CN102807896B - Hydrotreating method for maximum production of middle distillates - Google Patents
Hydrotreating method for maximum production of middle distillates Download PDFInfo
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Abstract
The invention relates to a hydrotreating method for maximum production of middle distillates. The method comprises the following steps that: fresh feedstock oils are simultaneously introduced into a hydrofining reactor and a hydrocracking reactor in a co-current flow way; the hydrofining reactor is sequentially filled with a hydrofining catalyst and an amorphous hydrocracking catalyst; the hydrocracking reactor is sequentially filled with an amorphous hydrocracking catalyst and a zeolite hydrocracking catalyst; and all or part of the tail oil fractions are introduced into the hydrocracking reactor, and a reaction effluent from the hydrocracking reactor and part of the feedstock oils are introduced into the hydrofining reactor together. According to the method provided by the invention, the heavy distillates can be treated, and the maximum production of the middle distillates can be realized. Only the tail oil fractions are introduced into the hydrocracking reactor, so that the selectivity of middle distillates is improved; and part of the feedstock oils is introduced into the hydrocracking reactor, so that the phenomenon that more middle distillates are cracked secondarily in an ammonia-free environment in the hydrocracking reactor is avoided, and thus the yield of the middle distillates is effectively improved.
Description
Technical field
The invention belongs to a kind of method for hydrogen cracking obtaining low boiler cut hydrocarbon ils in the presence of hydrogen.
Background technology
Along with being deteriorated year by year and environmental requirement increasingly strict in world wide of crude quality, as the hydrocracking process of one of the Main Means of crude oil secondary operations, heavy oil lighting, because adaptability to raw materials is strong, production decision is flexible, liquid product yield is high, good product quality, produce in clean fuel process at sulfur-bearing and sour crude deep processing and play more and more important effect, its range of application is also increasingly extensive.
In recent years, market to all kinds of oil product especially to the sustainable growth of high-quality intermediate oil product consumption, the pressure of refinery's production high-quality midbarrel oil product is also increasing, and therefore, oil type hydrocracking technique plays more and more important effect in production clean fuel process.
Hydrocracking process generally can be divided into single dose single stage process, single hop tandem process and two-stage process.Adopt the single stage process of amorphous hydrocracking catalyst to be once that maximum produces the main processes of intermediate oil, but its deficiency to be initial reaction temperature higher, catalyst on-stream cycle time is shorter, and is difficult to process heavier inferior raw material.Although two-stage process device operating flexibility is comparatively large, adaptability to raw material is strong, flow process relative complex, the investment of infrastructure investment, catalyst and running cost all relatively high.One-stage serial technical process adopts the pattern of hydrofinishing, hydrocracking catalyst serial operation usually, usually active higher molecular sieve type catalyst is adopted in hydrocracking section, in raw material, organic nitrogen compound is to the adverse effect of hydrocracking catalyst activity, need first to carry out hydrofinishing pretreatment to raw material, the nitrogen impurity content in raw material is down to enough low level.Relative to amorphous hydrocracking catalyst, molecular sieve type hydrocracking catalyst activity is high, and initial reaction temperature is low, but intermediate oil yield is relatively low.
WO97/38066 discloses the inverted sequence series connection method in a kind of hydroprocessing reactor assembly.Fresh feed is delivered to hydrofinishing section by the method together with the effluent of hydrocracking reaction section, and the product of hydrofinishing section is at purification and cooling section removing NH
3and H
2s also obtains hydrogen-rich gas and liquid phase stream after cooling, and hydrogen-rich gas returns hydrocracking reaction section, and liquid phase stream enters the unconverted oil and other light fractions that distillation stage obtains, and gained unconverted oil returns hydrocracking reaction section.The method can further improve hydrocracked product quality.
US6296758 discloses a kind of method for hydrogen cracking improving intermediate oil yield.The method is on the basis of WO97/38066 method, and arrange a special Reaction Separation device, top is gas phase hydrogenation refining reaction section, and bottom is air lift segregation section.The method can realize unconverted oil circulation under operating pressure, thus realizes the economical operation under low conversion per pass, improves product quality.
CN1216967C discloses the two-stage reforming technique that a kind of maximum produces intermediate oil.The method adopts " order stream " and the group technology route of " concurrent flow ".Adopt hydrotreatment and hydrocracking series connection at " order stream " hydrocracking section, obtain the light-end products of about 50%, only adopt amorphous hydrocracking catalyst to carry out the circulation cracking of tail oil at " concurrent flow " hydrocracking section.The method maximum can produce intermediate oil, and according to circumstances can adjust production decision flexibly, maximum diesel oil yield or jet fuel.
Prior art adopts the pattern of hydrofinishing, hydrocracking catalyst serial operation usually.The present inventor finds, under this operator scheme, because raw material has carried out weighted BMO spaces through hydrofinishing section, while refining stage carries out desulfurization, denitrification reaction, also a small amount of lighting reaction can be there is, relative in this cracking zone charging of feedstock oil by containing part (usually 10% ~ 20%) midbarrel, feedstock oil after refining directly contacts the very high hydrocracking catalyst of cracking activity, easily there is more secondary cracking reaction in midbarrel, thus reduces the yield of intermediate oil.The present invention is in order to overcome this problem, and first refining stage outlet oil be separated through fractionating column before entering cracker, midbarrel separated, and avoids the possibility that secondary cracking occurs on hydrocracking catalyst.Relative to the inverted sequence serial hydrocracking method of prior art, the invention provides the technical scheme that fresh feed oil enters the also stream of hydrofinishing section and hydrocracking section simultaneously; At the direct introducing portion fresh feed of hydrocracking section, the cracking activity of hydrocracking catalyst is suppressed by organonitrogen compound in fresh feed, under preventing hydrocracking reaction Duan Wu ammonia environment, cracking activity is excessively strong, cause the secondary cracking of more intermediate oil, thus further increase the yield of intermediate oil.In addition, this part fresh feed oil enters the technical scheme of hydrocracking section, can prevent the too low concentration of hydrogen sulfide of hydrocracking reaction section from causing hydrocracking catalyst to reduce under high hydrogen partial pressure conditions, make the problem of the activity of hydrocracking catalyst, the hydraulic performance decline such as selective.In addition, the hydrogen-rich stream effluent of hydrocracking reactor enters into hydrofining reactor again, can save recycle hydrogen consumption.The ratio that described feedstock oil enters hydrofining reactor and hydrocracking reactor is 20:1 ~ 1:2.H in the atmosphere of described hydrocracking reactor
2s dividing potential drop is 0.01 ~ 0.30MPa, NH
3dividing potential drop is 0.001 ~ 0.05MPa.
The charging of described hydrofining reactor is: the reaction effluent of part fresh feed oil and whole hydrocracking reactor.Reaction condition in described hydrofining reactor: reaction temperature 300 ~ 450 DEG C, reaction pressure 3.0 ~ 20.0MPa, hydrogen to oil volume ratio 300 ~ 2000 is 0.1 ~ 5.0h to the volume space velocity of fresh feed oil
-1.In addition, hydrofining reactor bottom filling part amorphous hydrocracking catalyst, relative to molecular sieve type hydrocracking catalyst, the feature of amorphous hydrocracking catalyst is that to have high intermediate oil selective, transformed by the high selectivity making feedstock oil carry out to a certain degree at refining stage, and by being separated by the intermediate oil of hydrofinishing section product before entering hydrocracking reactor, can further improve the yield of intermediate oil.
Described Hydrobon catalyst be load at amorphous alumina or/and the loaded catalyst of group vib base metal on silica or VIII base metal or its combination.Preferred Hydrobon catalyst is with γ-Al
2o
3for carrier, catalyst activity component is selected from one or more in Mo, W, Co, Ni of group vib and group VIII metal component.
Amorphous hydrocracking catalyst by amorphous aluminum silicate or/and aluminium oxide and load base metal thereon forms.The difference of amorphous aluminum silicate and alumina/silica mechanical impurity is to form chemical bond between the former Silicified breccias.
Preferred amorphous hydrocracking catalyst: overall for benchmark with amorphous hydrocracking catalyst, with oxide basis, amorphous hydrocracking catalyst consists of: aluminium oxide 10 % by weight ~ 45 % by weight, amorphous aluminum silicate 55 % by weight ~ 73 % by weight, group vib metal 15 % by weight ~ 35 % by weight, group VIII metal 2 % by weight ~ 8 % by weight.Described group vib metal, group VIII metal are selected from one or more in Mo, W, Ni, Co.
The reaction effluent of hydrofining reactor successively through fractionation be separated, obtain light naphtha fraction (being less than 65 DEG C), heavy naphtha fraction (65 ~ 145 DEG C), intermediate oil (145 ~ 370 DEG C) and tail oil fraction (being greater than 370 DEG C).
The charging of described hydrocracking reactor is: all or part of tail oil, and part fresh feed oil.Reaction condition in described hydrocracking reactor: reaction temperature is 300 ~ 450 DEG C, reaction pressure 3.0 ~ 25.0MPa, hydrogen to oil volume ratio 300 ~ 2000, volume space velocity is 0.5 ~ 8.0h
-1(for chargings all in hydrocracking reactor).
Hydrocracking reactor loads two kinds of Cracking catalyst, load on the top of molecular sieve hydrocracking catalyst that anti-nitrogen performance is good, the selective good amorphous hydrocracking catalyst of intermediate oil, the adaptability of cracking reaction district to raw material can be improved, be conducive to the yield improving product intermediate oil further.
Amorphous hydrocracking catalyst by amorphous aluminum silicate or/and aluminium oxide and load base metal thereon forms.The amorphous Cracking catalyst that the amorphous Cracking catalyst of hydrofining reactor bottom filling and hydrocracking reactor top are loaded, can be identical, also can be different.Preferred amorphous hydrocracking catalyst: overall for benchmark with amorphous hydrocracking catalyst, with oxide basis, amorphous hydrocracking catalyst consists of: aluminium oxide 10 % by weight ~ 45 % by weight, amorphous aluminum silicate 55 % by weight ~ 73 % by weight, group vib metal 15 % by weight ~ 35 % by weight, group VIII metal 2 % by weight ~ 8 % by weight.Described group vib metal, group VIII metal are selected from one or more in Mo, W, Ni, Co.
Described molecular sieve hydrocracking catalyst is made up of a kind of carrier and load base metal on this carrier, and this carrier is made up of amorphous aluminum silicide and molecular sieve; Described amorphous aluminum silicide is selected from one or more in silica, aluminium oxide, amorphous aluminum silicate.
Preferred molecular sieve hydrocracking catalyst: overall for benchmark with molecular sieve hydrocracking catalyst, with oxide basis, molecular sieve hydrocracking catalyst consists of: aluminium oxide 30 % by weight ~ 72 % by weight, amorphous aluminum silicate 10 % by weight ~ 52 % by weight, molecular sieve 1 % by weight ~ 15 % by weight, group vib metal 15 % by weight ~ 35 % by weight.Group VIII metal 2 % by weight ~ 8 % by weight.
One or more in faujasite, modenite, zeolite L, omega zeolite, Beta zeolite of described molecular screening.Described non-noble metal components is one or more of Mo, W, Co, the Ni being selected from group vib and group VIII metal component in the periodic table of elements.
Advantage of the present invention is:
1, method provided by the invention can process heavy distillate, and maximum produces intermediate oil.Compared with conventional one-stage serial hydrocracking method, the present invention only has tail oil fraction to enter hydrocracking section, improves the selective of intermediate oil.Compared with the inverted sequence serial hydrocracking method of prior art, after fresh feed oil is introduced hydrocracking reactor in the mode of " and stream " by the present invention, the ammonia that organonitrogen compound wherein and following reaction generate partly can suppress the cracking activity of hydrocracking catalyst, prevent in hydrocracking reactor excessively strong without the cracking activity of hydrocracking catalyst under ammonia environment, cause the generation of the secondary cracking phenomenon of more intermediate oil, thus be conducive to the yield improving intermediate oil.
2, compared with the inverted sequence serial hydrocracking method of prior art, the introducing of fresh feed oil adds the sulfur content in hydrocracking reaction system, improves H
2the dividing potential drop of S, can the activity and selectivity of available protecting sulphided state hydrocracking catalyst.
3, hydrofining reactor loads Hydrobon catalyst and has high intermediate oil optionally amorphous hydrocracking catalyst, and the conversion level of refining reaction product improves.Before hydrofining reaction product enters hydrocracking reactor, by fractionating system, midbarrel is wherein separated, improve the yield of intermediate oil.Hydrocracking reactor loads amorphous hydrocracking catalyst and molecular sieve hydrocracking catalyst, can improve the adaptability of hydrocracking reaction section to raw material, and is conducive to the yield improving product intermediate oil further.
Summary of the invention
The object of the invention is on prior art basis, provide a kind of maximum to produce the method for hydrotreating of intermediate oil.
Method provided by the invention comprises:
(1), after feedstock oil mixes with hydrogen, enter hydrofining reactor and hydrocracking reactor by a certain percentage simultaneously;
(2) reaction effluent of hydrofining reactor enters high-pressure separator, low pressure separator, fractionating column successively, is separated obtains light naphtha fraction, heavy naphtha fraction, intermediate oil and tail oil fraction by fractionating column;
(3) all or part of tail oil fraction enters hydrocracking reactor, and the reaction effluent of hydrocracking reactor enters hydrofining reactor together with part material oil.
(4) hydrofining reactor loads Hydrobon catalyst and amorphous hydrocracking catalyst successively, the admission space ratio of Hydrobon catalyst and amorphous hydrocracking catalyst is 4:1 ~ 1:2, hydrocracking reactor loads amorphous hydrocracking catalyst and molecular sieve hydrocracking catalyst successively, and the admission space ratio of amorphous hydrocracking catalyst and molecular sieve hydrocracking catalyst is 1:3 ~ 3:1.
Described feedstock oil is selected from one or more in straight run vacuum gas oil (VGO), wax tailings, deasphalted oil, and boiling range is 260-700 DEG C, and sulfur content is not more than 50000 μ g/g, and nitrogen content is not more than 5000 μ g/g.The sulfur content of preferred described feedstock oil is not more than 40000 μ g/g, and nitrogen content is not more than 2000 μ g/g.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet of the method for hydrotreating of production intermediate oil provided by the present invention.
Detailed description of the invention
Accompanying drawing is the schematic flow sheet that the invention provides method, eliminates much equipment in figure, as pump, heat exchanger, compressor etc., but for a person skilled in the art, is known.
Below in conjunction with accompanying drawing, to method provided by the present invention, be further described, but not thereby limiting the invention.As shown in drawings, feedstock oil enters storage tank 1 through pipeline 9, new hydrogen enters after make-up hydrogen compressor 2 supercharging through pipeline 10 and mixes with feedstock oil, mixture enters heating furnace 12 through pipeline 11, mixture after heating is divided into two-way: a route pipeline 13 enters hydrofining reactor 4, and another route pipeline 14 enters hydrocracking reactor 3.Under Hydrobon catalyst and amorphous hydrocracking catalyst and effect, desulfurization, denitrogenation, olefin saturated, aromatic saturation reaction and partial cracking reaction is there is at hydrofining reactor 4 Raw oil and hydrogen, reaction effluent enters high-pressure separator 5 through pipeline 28 after flowing through heat exchange, cooling and carries out gas-liquid separation, the hydrogen rich stream at high-pressure separator 5 top enters circulating hydrogen compressor 6 by pipeline 15, and after circulating hydrogen compressor supercharging, point two curb pipelines 18 and pipeline 29 enter hydrofining reactor 4 and hydrocracking reactor 3 respectively.Acid water bottom high-pressure separator 5 is discharged through pipeline 17, and high-pressure separator 5 lower liquid phase stream passes via line 16 enters low pressure separator 7, carries out further gas-liquid separation at this.The isolated gas of mortgage separator 7 is extracted out through pipeline 19; Acid water bottom low pressure separator 7 is discharged through pipeline 21; The liquid phase stream of low pressure separator 7 bottom enters fractionating column through pipeline 20.Fractionating column 8 tower top separates lighter hydrocarbons and light naphtha fraction is extracted out through pipeline 22, and heavy naphtha fraction is extracted out through top side line 23, and intermediate oil is extracted out through bottom side line 24, and tail oil fraction at the bottom of tower is extracted out through pipeline 25, after be divided into two-way.All or part of tail oil fraction through pipeline 27 Posterior circle to hydrocracking reactor 3 entrance, react under effect at amorphous hydrocracking catalyst and molecular sieve hydrocracking catalyst together with part fresh feed oil, the reaction product of bottom enters hydrofining reactor 4.Alternatively by part tail oil fraction through pipeline 26 withdrawing device.
The following examples to method provided by the invention, will be further described, but not thereby limiting the invention.
Feedstock oil A used in embodiment is a kind of VGO, and its main character is as shown in table 1.
In embodiment, the trade names of hydrofining reactor filling hydrogenation protecting catalyst are RG-1, and the trade names of the Hydrobon catalyst of top filling are RN-32V, and amorphous hydrocracking catalyst is loaded in bottom, its trade names RHC-140.Amorphous hydrocracking catalyst is loaded on hydrocracking reactor top, its trade names RHC-140, and bottom filling molecular sieve hydrocracking catalyst, its trade names are RHC-131.Identical catalyst and type of feed is adopted in comparative example.Above-mentioned catalyst is produced by Sinopec catalyst branch company.
Embodiment 1
Be 14.5MPa in reaction pressure, hydrofinishing section reaction temperature 380 DEG C, hydrocracking section reaction temperature 375 DEG C, hydrofinishing section volume space velocity (to fresh feed) is 1.8h
-1, hydrocracking section volume space velocity (to the whole charging of hydrocracking section) is 1.3h
-1reaction condition under, with method for hydrogen cracking provided by the invention, adopt raw material A carried out test.Volume ratio between RN-32V and the RHC-140 of hydrofining reactor filling is 3:1; Volume ratio between catalyst RHC-140 and the RHC-131 of hydrocracking reactor filling is 1:3.The ratio that fresh feed oil enters hydrofining reactor and hydrocracking reactor is 6:1, and tail oil fraction all loops back hydrocracking reactor.H in hydrocracking reactor reaction atmosphere
2s dividing potential drop is 0.021MPa, NH
3dividing potential drop is 0.005MPa.Result of the test is as shown in table 2, and in fresh feed 100%, product boat coal, diesel yield are respectively 42.93% and 39.72%, and intermediate oil total recovery is 82.65%, and total liquid product yield is 98.15%.
Embodiment 2
Be 14.5MPa in reaction pressure, hydrofinishing section reaction temperature 375 DEG C, hydrocracking section reaction temperature 380 DEG C, hydrofinishing section volume space velocity (to fresh feed) is 1.8h
-1, hydrocracking section volume space velocity (to the whole charging of hydrocracking section) is 1.3h
-1reaction condition under, with method for hydrogen cracking provided by the invention, adopt raw material A carried out test, hydrofining reactor filling RN-32V and RHC-140 catalyst ratio be 2:1; Volume ratio between catalyst RHC-140 and the RHC-131 of hydrocracking reactor filling is 1:1.The ratio that fresh feed oil enters hydrofining reactor and hydrocracking reactor is 2:1, and tail oil fraction all loops back hydrocracking reactor.H in hydrocracking reactor reaction atmosphere
2s dividing potential drop is 0.074MPa, NH
3dividing potential drop is 0.018MPa.Result of the test is as shown in table 3, and in fresh feed 100%, product boat coal, diesel yield are respectively 43.22% and 41.05%, and intermediate oil total recovery is 84.27%, and total liquid product yield is 98.40%.
Comparative example
Be 14.5MPa in reaction pressure, hydrofinishing section reaction temperature 380 DEG C, hydrocracking section reaction temperature 350 DEG C, hydrofinishing section volume space velocity (to fresh feed) is 1.8h
-1, hydrocracking section volume space velocity (to the whole charging of hydrocracking section) 1.3h
-1reaction condition under, with inverted sequence serial hydrocracking method, raw material A is adopted to carry out test, fresh feed oil all enters hydrofining reactor, react in hydrofining reactor together with the effluent of hydrocracking reactor, the product of hydrofining reactor is separated and after fractionation, obtain hydrogen-rich gas and return hydrocracking reactor, the tail oil fraction that fractionation obtains all loops back hydrocracking reactor.H in hydrocracking reactor reaction atmosphere
2s dividing potential drop, NH
3dividing potential drop is 0.Result of the test is as shown in table 4, and in fresh feed 100%, product boat coal, diesel yield are respectively 39.49% and 37.06%, and intermediate oil total recovery is 76.55%, and total liquid product yield is 96.30%.
Table 1 feedstock oil character
| Feedstock oil is numbered | A |
| Density (20 DEG C)/(g/cm 3) | 0.9035 |
| S content/% | 1.3 |
| N content/(μ g/g) | 1300 |
| Condensation point/DEG C | 33 |
| Index of refraction/n D 70 | 1.4861 |
| Boiling range (D-1160)/DEG C | |
| Initial boiling point | 277 |
| 10% | 388 |
| 90% | 466 |
| The end point of distillation | 532 |
Table 2
| Product | Naphtha | Boat coal | Diesel oil |
| Boiling range scope/DEG C | <145 | 145-230 | 230-370 |
| Product quality yield/% | 15.50 | 42.93 | 39.72 |
| Density (20 DEG C)/(g/cm 3) | 0.733 | 0.791 | 0.825 |
| Total sulfur/(μ g/g) | <1 | <10 | <10 |
| Total nitrogen/(μ g/g) | <0.5 | <1 | <1 |
| Arene underwater content/% | >45 | / | / |
| Smoke point/mm | / | >25 | / |
| Cetane number | / | / | >65 |
Table 3
| Product | Naphtha | Boat coal | Diesel oil |
| Boiling range scope/DEG C | <145 | 145-230 | 145-370 |
| Liquid product mass yield/% | 14.13 | 43.22 | 41.05 |
| Density (20 DEG C)/(g/cm 3) | 0.735 | 0.792 | 0.827 |
| Total sulfur/(μ g/g) | <1 | <10 | <10 |
| Total nitrogen/(μ g/g) | <0.5 | <1 | <1 |
| Arene underwater content/% | >45 | / | / |
| Smoke point/mm | / | >25 | / |
| Cetane number | / | / | >65 |
Table 4
| Product | Naphtha | Boat coal | Diesel oil |
| Boiling range scope/DEG C | <145 | 145-230 | 230-370 |
| Product quality yield/% | 19.75 | 39.49 | 37.06 |
| Density (20 DEG C)/(g/cm 3) | 0.732 | 0.792 | 0.826 |
| Total sulfur/(μ g/g) | <1 | <10 | <10 |
| Total nitrogen/(μ g/g) | <0.5 | <1 | <1 |
| Arene underwater content/% | >45 | / | / |
| Smoke point/mm | / | >25 | / |
| Cetane number | / | / | >65 |
Claims (13)
1. maximum produces a method of hydrotreating for intermediate oil, comprising:
(1), after feedstock oil mixes with hydrogen, enter hydrofining reactor and hydrocracking reactor by a certain percentage simultaneously;
(2) reaction effluent of hydrofining reactor enters high-pressure separator, low pressure separator, fractionating column successively, is separated obtains light naphtha fraction, heavy naphtha fraction, intermediate oil and tail oil fraction by fractionating column;
(3) all or part of tail oil fraction enters hydrocracking reactor, and the reaction effluent of hydrocracking reactor enters hydrofining reactor together with part material oil;
(4) hydrofining reactor loads Hydrobon catalyst and amorphous hydrocracking catalyst successively, the admission space ratio of Hydrobon catalyst and amorphous hydrocracking catalyst is 4:1 ~ 1:2, hydrocracking reactor loads amorphous hydrocracking catalyst and molecular sieve hydrocracking catalyst successively, and the admission space ratio of amorphous hydrocracking catalyst and molecular sieve hydrocracking catalyst is 1:3 ~ 3:1;
H in the atmosphere of described hydrocracking reactor
2s dividing potential drop is 0.01 ~ 0.30MPa, NH
3dividing potential drop is 0.001 ~ 0.05MPa.
2. in accordance with the method for claim 1, it is characterized in that, described feedstock oil is selected from one or more in straight run vacuum gas oil (VGO), wax tailings, deasphalted oil, and boiling range is 260-700 DEG C, sulfur content is not more than 50000 μ g/g, and nitrogen content is not more than 5000 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that, the sulfur content of described feedstock oil is not more than 40000 μ g/g, and nitrogen content is not more than 2000 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that, the ratio that described feedstock oil enters hydrofining reactor and hydrocracking reactor is 20:1 ~ 1:2.
5. in accordance with the method for claim 1, it is characterized in that, reaction condition in described hydrofining reactor: reaction temperature 300 ~ 450 DEG C, reaction pressure 3.0 ~ 20.0MPa, hydrogen to oil volume ratio 300 ~ 2000 is 0.1 ~ 5.0h to the volume space velocity of fresh feed oil
-1.
6. in accordance with the method for claim 1, it is characterized in that, reaction condition in described hydrocracking reactor: reaction temperature is 300 ~ 450 DEG C, reaction pressure 3.0 ~ 25.0MPa, hydrogen to oil volume ratio 300 ~ 2000, volume space velocity is 0.5 ~ 8.0h
-1.
7. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst be load at amorphous alumina or/and the loaded catalyst of group vib base metal on silica or VIII base metal or its combination.
8. in accordance with the method for claim 1, it is characterized in that, described amorphous hydrocracking catalyst by amorphous aluminum silicate or/and aluminium oxide and load base metal thereon forms.
9. in accordance with the method for claim 8, it is characterized in that, overall for benchmark with amorphous hydrocracking catalyst, with oxide basis, amorphous hydrocracking catalyst consists of: aluminium oxide 10 % by weight ~ 45 % by weight, amorphous aluminum silicate 55 % by weight ~ 73 % by weight, group vib metal 15 % by weight ~ 35 % by weight, group VIII metal 2 % by weight ~ 8 % by weight.
10. in accordance with the method for claim 9, it is characterized in that, described group vib metal, group VIII metal are selected from one or more in Mo, W, Ni, Co.
11. in accordance with the method for claim 1, it is characterized in that, described molecular sieve hydrocracking catalyst is made up of a kind of carrier and load base metal on this carrier, and this carrier is made up of amorphous aluminum silicide and molecular sieve; Described amorphous aluminum silicide is selected from one or more in silica, aluminium oxide, amorphous aluminum silicate.
12. in accordance with the method for claim 11, it is characterized in that, overall for benchmark with molecular sieve hydrocracking catalyst, with oxide basis, molecular sieve hydrocracking catalyst consists of: aluminium oxide 30 % by weight ~ 72 % by weight, amorphous aluminum silicate 10 % by weight ~ 52 % by weight, molecular sieve 1 % by weight ~ 15 % by weight, group vib metal 15 % by weight ~ 35 % by weight, group VIII metal 2 % by weight ~ 8 % by weight.
13., according to the method described in claim 11 or 12, is characterized in that, one or more in faujasite, modenite, zeolite L, omega zeolite, Beta zeolite of described molecular screening.
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| CN1478868A (en) * | 2002-08-29 | 2004-03-03 | 中国石油化工股份有限公司 | Hydrogenation cracking method for maximally producing intermediate distillate |
| CN1766054A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for increasing yield of middle distillate oil |
| CN101760233A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Method for hydrocracking of coked wax oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1478868A (en) * | 2002-08-29 | 2004-03-03 | 中国石油化工股份有限公司 | Hydrogenation cracking method for maximally producing intermediate distillate |
| CN1766054A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for increasing yield of middle distillate oil |
| CN101760233A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Method for hydrocracking of coked wax oil |
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