CN104277879A - Two-stage slurry bed hydrogenation process of medium and low temperature coal tar - Google Patents
Two-stage slurry bed hydrogenation process of medium and low temperature coal tar Download PDFInfo
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- CN104277879A CN104277879A CN201310282780.9A CN201310282780A CN104277879A CN 104277879 A CN104277879 A CN 104277879A CN 201310282780 A CN201310282780 A CN 201310282780A CN 104277879 A CN104277879 A CN 104277879A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
Abstract
The invention provides a two-stage slurry bed hydrogenation process of medium and low temperature coal tar, and the a two-stage slurry bed hydrogenation process comprises the following steps: (1) performing purification on the medium and low temperature coal tar; (2) performing decompression or atmospheric distillation on the medium and low temperature coal tar purified by the step (1) for cutting into light oil fractions and heavy oil fractions, wherein the cutting point temperature range is 320 to 380 DEG; (3) mixing the heavy oil fractions higher than the cutting point of the step (2) with a hydrocracking catalyst and H2, mixing evenly, and in turn getting into a first stage slurry bed and a second slurry bed for two-stage hydrocracking reaction, processing the prepared hydrocracking products by fractionation, performing fractional distillation on the hydrocracking products by the cutting point temperature range in the step (2) to distil off fractions lower than the cutting point; discharging 3-8% fractions higher than 540 DEG C out, and recycling the rest fractions back to a first stage slurry bed reactor. A liquid fuel prepared by the process has the advantages of low hydrogen consumption and high product yield.
Description
Technical field
The present invention relates to a kind of two-stage slurry bed system hydrogenation technique of middle coalite tar, belong to technical field of coal chemical industry.
Background technology
Liquid fuel occupies very consequence in the various energy.The transportation means such as various automobile, boats and ships, aircraft, engineering machinery use liquid fuel all in a large number.Liquid fuel is mainly derived from from underground mining oil out.And in recent years, along with the continuous intensification of exhaustion and China's energy dilemma day by day of world petroleum resource, find reasonable, economic substitute energy, change energy consumption structure, become the task of top priority that China faces.
Along with the fast development of China's iron and steel and coal chemical industry, the output of coal tar is increasing, and effective utilization of coal tar also becomes more and more important.And be raw material with coal tar, under the effect of catalyzer, carry out technology that hydrofining or hydrocracking prepare liquid fuel also just to receive much concern as the substitute products of petrochemical complex, it can not only supplement the deficiency of domestic petroleum resource by petroleum replacing chemical industry, and for guarantee energy strategy safety, there is reality and long-range strategic importance.
According to the difference of pyrolysis of coal pyrolysis temperature and process approach, coal tar can be divided into coalite tar in low temperature, middle gentleness usually, and its composition difference is larger.At present, coal tar hydrogenating technology can roughly be summarized as according to its technical characterstic: coal tar hydrorefining technology, delayed coking-hydrocracking process integration technology, the fixed bed hydrogenation cracking technology of coal tar and the slurry bed system hydrocracking technology of coal tar.Such as Chinese patent literature CN103059973A discloses a kind of slurry bed system and fixed bed coupling process of full fraction of coal tar hydrogenation, full fraction of coal tar that the method mainly comprises the steps: (1) oil is after the pre-treatment of dehydration, udst separation, mix with hydrocracking catalyst, enter slurry bed system Hydrocracking unit through preheating; (2) at slurry bed system Hydrocracking unit, described full fraction of coal tar oil carries out hydrocracking under hydrocracking catalyst effect, and this process is continuously feeding, and first hydrogenated products enter fractionation unit; (3) at fractionation unit, described just hydrogenated products through fractionation operation wherein light component enter fixed bed hydrogenation refined unit, middle runnings loops back paste state bed reactor together with catalyzer, still loops back step (1) after the heavy component coke that remove portion catalyzer and cracking process produce after filtration; (4) at fixed bed hydrogenation refined unit, the light component of described just hydrogenated products carries out hydrotreated lube base oil, desulfurization, holder folk prescription speech under Hydrobon catalyst effect, obtains hydrogenated products; (5) at product rectification cell, hydrogenated products enter rectifying tower, carry out cut cutting and obtain the finished product vapour, diesel oil.
First above-mentioned technology carries out hydrocracking to full fraction of coal tar after pretreatment at slurry bed system Hydrocracking unit, the first hydrogenated products obtained are again through fractionation, light component enters fixed bed hydrogenation refined unit and carries out hydrofining, middle runnings is circulated to paste state bed reactor and carries out hydrocracking, and heavy component processes Posterior circle after filtration and carries out pre-treatment to pretreatment unit.The petrol and diesel oil target product prepared through above-mentioned technology is the petrol and diesel oil meeting Standard.But because above-mentioned technology directly carries out slurry bed system hydrocracking to full fraction of coal tar, and not only containing heavy ends in full fraction of coal tar, also containing middle runnings and light ends, and light ends is when carrying out slurry bed system hydrocracking, light ends forms diluting effect to heavy ends, reduces reactant concn, and hydrogen consumption in slurry bed system hydrocracking process can be caused like this to increase, cause the wasting of resources, also can affect the yield that coal tar hydrogenating prepares liquid fuel simultaneously.。
In prior art, also have and first full fraction of coal tar is carried out reducing pressure or after air distillation, cutting into light oil distillate and heavy oil fraction, then the report that shortening prepares liquid fuel is carried out respectively to light oil distillate and heavy oil fraction.Such as Chinese patent literature CN101864327A discloses a kind of coal tar hydrogenation modification method, and the method mainly comprises the steps: that first coal tar is cut into the light oil distillate of < 205 DEG C and the heavy oil fraction of > 205 DEG C through air distillation or underpressure distillation; Carry out one section of fixed bed hydrogenation to the light oil distillate of < 205 DEG C again to refine, alkylated reaction is carried out to this hydrotreated product, obtains gasoline products; The heavy oil fraction of > 205 DEG C to be mixed afterwards and hydrogen is mixed into two ends fixed bed hydrogenation reactor and carries out deep hydrofinishing by weight adding thinning oil for 1:1, after fractionation process, obtains diesel oil distillate.Although above-mentioned technology has first carried out decompression or air distillation to full fraction of coal tar, again respectively hydrofining is carried out to the light ends obtained and heavy ends, but in above-mentioned technology, when shortening is carried out to heavy distillate, thinning oil is adopted again first to dilute heavy distillate, again to the hydrofining that the heavy distillate after dilution adopts fixed bed to carry out, and the existence of thinning oil can cause hydrogen consumption in unifining process to increase equally, cause the wasting of resources, also can affect the yield that coal tar hydrogenating prepares liquid fuel simultaneously.
That is, in prior art when carrying out slurry bed system or fixed bed hydrogenation reaction to the heavy distillate in coal tar, all carry out hydrogenation reaction again after adopting light ends or thinning oil to dilute heavy ends, and the present inventor is found by research, light ends is too much present in heavy ends, when jointly carrying out hydrogenation reaction with heavy ends, there is hydrogen consumption high, also cause coal tar hydrogenating to prepare the low problem of the cetane value content of the diesel product that the yield of liquid fuel is low, the S of liquid fuel, N content are high, especially obtain simultaneously.
Summary of the invention
Technical problem to be solved by this invention is when carrying out shortening to coal tar in prior art, hydrogenation is carried out again after needing first to adopt light ends or thinner to dilute heavy ends, reactant concn can be reduced like this, hydrogen consumption in catalytic hydrogenation is caused to increase, and the yield of liquid fuel is low, S in liquid fuel, N content is high, the cetane value content of the diesel product especially obtained is low, and then provide a kind of by after carrying out suitable fractionation to coalite tar, to different fractions be fixed respectively bed hydroprocessing refine and slurry bed system hydrocracking hydrogen consumption low, liquid fuel yield is high, the Unionfining technique of excellent quality.
In order to solve the problems of the technologies described above, the invention provides a kind of two-stage slurry bed system hydrogenation technique of middle coalite tar, comprising the steps:
(1) centering coalite tar carries out purifying treatment;
(2) carried out reducing pressure or air distillation by the middle coalite tar after purifying 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, H
2mixing, enter one-level slurry bed system successively after mixing, secondary slurry bed system carries out two-stage hydrocracking reaction, fractionation process is carried out to the hydrocracked product prepared, the temperature range of cut point described in step (2) is adopted to carry out fractionation to hydrocracked product, cut lower than above-mentioned cut point is distillated, obtain petroleum naphtha and diesel product after the further fractionation of the product distillated, the cut of the > 540 DEG C of 3 ~ 8% is arranged outward, and all the other loop back one-level paste state bed reactor.Light oil distillate lower than cut point in described step (2) is carried out phenol removal, and the phenol removed goes out device as product; Light oil distillate after phenol removal mixes the charging as fixed bed hydrogenation device with the cut distillated lower than cut point described in step (3), hydrofining reaction is carried out under Hydrobon catalyst effect, fractionation is carried out to hydrorefined product, obtains petroleum naphtha and diesel oil.
Described Hydrobon catalyst is any one or a few in Co-Mo, Ni-Mo, Co-W, Ni-W.
The condition of described fixed bed hydrogenation reaction is: temperature be 220 ~ 450 DEG C, pressure is 12.0 ~ 18.0MPa, volume space velocity is 0.5 ~ 2.0h
-1, hydrogen to oil volume ratio is 500 ~ 3000.
In the middle coalite tar in described step (1), add one or more in coal-tar heavy oil, residual oil, one or more in high-sulfur heavy resid, high asphalt content heavy resid, high heavy metal content heavy resid selected by wherein said residual oil.
Described hydrocracking catalyst is the nanometer materials containing any one or a few in hydrogenation active component Fe, Co, Ni, Mo, W.
In described step (3) higher than the heavy oil fraction of cut point first after thermal pretreatment, then with hydrocracking catalyst, H
2mixing.
Described preheating temperature is 100 ~ 250 DEG C.
Described one-level slurry reactor temperature 350 ~ 550 DEG C, secondary slurry reactor temperature is 350 ~ 550 DEG C, and other reaction conditionss 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 is 1200 ~ 5000.
The present invention compared with prior art tool has the following advantages:
(1) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, first centering coalite tar carries out purifying treatment, and the object of purifying treatment is the solid impurity, water etc. that contain in coalite tar in removing; And then coalite tar in after purifying treatment is reduced pressure or air distillation, cut into light oil distillate and heavy oil fraction, the temperature range being cut point with 320 ~ 380 DEG C, because the light oil distillate of sufficient quantity can be contained in the heavy oil fraction in this cutting temperature scope, and the existence of this part light oil distillate has collaborative promoter action to heavy oil fraction in follow-up secondary slurry bed system hydrocracking, it can improve the hydrogenation conversion of this part heavy oil fraction greatly.The liquid fuel adopting the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention to prepare has the advantage that hydrogen consumption is low, product yield is high, and obtain S in the product petroleum naphtha that obtains through further fractionation lower than the light oil distillate of cut point temperature and diesel oil, N content after the hydrocracking of two-stage slurry bed system far below S, N content in the liquid fuel prepared in prior art, and diesel-fuel cetane number improves greatly.
(2) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, further define after first phenol removal is carried out to the light oil distillate lower than cut point, mix with the cut lower than the cut point of 320 ~ 380 DEG C obtained after the hydrocracking of two-stage slurry bed system again, then be fixed bed hydroprocessing to refine, this is because containing a large amount of phenols in middle coalite tar light ends, suitable technology is adopted to propose in phenol therefrom coalite tar lighting end, as product, it has very high marketable value, simultaneously because a large amount of phenols is suggested, it is lower that the oxygen level of middle coalite tar lighting end is fallen, significantly reduce its hydrogenation hydrogen consumption, and avoid the phenols of high value to become the hydro carbons such as benzene.The cut distillated lower than cut point described in light oil distillate after dephenolize goes out with through two-stage slurry bed system hydrogenation aftercut mixes the charging as fixed bed hydrogenation device, be fixed the transformation efficiency that can improve middle coalite tar of the present invention after bed hydroprocessing is refined further again, and obtain the S of product petroleum naphtha and diesel oil after hydrofining, N content reduces further, diesel-fuel cetane number improves further.
(3) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, further, coal-tar heavy oil can also be added in middle coalite tar, one or more in residual oil form mixture, above-mentioned steps is adopted to carry out shortening to this mixture again, owing to being provided with the cut point of 320 ~ 380 DEG C equally to this mixture, and can light oil distillate containing sufficient quantity in heavy oil fraction in mixture on this cut point, and the existence of this part light oil distillate has collaborative promoter action to the heavy oil fraction in mixture in follow-up two-stage slurry bed system hydrocracking, it can improve the hydrogenation conversion of the heavy oil fraction in this part mixes greatly.Therefore, adopt the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, not only can carry out shortening by centering coalite tar, can also carry out shortening by the mixture that formed of centering coalite tar, coal-tar heavy oil, residual oil, and the liquid fuel prepared has equally, and hydrogen consumption is low, advantage that product yield is high.
(4) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, further, can also select the heavy oil fraction to being greater than cut point temperature to carry out thermal pretreatment, then with hydrocracking catalyst, H
2mixing, can make this part heavy oil fraction and catalyzer, H like this
2what mix is more even, so that improve its hydrogenation catalyst efficiency further.
(5) the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention, the cut lower than cut point obtained after slurry bed system hydrotreatment enters fixed bed hydrogenation device under hot, greatly improves thermo-efficiency; And adopt the cut in slurry bed system process in coalite tar more than cutting temperature, the problem that the on-stream time that causes hydrogenation unit pressure drop to be risen fast causing due to coking and metal deposition is short can be avoided; In addition the present invention also controls slurry bed system device per pass conversion, and outer row's part high boiling fraction, can by remove metal, Jiao of knot and used catalyst discharger, the steady running of assurance device long period.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the two-stage slurry bed system hydrogenation technique of middle coalite tar of the present invention;
Reference numeral is as follows:
1. coalite tar raw material in; 2. purifying treatment; 3. normal pressure or vacuum still; 4. higher than the cut of cut point; 5. lower than the cut of cut point; The cut of the > 540 DEG C of 6.3 ~ 8%; 7. one-level slurry reactor device; 8. secondary slurry reactor device; 9. fixed-bed reactor; 10. all the other cuts; 11. petroleum naphthas; 12. diesel oil.
Embodiment
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 dewatering, the purifying treatment of removal of impurities, in after dehydration, coalite tar water content is less than 0.5wt%;
(2) by the middle coalite tar air distillation after purifying treatment in described step (1), cut 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 hydrocracking catalyst, H
2mixing, wherein, described hydrocracking catalyst is nanometer materials, and it consists of 50wt% alpha-feooh, and surplus is γ-Al
2o
3enter one-level slurry bed system successively after mixing, secondary slurry bed system carries out two-stage hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactor temperature is 350 DEG C, secondary slurry reactor temperature is 350 DEG C, and other reaction conditions of one-level slurry bed system and secondary slurry bed system is: pressure is 18.0MPa, volume space velocity is 0.5h
-1, hydrogen to oil volume ratio is 1200; Fractionation process is carried out to the hydrocracked product prepared, adopts the temperature range of cut point described in step (2) to carry out fractionation to hydrocracked product, the cut lower than 320 DEG C is distillated, continue fractionation and obtain petroleum naphtha and diesel product; The cut of the > 540 DEG C of 3 ~ 8% is arranged outward, and all the other loop back one-level paste state bed reactor.
In in above-described embodiment, the total conversion rate of coalite tar is 92.4%, diesel oil total recovery 39.7%.
Embodiment 2
(1) in purification apparatus centering coalite tar carry out dewatering, the purifying treatment of removal of impurities, in after dehydration, coalite tar water content is less than 0.5wt%;
(2) by the middle coalite tar underpressure distillation after purifying treatment in described step (1), cut 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 hydrocracking catalyst, H
2mixing, wherein, described hydrocracking catalyst is nanometer materials, and it consists of 25wt%MoO
3, 5wt%NiO, surplus be γ-Al
2o
3enter one-level slurry bed system successively after mixing, secondary slurry bed system carries out two-stage hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactor temperature is 400 DEG C, secondary slurry reactor temperature is 400 DEG C, and other reaction conditions of one-level slurry bed system and secondary slurry bed system is: pressure is 16.0MPa, volume space velocity is 1.0h
-1, hydrogen to oil volume ratio is 1600; Fractionation process is carried out to the hydrocracked product prepared, adopts the temperature range of cut point described in step (2) to carry out fractionation to hydrocracked product, the cut lower than 340 DEG C is distillated, continue fractionation and obtain petroleum naphtha and diesel product; The cut of the > 540 DEG C of 3 ~ 8% is arranged outward, and all the other loop back one-level paste state bed reactor;
(4) light oil distillate lower than 340 DEG C of cut points in described step (2) is carried out phenol removal, the phenol removed goes out device as product; Light oil distillate after phenol removal mixes the charging as fixed bed hydrogenation device with the cut lower than 340 DEG C described in step (3), under Hydrobon catalyst effect, carry out hydrofining reaction, the condition of described fixed bed hydrogenation reaction is: temperature be 220 DEG C, pressure is 18.0MPa, volume space velocity is 0.5h
-1, hydrogen to oil volume ratio is 500; Hydrofining reaction is carried out, wherein said Hydrobon catalyst composed as follows: 7wt%NiO, 20wt%MoO under Hydrobon catalyst effect
3, surplus is ZSM-5 molecular sieve, fractionation is carried out to hydrorefined product, obtains petroleum naphtha and diesel oil;
In in above-described embodiment, the total conversion rate of coalite tar is 94.7%, diesel oil total recovery 73%, phenol yield 9.7%.
Embodiment 3
(1) in purification apparatus the mixture of centering coalite tar, residual oil carry out dewatering, the purifying treatment of removal of impurities, wherein said residual oil is chosen as the mixture of high-sulfur heavy resid, high heavy metal content heavy resid, the mass ratio of described middle coalite tar, high-sulfur heavy resid, high heavy metal content heavy resid is 5:0.5:0.5, and the mixture water content after dehydration is less than 0.5wt%;
(2) by the middle coalite tar underpressure distillation after purifying treatment in described step (1), cut into light oil distillate and heavy oil fraction, cut point is 360 DEG C;
(3) heavy oil fraction higher than 360 DEG C of cut points in described step (2) is carried out thermal pretreatment at 100 DEG C, then with hydrocracking catalyst, H
2mixing, wherein, described hydrocracking catalyst is nanometer materials, and it consists of 5wt%NiO, 30wt%WO
3surplus is natural zeolite molecular sieve, enter one-level slurry bed system successively after mixing, secondary slurry bed system carries out two-stage hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactor temperature is 455 DEG C, secondary slurry reactor temperature is 455 DEG C, and other reaction conditions of one-level slurry bed system and secondary slurry bed system is: pressure is 12.0MPa, volume space velocity is 0.5h
-1, hydrogen to oil volume ratio is 2500; Fractionation process is carried out to the hydrocracked product prepared, adopts the temperature range of cut point described in step (2) to carry out fractionation to hydrocracked product, the cut lower than 360 DEG C is distillated, continue fractionation and obtain petroleum naphtha and diesel product; The cut of the > 540 DEG C of 3 ~ 8% is arranged outward, and all the other loop back one-level paste state bed reactor;
(4) light oil distillate lower than 360 DEG C of cut points in described step (2) is carried out phenol removal, the phenol removed goes out device as product; Light oil distillate after phenol removal mixes the charging as fixed bed hydrogenation device with the cut lower than 360 DEG C described in step (3), under Hydrobon catalyst effect, carry out hydrofining reaction, the condition of described fixed bed hydrogenation reaction is: temperature be 360 DEG C, pressure is 14.0MPa, volume space velocity is 1.0h
-1, hydrogen to oil volume ratio is 900; Hydrofining reaction is carried out, wherein said Hydrobon catalyst composed as follows: 7wt%NiO, 35wt%CoO, surplus are ZSM-5 molecular sieve, carry out fractionation to hydrorefined product, obtain petroleum naphtha and diesel oil under Hydrobon catalyst effect;
In above-described embodiment, the total conversion rate of coal oil mixture is 95.2%, diesel oil total recovery 78%, phenol yield 9%.
Embodiment 4
(1) in purification apparatus the mixture of centering coalite tar and coal-tar heavy oil carry out dewatering, the purifying treatment of removal of impurities, wherein, the mass ratio of described middle coalite tar and coal-tar heavy oil is 3:1, and the mixture water content after dehydration is less than 0.5wt%;
(2) by the middle coalite tar air distillation after purifying treatment in described step (1), cut into light oil distillate and heavy oil fraction, cut point is 355 DEG C;
(3) heavy oil fraction higher than 355 DEG C of cut points in described step (2) is carried out thermal pretreatment at 150 DEG C, then with hydrocracking catalyst, H
2mixing, wherein, described hydrocracking catalyst is nanometer materials, and it consists of it and consists of 5wt%CoO, 35wt%MoO
3surplus is natural zeolite molecular sieve, enter one-level slurry bed system successively after mixing, secondary slurry bed system carries out two-stage hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactor temperature is 500 DEG C, secondary slurry reactor temperature is 500 DEG C, and other reaction conditions of one-level slurry bed system and secondary slurry bed system is: pressure is 16.0MPa, volume space velocity is 1.5h-1, hydrogen to oil volume ratio is 3500; Fractionation process is carried out to the hydrocracked product prepared, adopts the temperature range of cut point described in step (2) to carry out fractionation to hydrocracked product, the cut lower than 355 DEG C is distillated, continue fractionation and obtain petroleum naphtha and diesel product; The cut of the > 540 DEG C of 3 ~ 8% is arranged outward, and all the other loop back one-level paste state bed reactor;
(4) light oil distillate lower than 355 DEG C of cut points in described step (2) is carried out phenol removal, the phenol removed goes out device as product; Light oil distillate after phenol removal mixes the charging as fixed bed hydrogenation device with the cut lower than 355 DEG C described in step (3), under Hydrobon catalyst effect, carry out hydrofining reaction, the condition of described fixed bed hydrogenation reaction is: temperature be 400 DEG C, pressure is 14.0MPa, volume space velocity is 1.5h
-1, hydrogen to oil volume ratio is 2000; Hydrofining reaction is carried out, wherein said Hydrobon catalyst composed as follows: 27wt%WO under Hydrobon catalyst effect
3, 10wt%CoO, surplus be ZSM-5 molecular sieve, fractionation is carried out to hydrorefined product, obtains petroleum naphtha and diesel oil.
In above-described embodiment, the total conversion rate of coal oil mixture is 98.8%, diesel oil total recovery 79.4%, phenol yield 10.6%.
Embodiment 5
(1) in purification apparatus the mixture of centering coalite tar, residual oil carry out dewatering, the purifying treatment of removal of impurities, high asphalt content heavy resid selected by wherein said residual oil, the mass ratio of described middle coalite tar, residual oil is 5:1, and the coal oil mixture water content after dehydration is less than 0.5wt%;
(2) by the middle coalite tar air distillation after purifying treatment in described step (1), cut into light oil distillate and heavy oil fraction, cut point is 380 DEG C;
(3) heavy oil fraction higher than 380 DEG C of cut points in described step (2) is carried out thermal pretreatment at 250 DEG C, then with hydrocracking catalyst, H
2mixing, wherein, described hydrocracking catalyst is nanometer materials, and it consists of it and consists of 5wt%Fe
2o
3, 35wt%WO
3surplus is natural zeolite molecular sieve, enter one-level slurry bed system successively after mixing, secondary slurry bed system carries out two-stage hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactor temperature is 550 DEG C, secondary slurry reactor temperature is 550 DEG C, and other reaction conditions of one-level slurry bed system and secondary slurry bed system is: pressure is 10.0MPa, volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 5000; Carry out fractionation process to the hydrocracked product prepared, adopt the temperature range of cut point described in step (2) to carry out fractionation to hydrocracked product, distillated by the cut lower than 380 DEG C, overhead product continues after fractionation, obtain petroleum naphtha and diesel product; The cut of the > 540 DEG C of 3 ~ 8% is arranged outward, and all the other loop back one-level paste state bed reactor;
(4) light oil distillate lower than 380 DEG C of cut points in described step (2) is carried out phenol removal, the phenol removed goes out device as product; Light oil distillate after phenol removal mixes the charging as fixed bed hydrogenation device with the cut lower than 380 DEG C described in step (3), under Hydrobon catalyst effect, carry out hydrofining reaction, the condition of described fixed bed hydrogenation reaction is: temperature be 450 DEG C, pressure is 12.0MPa, volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 3000; Hydrofining reaction is carried out, wherein said Hydrobon catalyst composed as follows: 7wt%NiO, 35wt%CoO, surplus are ZSM-5 molecular sieve, carry out fractionation to hydrorefined product, obtain petroleum naphtha and diesel oil under Hydrobon catalyst effect;
In above-described embodiment, the total conversion rate of coal oil mixture is 97.4%, diesel oil total recovery 76.4%, phenol yield 8.7%.
In addition, present invention also offers coal-tar heavy oil used, middle coalite tar, slag oil properties in above-mentioned all embodiments, as shown in table 1, and further provide the petroleum naphtha and bavin oil properties that prepare, as shown in table 2.
Table 1 raw material oil properties
| Stock oil | Coal-tar heavy oil | Middle coalite tar | Residual oil |
| Density g/cm 3 | 1.18 | 1.002 | 0.94 |
| S，wt% | 0.3 | 0.3 | 2.1 |
| O，wt% | 1 | 6.5 | - |
| N，wt% | 0.8 | - | - |
| Ash content, wt% | - | - | 0.045 |
| Ni+V，ppm | - | - | 110 |
| C7 insolubles, wt% | ＜9 | 4.5 | - |
The petroleum naphtha that table 2 prepares and bavin oil properties
comparative example
The present invention adopts the embodiment provided in documents CN103059973A as comparative example of the present invention, its with the full cut of coal-tar heavy oil for raw material, adopt following technique: the water in pre-treatment removing raw material and mechanical impurity, mix with hydrocracking catalyst and enter paste state bed reactor, hydrocracking catalyst is 35%WO
3, 10%NiO, 3%P
2o
5, surplus is USY molecular sieve, hydrocracking condition is as follows: preheating temperature 150 DEG C, reaction pressure break 12MPa, temperature of reaction are 390 DEG C, volume space velocity 0.5h
-1, hydrogen to oil volume ratio is 1600, head product after hydrocracking enters separation column, lighting end enters back segment fixed-bed reactor and carries out hydrofining, this part cut accounts for 15wt%, middle runnings is about 65wt% and loops back paste state bed reactor continuation hydrocracking, raw material storage tank is entered after the coke that the heavy ends of about 20wt% produces in remove portion catalyzer and reaction process after filtration, the cyclic utilization rate of catalyzer is about 80%, wherein light ends fixed bed hydrogenation refining reaction condition is as follows: reaction pressure 8MPa, temperature of reaction 375 DEG C, volume space velocity 0.5h
-1, hydrogen to oil volume ratio 1600; Fixed bed refine after product obtain gasoline and diesel oil through fractionation, the performance of the gasoline prepared is as follows: density 0.7995g/cm
-3, sulphur content < 50ppm, nitrogen content < 50ppm, octane value 91.5, the performance of the diesel oil distillate prepared is as follows: density 0.7995g/cm
-3, sulphur content < 50ppm, nitrogen content < 50ppm, cetane value 35.6;
From above-mentioned comparative example, the petroleum naphtha adopting the method for the invention to prepare, the sulphur content of diesel oil, nitrogen content reduce greatly, and diesel-fuel cetane number also improves greatly.
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 claim.
Claims (9)
1. in, a two-stage slurry bed system hydrogenation technique for coalite tar, comprises the steps:
(1) centering coalite tar carries out purifying treatment;
(2) carried out reducing pressure or air distillation by the middle coalite tar after purifying 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, H
2mixing, enter one-level slurry bed system successively after mixing, secondary slurry bed system carries out two-stage hydrocracking reaction, fractionation process is carried out to the hydrocracked product prepared, the temperature range of cut point described in step (2) is adopted to carry out fractionation to hydrocracked product, cut lower than above-mentioned cut point is distillated, obtain petroleum naphtha and diesel product after the further fractionation of the product distillated, the cut of the > 540 DEG C of 3 ~ 8% is arranged outward, and all the other loop back one-level paste state bed reactor.
2. according to claim 1 in the two-stage slurry bed system hydrogenation technique of coalite tar, it is characterized in that, the light oil distillate lower than cut point in described step (2) is carried out phenol removal, and the phenol removed goes out device as product; Light oil distillate after phenol removal mixes the charging as fixed bed hydrogenation device with the cut distillated lower than cut point described in step (3), hydrofining reaction is carried out under Hydrobon catalyst effect, fractionation is carried out to hydrorefined product, obtains petroleum naphtha and diesel oil.
3. according to claim 2 in the two-stage slurry bed system hydrogenation technique of coalite tar, it is characterized in that, described Hydrobon catalyst is any one or a few in Co-Mo, Ni-Mo, Co-W, Ni-W.
4. the two-stage slurry bed system hydrogenation technique of coalite tar according to Claims 2 or 3, is characterized in that, the condition of described fixed bed hydrogenation reaction is: temperature be 220 ~ 450 DEG C, pressure is 12.0 ~ 18.0MPa, volume space velocity is 0.5 ~ 2.0h
-1, hydrogen to oil volume ratio is 500 ~ 3000.
5., according to the two-stage slurry bed system hydrogenation technique of the arbitrary described middle coalite tar of Claims 1 to 4, it is characterized in that, add in the middle coalite tar in described step (1) coal-tar heavy oil, residual oil, one or more.
6. according to the two-stage slurry bed system hydrogenation technique of the arbitrary described middle coalite tar of Claims 1 to 5, it is characterized in that, described hydrocracking catalyst is the nanometer materials containing any one or a few in hydrogenation active component Fe, Co, Ni, Mo, W.
7., according to the two-stage slurry bed system hydrogenation technique of the arbitrary described middle coalite tar of claim 1 ~ 6, it is characterized in that, in described step (3) higher than the heavy oil fraction of cut point first after thermal pretreatment, then with hydrocracking catalyst, H
2mixing.
8. according to claim 7 in the two-stage slurry bed system hydrogenation technique of coalite tar, it is characterized in that, described preheating temperature is 100 ~ 250 DEG C.
9. according to the two-stage slurry bed system hydrogenation technique of the arbitrary described middle coalite tar of claim 1 ~ 8, it is characterized in that, described one-level slurry reactor temperature 350 ~ 550 DEG C, secondary slurry reactor temperature is 350 ~ 550 DEG C, and other reaction conditionss 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 is 1200 ~ 5000.
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