt%NiO, 35wt%CoO, surplus are ZSM-5
Molecular sieve, carries out fractional distillation to hydrorefined product, obtains Petroleum and diesel oil；
In above-described embodiment, the total conversion of coal oil mixture is 97.4%, diesel oil total recovery
76.4%, phenol yield 8.7%.
Additionally, present invention also offers in above-mentioned all embodiments high temperature coal-tar used, in low
Temperature coal tar, slag oil properties, as shown in table 1, and further provide the stone prepared
Cerebrol and bavin oil properties, as shown in table 2.
Table 1 raw material oil properties
| Raw oil | High temperature coal-tar | Middle coalite tar | Residual oil |
| Density g/cm3 | 1.18 | 1.002 | 0.94 |
| S, wt% | 0.3 | 0.3 | 2.1 |
| O, wt% | 1 | 6.5 | - |
| N, wt% | 0.8 | - | - |
| Ash, wt% | - | - | 0.045 |
| Ni+V, ppm | - | - | 110 |
| C7 insoluble matter, wt% | ＜ 9 | 4.5 | - |
Petroleum that table 2 prepares and bavin oil properties
Comparative example
The present invention uses the embodiment provided in documents CN103059973A as this
Bright described comparative example, it, with the full fraction of high temperature coal-tar as raw material, uses following technique: locate in advance
Reason removes the water in raw material and mechanical admixture, mixs homogeneously with hydrocracking catalyst and enters slurry
Bed reactor, hydrocracking catalyst is 35%WO3、10%NiO、3%P2O5, surplus be
USY molecular sieve, hydrocracking condition is as follows: preheating temperature 150 DEG C, reaction pressure break 12MPa,
Reaction temperature is 390 DEG C, volume space velocity 0.5h-1, hydrogen to oil volume ratio be 1600, hydrogenated split
Head product after change enters fractionating column, and light fraction enters back segment fixed bed reactors and carries out hydrogenation essence
System, this part fraction accounts for 15wt%, and midbarrel about 65wt% loops back slurry reactor
Device continues to be hydrocracked, and the heavy end of about 20wt% is removed by filtration partial catalyst and reaction
During produce coke after enter raw material storage tank, the cyclic utilization rate of catalyst is about 80%,
Wherein light ends fixed bed hydrogenation refining reaction condition is as follows: reaction pressure 8MPa, reaction
Temperature 375 DEG C, volume space velocity 0.5h-1, hydrogen to oil volume ratio 1600；Product after fixed bed is refined
Product are fractionated into obtaining gasoline and diesel oil, and the performance of the gasoline prepared is as follows: density
0.7995g/cm-3, sulfur content ＜ 50ppm, nitrogen content ＜ 50ppm, octane number 91.5, preparation
The performance of the diesel oil distillate obtained is as follows: density 0.7995g/cm-3, sulfur content ＜ 50ppm,
Nitrogen content ＜ 50ppm, Cetane number 35.6；
From above-mentioned comparative example, use Petroleum, bavin that the method for the invention prepares
The sulfur content of oil, nitrogen content are substantially reduced, and diesel-fuel cetane number is also greatly improved.
Obviously, above-described embodiment is only for clearly demonstrating example, and the most right
The restriction of embodiment.For those of ordinary skill in the field, in described above
On the basis of can also make other changes in different forms.Here without also cannot
All of embodiment is given exhaustive, and the obvious change thus extended out or
Change among still in the invention scope of the claims.
Claims (9)
1. in, a two-stage slurry bed system hydrogenation technique for coalite tar, comprises the steps:
(1) centering coalite tar carries out purified treatment；
(2) carrying out reducing pressure or air-distillation by the middle coalite tar after purified treatment in described step (1), cut into light oil distillate and heavy oil fraction, the temperature range of cut point is 320～380 DEG C；
(3) by the heavy oil fraction higher than cut point in described step (2) and hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, the hydrocracked product prepared is carried out fractional distillation process, use the temperature range of cut point described in step (2) that hydrocracked product is carried out fractional distillation, the fraction that will be less than above-mentioned cut point distillates, obtain Petroleum and diesel product after the further fractional distillation of product distillated, 3～8% ＞ 540 DEG C fraction outside arrange, remaining loops back one-level paste state bed reactor.
The two-stage slurry bed system hydrogenation technique of coalite tar in the most according to claim 1, it is characterised in that the light oil distillate being less than cut point in described step (2) is carried out phenol removal, and the phenol of removing goes out device as product；Light oil distillate after phenol removal mixes the charging as fixed bed hydrogenation device with the fraction distillated less than cut point described in step (3), hydrofining reaction is carried out under Hydrobon catalyst effect, hydrorefined product is carried out fractional distillation, obtains Petroleum and diesel oil.
The two-stage slurry bed system hydrogenation technique of coalite tar in the most according to claim 2, it is characterised in that described Hydrobon catalyst is any one or a few in Co-Mo, Ni-Mo, Co-W, Ni-W.
4. according to the two-stage slurry bed system hydrogenation technique of coalite tar in described in Claims 2 or 3, it is characterised in that the condition of described fixed bed hydrogenation reaction is: temperature be 220～450 DEG C, pressure be 12.0～18.0MPa, volume space velocity be 0.5～2.0h-1, hydrogen to oil volume ratio be 500～3000.
5. according to the two-stage slurry bed system hydrogenation technique of coalite tar according to any one of claim 1-3, it is characterised in that the middle coalite tar in described step (1) adds high temperature coal-tar, residual oil one or more.
The two-stage slurry bed system hydrogenation technique of coalite tar in the most according to claim 5, it is characterised in that described hydrocracking catalyst is containing any one or a few the nanometer materials in hydrogenation active component Fe, Co, Ni, Mo, W.
The two-stage slurry bed system hydrogenation technique of coalite tar in the most according to claim 6, it is characterised in that in described step (3) higher than the heavy oil fraction first preheated process of cut point after, then with hydrocracking catalyst, H2Mixing.
The two-stage slurry bed system hydrogenation technique of coalite tar in the most according to claim 7, it is characterised in that described preheating temperature is 100～250 DEG C.
9. according to the two-stage slurry bed system hydrogenation technique of coalite tar middle described in claim 1,2,3,6,7 or 8, it is characterized in that, described one-level slurry reactor temperature 350～550 DEG C, two grades of slurry reactor temperature are 350～550 DEG C, and other reaction conditions of two paste state bed reactors are: pressure is 10.0～18.0MPa, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio be 1200～5000.
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| CN102786984A (en) * | 2011-05-16 | 2012-11-21 | 北京三聚创洁科技发展有限公司 | Process for preparing needle coke raw material by using medium and low temperature coal tar |
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| CN102786984A (en) * | 2011-05-16 | 2012-11-21 | 北京三聚创洁科技发展有限公司 | Process for preparing needle coke raw material by using medium and low temperature coal tar |
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