CN104611053A - High dry point raw material hydrocracking process - Google Patents
High dry point raw material hydrocracking process Download PDFInfo
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- CN104611053A CN104611053A CN201310540550.8A CN201310540550A CN104611053A CN 104611053 A CN104611053 A CN 104611053A CN 201310540550 A CN201310540550 A CN 201310540550A CN 104611053 A CN104611053 A CN 104611053A
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a high dry point raw material hydrocracking process. According to the high dry point raw material hydrocracking process, a high dry point raw material firstly is subjected to a first-stage hydrorefining reaction, and a gas-liquid co-current flow process and a gas-liquid counter flow process are concurrently adopted in the first stage; the generated oil obtained in the first stage enters a second-stage refining stage to carry out a deep denitrogenation and aromatic hydrocarbon saturation reaction, and a gas-liquid co-current flow process is adopted in the second stage; and the second-stage reaction effluent is mixed with supplemental hydrogen gas, and then enters a third-stage reaction zone to carry out a hydrocracking reaction. With the method of the present invention, the nitrogen-containing impurities in the high dry point raw material can be subjected to hydrotreating under the relatively mild condition so as to make the high dry point raw material meet the hydrocracking feeding requirement, such that the hydrocracking raw material source is broadened; and the hydrorefining temperature is substantially reduced so as to increase the operation period of the device and process the poor-quality raw material, or increase the processing capacity of the device in the same operation period.
Description
Technical field
The invention discloses a kind of hydrocracking process, particularly a kind ofly process the high hydrocracking process doing raw material.
Background technology
Along with China's rapid development of economy, refining of petroleum ability increases fast.Meanwhile, domestic hydrocracking technology also obtain large-scale industrial application, and by the end of the year 2011, the hydroeracking unit that China is running will have cover more than 40, and total working ability is more than 50.0Mt/a, and working ability leaps to second place of the world.World's crude resources is day by day exhausted simultaneously, and international oil price is hovered in a high position always.China in 2011 is imported crude oil 2.54 hundred million tons altogether, and crude oil import dependency degree reaches 56.5%, and serious threat, to the health of national economy, fast development, makes full use of the vital task that crude resources has become oil refining industry.In addition, due to the variation year by year of domestic crude quality, the significantly increase of imported high sulfur crude oil amount of finish, the requirement of environmental protection to oil refining process and petroleum product-quality is increasingly strict, and market is to the continuous increase of clean fuel oil and industrial chemicals demand, especially as the clean intermediate oil of transportation fuel and the high-quality charging that provides for devices such as reformation, ethene, therefore the progress of market to hydrocracking technology level is had higher requirement.The wide scope of material that hydrocracking is processed, products scheme is flexible, and liquid product yield is high, can obtain high-quality power fuel and industrial chemicals, and hydrocracking process and technology are more and more subject to the most attention of each major oil companies of the world.In order to improve crude oil utilization ratio, improve the productive rate of high value added product, enterprise of each great oil refining adopts deep drawing technology one after another, and decompressed wax oil is done and reached more than 590 DEG C, even reaches 620 DEG C, and hydrocracking technology can meet this demand well.
Hydrocracking process generally can be divided into one-stage process and two-stage method, and wherein one-stage process comprises again single hop (also claiming single hop potion) and single hop series connection.Operating method is mainly divided into cyclical operation mode and once-through operation mode.Single stage process uses a kind of hydrocracking catalyst of resistance to organonitrogen, and raw material is directly by hydrocracking catalyst, and technological process is the simplest, and operation air speed is higher, but the raw material range of processing is narrow, and product Air China coal is second-rate.Single hop series connection uses Hydrobon catalyst and hydrocracking catalyst series connection, middle without the need to being separated, because hydrocracking catalyst used does not have the ability of resistance to organonitrogen, require at hydrofining reactor, sulphur nitrogen impurity to be removed totally, so generally can only operate under comparatively low-speed.Along with the maximization increasingly of oil refining enterprise, the large-scale hydroeracking unit of planning construction gets more and more, to reach scale and benefit.The list cover working ability of these devices is mostly more than 2,000,000 tons/year.If these large-scale hydroeracking units adopt the series connection of conventional single hop or single stage process technology by single covering device construction, due to the manufacturing expense of the large equipments such as reactor, feedstock pump, interchanger and trucking costs huge, plant construction will be made to invest greatly increase, affect the economic benefit of enterprise; And if build up two covering devices, then will increase due to table of equipment digital display work, equally also will increase the construction investment of device, and will process cost be increased.
Existing two-stage hydrocracking technique, as US3702818, relate to first paragraph stock oil first through hydrofining section imurity-removal, the liquid of separation enters hydrocracking section, first paragraph tail oil enters second segment and continues cracking, and this is conventional two-stage hydrocracking technological process.US3549515 first paragraph uses one-stage serial flow process, and first paragraph tail oil enters second segment and continues cracking, there is the deficiency of above-mentioned one-stage serial technique.US4404088 relates to increase hydrocracking reaction section, improve liquid product yield, but flow process is longer when changing products scheme.Although these technology schemes are flexible, technical process is complicated, and investment increases.CN100526433 relates to first paragraph and adopts single hop two doses of flow processs, and first paragraph tail oil enters second segment and continues cracking, and maximum produces intermediate oil, does not all relate to that processing is high does raw material.
The stock oil that tradition hydrocracking process is processed is done and is generally less than 530 DEG C.After employing crude oil deep vacuum distillation technology, doing of Hydrocracking Raw Oil significantly improves, and nitrogen content, sulphur content, bituminous matter, carbon residue and trace metal impurities content are obviously increased.Except causing the speed that stock oil spreads to catalytic inner to slow down because viscosity increases, thus outside reduction speed of response, also bring the impurity such as more, that structure is more complicated non-hydrocarbon compound and polycyclic aromatic hydrocarbons, colloid, bituminous matter, heavy metal, considerably increase hydrogenation difficulty.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of hydrocracking process of improvement, highly doing raw material (as deep drawing wax oil) for processing.Compare with existing two-stage hydrocracking technology, technical process is more flexible, can process raw material more inferior; Compare with existing one-stage serial hydrocracking technology, greatly can improve the working ability of device.
One of the present invention is high does raw material hydrocracking process, comprises following content:
(1) under Hydrofinishing conditions, height does stock oil and hydrogen is mixed into first paragraph reaction zone, first paragraph reaction zone uses Hydrobon catalyst, the top of first paragraph reaction zone is gas and liquid flowing reaction zone, and flow reaction effluent and enter gas-liquid separation zone and be separated, gas draws reactor; Liquid enters the beds of bottom, and the hydrogen introduced with reactor bottom carries out counter current contact reaction, and reacted gas leaves reactor from gas-liquid separation zone; The denitrification percent general control of first paragraph reaction zone is 60wt% ~ 95wt%;
(2) enter second segment reaction zone after the generation oil that first paragraph reaction zone obtains mixes with hydrogen, carry out Deep Hydrotreating reaction, second segment reaction zone uses Hydrobon catalyst;
(3) reaction effluent that second segment reaction zone obtains enters the 3rd section of reaction zone together with hydrogen make-up, uses hydrocracking catalyst in the 3rd section of reaction zone;
(4) the 3rd sections of reaction effluents that reaction zone obtains enter separator, obtain gas and liquid; Gas after gas-liquid separation can recycle after removing impurities matter, and liquid directly obtains various hydrocracked product after fractionation.
In the inventive method, described height is done the final boiling point of raw material (or doing) and is generally more than 550 DEG C, is preferably more than 570 DEG C, most preferably is 580 ~ 620 DEG C.Height does the nitrogen content of raw material generally at 500mgg
-1above.
In the inventive method, the denitrification percent general control of first paragraph reaction zone is 60wt% ~ 95wt%, preferably controls as 70wt% ~ 90wt%.The processing condition of Zhong Bingliu reaction zone, first paragraph reaction zone are: average reaction temperature is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 1.0 ~ 10.0h
-1, be preferably 1.0 ~ 4.0h
-1.In first paragraph reaction zone, the processing condition of counter-flow reaction zone are: average reaction temperature is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 2000:1, is preferably 400:1 ~ 1000:1; During liquid, volume space velocity is 1.0 ~ 10.0h
-1, be preferably 1.0 ~ 4.0h
-1.
Wherein in the first paragraph reaction zone of step (1), the hydrodenitrification rate of character and first paragraph that the gas and liquid flowing reaction zone on top and the catalyst loading volume ratio of gas-liquid counter current reaction zone, bottom can do raw material according to height is specifically determined.
In the inventive method, the processing condition of second segment reaction zone are: average reaction temperature is 330 ~ 480 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 0.2 ~ 4.0h
-1.Preferred operational condition is: average reaction temperature is 350 ~ 450 DEG C, and reaction pressure is 8.0 ~ 17.0MPa, and hydrogen to oil volume ratio is 400:1 ~ 2000:1, and during liquid, volume space velocity is 0.5 ~ 3.0h
-1.
In the inventive method, the processing condition of the 3rd section of reaction zone hydrocracking are: average reaction temperature is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 1.0 ~ 10.0h
-1, be preferably 1.0 ~ 4.0h
-1.
In the inventive method, according to unit scale, first paragraph reaction zone can arrange one or several reactors, and second segment reaction zone also can arrange one or several reactors, and the 3rd section of reaction zone generally arranges a reactor.
In the inventive method, the gas phase that gas-liquid separation zone, first paragraph reaction zone obtains can recycle after removing hydrogen sulfide and ammonia, and liquid phase enters second segment reaction zone.Second segment reaction zone reaction effluent enters the 3rd section of reaction zone and carries out hydrocracking reaction.First 3rd section of reaction effluent carry out gas-liquid separation, and gas phase removal hydrogen sulfide and ammonia Posterior circle use, and liquid phase enters one or more and the hydrocracking tail oil that separation column obtains naphtha fraction, kerosene(oil)fraction, diesel oil distillate.Tail oil partly or entirely can loop back first paragraph or second segment reaction zone, or directly goes out device.
In the inventive method, the stock oil adopting deep vacuum distillation technology to obtain is done and is significantly improved, and nitrogen content, sulphur content, bituminous matter, carbon residue and trace metal impurities content are obviously increased.Except causing the speed that stock oil spreads to catalytic inner to slow down because viscosity increases, thus outside reduction speed of response, also bring the impurity such as more, that structure is more complicated non-hydrocarbon compound and polycyclic aromatic hydrocarbons, colloid, bituminous matter, heavy metal, substantially increase hydrogenation difficulty.
In the inventive method, the Hydrobon catalyst that first paragraph reaction zone and second segment reaction zone use can be the arbitrary product in this area.Hydrocracking catalyst can select suitable product according to the Spreading requirements of reaction product, as oil type hydrocracking catalyst in then selecting for voluminous intermediate oil (kerosene and diesel oil), as then selected light oil type hydrogen cracking catalyst for voluminous petroleum naphtha, as then selected mobile type hydrocracking catalyst for flexible production petroleum naphtha and intermediate oil.Above-mentioned selection is content well-known to those skilled in the art.Hydrobon catalyst and hydrocracking catalyst are under response behaviour, and hydrogenation active component is sulphided state.
In the inventive method, mainly there is the reaction such as hydrogenating desulfurization, denitrogenation, deoxidation, aromatic saturation of raw material in first paragraph reaction zone; The Hydrobon catalyst of second segment reaction zone proceeds the reactions such as hydrogenating desulfurization, denitrogenation, deoxidation, aromatic saturation, three-zone hydrocracking catalyzer carries out hydrocracking reaction.
Compared with prior art, hydrocracking process of the present invention has the following advantages:
1, those skilled in the art know, the height being representative for deep drawing wax oil does raw material, although its nitrogen content may not be certain very high, because the structure of nitrogenous compound is very complicated, the nitrogen in high boiling fraction is but difficult to be removed by conventional hydro method.In the inventive method, first by first paragraph hydrofining, remove most nitrogen impurity; Then in second segment reaction zone, under the atmosphere of low ammonia, further hydrofining is carried out to the wax oil being stripped of most of the nitrogen impurity, lower ammonia dividing potential drop greatly slow down the restraining effect of ammonia for advanced nitrogen and aromatic saturation, thus can under the condition comparing mitigation, the nitrogen impurity of this part stubbornness is removed, thus is provided qualified raw material for the hydrocracking in downstream.
2, in first paragraph reaction zone, in the beds on top, height does stock oil and hydrogen carries out hydrofining reaction, and flow reaction effluent and be separated in gas-liquid separation zone, the ammonia inhibited to denitrogenation hydrogenation process generated in time is removed by being separated, thus is conducive to the carrying out of countercurrent hydrogenation reaction; And flow hydrogenated liquid then with hydrogen in lower catalyst bed layer counter current contact carry out hydrogenation reaction, reaction process generate ammonia also leave reactor through gas-liquid separation zone.Take gas and liquid flowing and gas-liquid countercurrent flow in first paragraph simultaneously, further provide a kind of be especially applicable to advanced nitrogen and saturated aromatic hydrocarbons add hydrogen atmosphere.And the restraining effect of ammonia to Hydrobon catalyst is reduced to minimum, give full play to the activity of Hydrobon catalyst, thus advanced nitrogen can be carried out under the condition relaxed.
3, the present invention does height according to stock oil, nitrogenous compound is difficult to the feature removed, in first paragraph reaction zone, preferably adopt the Hydrobon catalyst being prepared carrier production by chloride process, be characterized in that duct is large and concentrated, foreign matter content is low, the effect of carrier and metal is strong, more effectively can reduce the restraining effect of ammonia to catalyzer, especially has better activity stability to processing high raw material of doing inferior; And prepare the Hydrobon catalyst of carrier production at second segment reactor choice for use by sulphate method, be characterized in that duct is relatively little and disperse, the effect of carrier and metal is relatively weak.Hydrobon catalyst in second segment has higher activity and better activity stability for the raw material being stripped of most of the nitrogen impurity.Thus the grating system of these two kinds of catalyzer can better play the activity of hydrogenation catalyst, the running period of extension fixture while realizing advanced nitrogen.
4, the 3rd section of hydrocracking tail oil that reaction zone obtains can also return the hydrofining reactor of first paragraph or second segment by component loops, the high viscosity doing raw material can be reduced on the one hand, greatly improve stock oil velocity of diffusion on a catalyst, improve reaction efficiency; Deep hydrofinishing can be carried out further on the other hand to unsaturated aromatic hydrocarbons.
5, because hydrofining reaction temperature reduces greatly, thus the running period of device can be improved, process raw material more inferior or under same running period, improve the working ability of device.
Accompanying drawing explanation
Fig. 1 is a kind of principle process flow sheet of the present invention.
Embodiment
The present invention's height used does one or more in deasphalted oil that stock oil can be crude oil, shale oil, coal synthetic oil and crude oil deep vacuum distillation cut wet goods cut.
The Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone can be conventional heavy distillate Hydrobon catalyst.Conventional hydro catalyst for refining generally comprises carrier and is loaded in hydrogenation metal component on carrier, to generally include in the periodic table of elements group VIB active metal component as tungsten and/or molybdenum, in metal oxide weight 8% ~ 35%, and preferably 12% ~ 30%; And the VIIIth race's active metal component as nickel and/or cobalt, in metal oxide weight 1% ~ 7%, preferably 1.5% ~ 6%.The carrier that Hydrobon catalyst uses is inorganic refractory oxide, one or more as being selected from aluminum oxide, amorphous silicon aluminium, silicon oxide and titanium oxide.Suitable adjuvant component can also be comprised, as the element such as phosphorus, boron in catalyzer.
In the inventive method, special recommendation uses the catalyzer with following character in first paragraph reaction zone: the average pore diameter of catalyzer is 7.5 ~ 9.5nm, preferably 8 ~ 9nm; The volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is 70% ~ 90%, is preferably 75% ~ 85%; The pore volume in <4nm hole accounts for less than 5% of total pore volume.The Hydrobon catalyst that first paragraph reaction zone uses, be generally the catalyzer being prepared carrier production by chloride process, the maturing temperature of catalyzer is generally at about 480 DEG C.The catalyzer used in first paragraph reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyzer according to the method for this area.
Because the nitrogen content of stock oil is removed to relatively low level by first paragraph reaction zone, the Hydrobon catalyst that second segment reaction zone can use first paragraph reaction zone to use.The present invention preferably uses in second segment reaction zone has the catalyzer of following character: the average pore diameter of catalyzer is 4 to being less than 7.5nm, preferably 5 ~ 7nm; Its median pore diameter is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 50 ~ 75%, preferably 55 ~ 65%; The pore volume in the hole of <4nm accounts for the volume fraction of total pore volume generally lower than 10%.Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants little 0.5 ~ 3nm, preferably little 1.0 ~ 2.5nm; The hole of aperture 4 ~ 10nm accounts for little 10 ~ 30 percentage ratios of volume fraction of total pore volume, preferably little 15 ~ 25 percentage ratios.Catalyzer in second segment reaction zone be generally by sulphate as Tai-Ace S 150 method prepare carrier produce catalyzer, the maturing temperature of catalyzer is generally at about 450 DEG C.The catalyzer used in second segment reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyzer according to the method for this area.
Or body phase hydrogenation catalyst can also be used in second segment reaction zone in the present invention, to improve the hydrogenation temperature of second segment reaction zone further.Body phase hydrogenation catalyst contains Mo, W, Ni tri-kinds of metal components, and in oxidized catalyst, W, Ni exist with composite oxides form: Ni
xw
yo
z, z=x+3y, Mo exist with oxide form: MoO
3; Composite oxides Ni
xw
yo
zthe ratio of middle x and y is 1:8 ~ 8:1, composite oxides Ni
xw
yo
zwith oxide M oO
3weight ratio be 1:10 ~ 10:1; Composite oxides Ni in bulk phase catalyst
xw
yo
zwith oxide M oO
3gross weight content be 40% ~ 100%.One or more in the components such as aluminum oxide, silicon oxide, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve can be contained as required in bulk phase catalyst, these components weight content is in the catalyst 0 ~ 60%, is preferably 20% ~ 50%.The specific surface area of bulk phase catalyst is 120 ~ 400m
2/ g, pore volume is 0.10 ~ 0.50mL/g.The commercial catalysts that body phase hydrogenation catalyst can select Fushun Petrochemical Research Institute to develop, or be prepared according to the Conventional wisdom of this area.
The hydrocracking reaction district of the 3rd section can use routine business hydrocracking catalyst, owing to can the foreign matter content of charging be taken off lower, the hydrocracking catalyst of resistance to nitrogen need not be adopted, operable business hydrocracking catalyst is except selecting the business Catalyst For Single-stage Hydrocracking with resistance to organonitrogen function, as ZHC-01, ZHC-02, ZHC-04, FC-14, FC-28 that Fushun Petrochemical Research Institute develops, the ICR126 etc. that FC-34, CHEVRON company develops.Can also use as DHC-32, DHC-39, HC-43, HC-115 etc. of Uop Inc., Fushun Petrochemical Research Institute develop 3971,3974,3976, FC-12, FC-16, FC-26 etc.
The present invention is explained further below in conjunction with drawings and Examples.
As shown in Figure 1: height is done that stock oil enters first paragraph hydrofining reactor 3 after pipeline 1 mixes with the recycle hydrogen of pipeline 2 and flowed A district, reaction zone and carry out hydrofining reaction, remove the impurity such as part S, N, O, A district effluent enters C district, gas-liquid separation zone and is separated, gas-phase reaction effluent draws reactor through pipeline 4, and the new hydrogen that C district obtains introducing through pipeline 5 bottom liquid phase and B district carries out hydrofining reaction in B district counter current contact, after countercurrent hydrogenation, gas enters C district, gas-liquid separation zone and discharges, the liquid that first paragraph hydrofining reactor obtains mixes through the recycle hydrogen of pipeline 6 with pipeline 7, enter second segment hydrofining reactor 8 and proceed deep hydrofinishing reaction, second segment reaction effluent enters hydrocracking reactor 11 and carries out hydrocracking reaction after pipeline 9 mixes with the hydrogen make-up of pipeline 10, hydrocracking reaction effluent enters separator 13 through pipeline 12 and is separated, after isolating gas 14, liquid through line 15 enters separation column 16, isolate gas 17, petroleum naphtha 18, kerosene 19, diesel oil 20 and tail oil 21, separator 13 generally includes high-pressure separator and light pressure separator.A part for tail oil 21 can return the entrance of first paragraph hydrofining reactor 3 or second segment hydrofining reactor 8.
Below by embodiment, the present invention program and effect are described.Hydrocracking catalyst used is the commercial catalyst of Fushun Petrochemical Research Institute's development and production, and raw materials used oil properties lists in table 1.Use the character of Hydrobon catalyst to list in table 2.In the present invention, wt% is weight percentage or weight content.
Embodiment 1
Adopt the technical process shown in Fig. 1, three-zone hydrocracking adopts one way to pass through flow process.Loading catalyst A in first paragraph, second segment loading catalyst A.First paragraph refining reaction device top adopts gas and liquid flowing flow process, and bottom adopts gas-liquid counter current flow process, and the section of stream is 1:1 with the catalyst loading volume ratio of adverse current section.
Embodiment 2
First paragraph and the equal loading catalyst B of second segment, other are with embodiment 1.
Embodiment 3
First paragraph loading catalyst A, second segment loading catalyst B.Other are with embodiment 1.
Comparative example 1
Adopt conventional two-stage hydrocracking technique.Hydrofining reaction district only uses Hydrobon catalyst A, and hydrocracking section uses FC-50 catalyzer.Wherein control hydrocracking reaction section >370 DEG C of transformation efficiency and be about 70wt%.
Comparative example 2
Adopt conventional two-stage hydrocracking technique.Hydrofining reaction district only uses Hydrobon catalyst B, and hydrocracking section uses FC-50 catalyzer.Wherein control hydrocracking reaction section >370 DEG C of transformation efficiency and be about 70wt%.
Comparative example 3
Technique basic procedure is with embodiment 1.Only adopt in first paragraph reaction zone and flow technical process, first paragraph reaction zone effluent is separated, liquid and hydrogen enter second segment reaction zone and carry out deep hydrofinishing reaction, and second segment hydrogenation reaction effluent and hydrogen make-up enter the 3rd section of reaction zone and carry out hydrocracking reaction.
Wherein first paragraph reaction zone uses Hydrobon catalyst A, and second segment reaction zone uses Hydrobon catalyst B, and the 3rd section uses FC-50 catalyzer.Wherein control hydrocracking reaction section >370 DEG C of transformation efficiency and be about 70wt%.
The embodiment 1-3 running test-results of 500 and 6000 hours lists in table 3.The test-results that comparative example 1-3 operates 500 hours lists in table 4.
Table 1 stock oil.
| Stock oil | Deep drawing wax oil |
| Density/kgm -3 | 929.3 |
| Boiling range/DEG C | 367~600 |
| Sulphur content/wt% | 2.99 |
| Nitrogen content/mgg -1 | 1073 |
| Condensation point/DEG C | 28 |
| BMCI value | 50.7 |
Table 2 Hydrobon catalyst.
| Numbering | A | B |
| Carrier | Aluminum oxide | Aluminum oxide |
| MoO 3，wt% | 24.9 | 24.5 |
| NiO，wt% | 4.12 | 4.26 |
| P，wt% | 2.67 | 2.71 |
| Average pore diameter, nm | 8.4 | 6.5 |
| 4 ~ 10nm hole accounts for the ratio of total pore volume, v% | 85 | 61 |
Table 3 test-results.
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Processing condition | |||
| Catalyzer | (A/A)/A/FC-50 * | (B/B)/B/FC-50 * | (A/A)/B/FC-50 * |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Volume space velocity/h -1 | (2.4/2.4)/1.2/1.8 | (2.4/2.4)/1.2/1.8 | (2.4/2.4)/1.2/1.8 |
| Hydrogen to oil volume ratio | 900/(900/900)/1300 | 900/(900/900)/1300 | 900/900/1300 |
| First paragraph denitrification percent, wt% | 86 | 86 | 86 |
| Cracking zone > 370 DEG C of per pass conversion, wt% | 70.7 | 70.9 | 71.1 |
| Operate 500 hours | |||
| Temperature of reaction/DEG C | (368/368)/374/382 | (365/365)/371/382 | (368/368)/371/382 |
| Main products character | |||
| Rocket engine fuel | |||
| Yield, wt% | 16.69 | 16.71 | 17.02 |
| Smoke point, mm | 28 | 27 | 28 |
| Diesel oil | |||
| Yield, wt% | 6.88 | 6.91 | 7.11 |
| Cetane value | 68.3 | 67.1 | 68.5 |
| Tail oil | |||
| Yield | 29.3 | 29.1 | 28.9 |
| BMCI value | 10.4 | 10.3 | 10.2 |
| Viscosity index | 138 | 137 | 138 |
| Operate 6000 hours | |||
| Temperature of reaction/DEG C | (374/374)/377/385 | (377/377)/378/385 | (374/374)/378/385 |
| Main products character | |||
| Rocket engine fuel | |||
| Yield, wt% | 17.45 | 17.76 | 17.43 |
| Smoke point, mm | 27 | 26 | 27 |
| Diesel oil | |||
| Yield, wt% | 6.63 | 6.81 | 6.72 |
| Cetane value | 67.7 | 66.8 | 67.5 |
| Tail oil | |||
| Yield | 29.2 | 29.2 | 29.2 |
| BMCI value | 10.7 | 10.6 | 10.7 |
| Viscosity index | 137 | 136 | 137 |
Table 4 test-results.
| Numbering | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Catalyzer | A/FC-50 * | B/FC-50 * | A/B/FC-50 # |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Hydrogen to oil volume ratio | 900/1300 | 900/1300 | 900/900/1300 |
| Volume space velocity/h -1 | 0.6/1.8 | 0.6/1.8 | 1.2/1.2/1.8 |
| Temperature of reaction/DEG C | 395/382 | 388/382 | 377/371/382 |
| First paragraph denitrification percent, wt% | — | -— | 86 |
| Cracking zone > 370 DEG C of per pass conversion, wt% | ~70 | ~70 | ~70 |
| Main products character | |||
| Rocket engine fuel | |||
| Yield, wt% | 17. 87 | 17.71 | 17.83 |
| Smoke point, mm | 24.0 | 24.0 | 28.0 |
| Diesel oil | |||
| Yield, wt% | 7.57 | 7.68 | 7.62 |
| Cetane value | 62.4 | 62.9 | 62.7 |
| Tail oil | |||
| Yield | 30.0 | 30.0 | 30.0 |
| BMCI value | 12.1 | 11.9 | 11.0 |
| Viscosity index | 129 | 128 | 137 |
Shown by above embodiment, the inventive method process high do raw material time, the activity of Hydrobon catalyst and hydrocracking catalyst can be given full play to.
Because hydrofining and hydrocracking reaction temperature reduce greatly, thus the running period of device can be improved, or improve the working ability of device under same running period.
Claims (15)
1. highly do a raw material hydrocracking process, comprise following content:
(1) under Hydrofinishing conditions, height does stock oil and hydrogen is mixed into first paragraph reaction zone, first paragraph reaction zone uses Hydrobon catalyst, the top of first paragraph reaction zone is gas and liquid flowing reaction zone, and flow reaction effluent and enter gas-liquid separation zone and be separated, gas draws reactor; Liquid enters the beds of bottom, and the hydrogen introduced with reactor bottom carries out counter current contact reaction, and reacted gas leaves reactor from gas-liquid separation zone; The denitrification percent of first paragraph reaction zone controls as 60wt% ~ 95wt%;
(2) enter second segment reaction zone after the generation oil that first paragraph reaction zone obtains mixes with hydrogen, carry out Deep Hydrotreating reaction, second segment reaction zone uses Hydrobon catalyst;
(3) reaction effluent that second segment reaction zone obtains enters the 3rd section of reaction zone together with hydrogen make-up, uses hydrocracking catalyst in the 3rd section of reaction zone;
(4) the 3rd sections of reaction effluents that reaction zone obtains enter separator, and obtain gas and liquid, liquid obtains various hydrocracked product after fractionation.
2. according to technique according to claim 1, it is characterized in that, the final boiling point that described height does raw material is more than 550 DEG C.
3. according to technique according to claim 2, it is characterized in that, the final boiling point that described height does raw material is more than 570 DEG C.
4. according to technique according to claim 3, it is characterized in that, the final boiling point that described height does raw material is 580 ~ 620 DEG C.
5., according to the arbitrary described technique of claim 2-4, it is characterized in that, described height does the nitrogen content of raw material at 500mgg
-1above.
6. according to technique according to claim 1, it is characterized in that, first paragraph and the Hydrobon catalyst described in second segment reaction zone comprise carrier and are loaded in the hydrogenation metal component on carrier, catalyzer to comprise in the periodic table of elements metal component of group VIB in metal oxide weight 8% ~ 35%, and metal component of group VIII is in metal oxide weight 1% ~ 7%.
7. according to technique according to claim 6, it is characterized in that, the Hydrobon catalyst used in first paragraph has following character: the average pore diameter of catalyzer is 7.5 ~ 9.5nm, and aperture is the volume fraction that the hole of 4 ~ 10nm accounts for total pore volume is 70 ~ 90%.
8. according to the technique described in claim 1,6 or 7, it is characterized in that, the Hydrobon catalyst that second segment reaction zone uses has following character: the average pore diameter of catalyzer is 4 to being less than 7.5nm, and aperture is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 50 ~ 75%; Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants the hole of little 0.5 ~ 3nm, aperture 4 ~ 10nm to account for little 10 ~ 30 percentage ratios of volume fraction of total pore volume.
9. according to technique according to claim 8, it is characterized in that, compared with the Hydrobon catalyst in first paragraph, the hole of the little 1.0 ~ 2.5nm of average pore diameter of second segment Hydrobon catalyst, aperture 4 ~ 10nm accounts for little 15 ~ 25 percentage ratios of volume fraction of total pore volume.
10. according to technique according to claim 7, it is characterized in that, the average pore diameter of the Hydrobon catalyst used in first paragraph reaction zone is 8 ~ 9nm, and the volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is 75% ~ 85%.
11., according to the technique described in claim 9 or 10, is characterized in that, the average pore diameter of Hydrobon catalyst that second segment reaction zone uses is 5 ~ 7nm, and its median pore diameter is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 55% ~ 65%.
12. according to technique according to claim 1, it is characterized in that, the processing condition of Zhong Bingliu reaction zone, first paragraph reaction zone are: average reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h
-1; In first paragraph reaction zone, the processing condition of counter-flow reaction zone are: average reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1 ~ 2000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h
-1.
13., according to technique according to claim 1, is characterized in that, the processing condition of second segment reaction zone are: average reaction temperature is 330 ~ 480 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 0.2 ~ 4.0h
-1.
14. according to technique according to claim 1, it is characterized in that, the processing condition of the 3rd section of reaction zone hydrocracking are: average reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h
-1.
15., according to technique according to claim 1, is characterized in that, use body phase hydrogenation catalyst in second segment reaction zone, and body phase hydrogenation catalyst contains Mo, W, Ni tri-kinds of metal components, and in oxidized catalyst, W, Ni exist with composite oxides form: Ni
xw
yo
z, z=x+3y, Mo exist with oxide form: MoO
3; Composite oxides Ni
xw
yo
zthe ratio of middle x and y is 1:8 ~ 8:1, composite oxides Ni
xw
yo
zwith oxide M oO
3weight ratio be 1:10 ~ 10:1; Composite oxides Ni in bulk phase catalyst
xw
yo
zwith oxide M oO
3gross weight content be 40% ~ 100%.
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| CN111100698A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrocracking method for high-dry-point high-nitrogen raw oil |
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