CN1940029A - Low-hydrogenloss hydrogenation of high-output qulified diesel oil - Google Patents
Low-hydrogenloss hydrogenation of high-output qulified diesel oil Download PDFInfo
- Publication number
- CN1940029A CN1940029A CN 200510105441 CN200510105441A CN1940029A CN 1940029 A CN1940029 A CN 1940029A CN 200510105441 CN200510105441 CN 200510105441 CN 200510105441 A CN200510105441 A CN 200510105441A CN 1940029 A CN1940029 A CN 1940029A
- Authority
- CN
- China
- Prior art keywords
- oil
- hydrocracking
- heavy
- hydrogen
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A low-hydrogen loss hydrogenation for qualified diesel oil is carried out by mixing raw oil with reactant from hydrogenation pyrolytic reactor, entering it into hydrogenation reactor to have refining reaction and light crack reaction, cooling for effluent, separating out light naphtha fraction, heavy naphtha fraction, diesel fraction and tail-oil fraction, circulating for tail-oil fraction to hydrogenation cracking reactor, reacting, mixing separated hydrogen-enriched gas with hydrogen and entering into hydrogenation cracking reactor. It has gentle reactive condition and produces qualified diesel oil with low-sulfur, low-nitrogen, low-arene and high-cetyl value characteristics.
Description
Technical field
The present invention relates to a kind of is the hydrocarbon ils cleavage method that obtains low boiler cut existing under the situation of hydrogen, and more particularly, the present invention is a kind of low-hydrogenloss hydrogenation of high-output qulified diesel oil.
Background technology
Along with the environmental consciousness enhancing of global range, many countries have especially formulated more strict standard to motor spirit to petroleum products.China carries out Europe III emission standard in beginning in 2005 in some main big cities, will carry out more strict Europe IV emission standard in 2008, and wherein the Europe IV specification requirement density of diesel oil is at 0.820～0.845g/cm
3In the scope, sulphur content ≯ 50ppm, the heavy % in polycyclic aromatic hydrocarbon content ≯ 11, cetane value ≮ 51.From China's oil product demand trend, supply falls short of demand always for diesel oil, and diesel and gasoline ratio requires more and more higher.Therefore, how adopting new hydrogen addition technology high-output qulified diesel oil is the problem that everybody pays close attention to.
As everyone knows, China's catalytic cracking diesel oil proportion is very high, accounts for 1/3rd of whole diesel pool greatly.The catalytic cracking diesel oil characteristics are: foreign matter content height such as density height, aromaticity content height, sulphur nitrogen, stability is poor, cetane index is low, can not directly dispatch from the factory as processed oil.And general diesel oil hydrofining can only partly solve sulphur in the diesel oil, problem that nitrogen content is high, is difficult to increase substantially cetane value, reduces aromaticity content and density.After particularly the diesel oil specification improved, this problem was more outstanding.
Hydrocracking technology, owing to can process heavy feed stock, and its product property is good, products scheme and device flexible operation and environmental protection, is oiling in conjunction with one of effective means of, heavy oil lighting always.Therefore, effectively utilize this technology, can to a certain degree solve the unfavorable situation of current international petroleum chemical industry, and produce great economic benefit and social benefit, so the hydrocracking technology application prospect is boundless.But, conventional hydrocracking technology investment and process cost height, particularly hydrogen consumption is higher, this technology is applied be subjected to certain restriction.For domestic refinery, because naphtha resource is limit, the reformer scale is generally little, and difficulty provides competent cheap hydrogen, causes the ratio of hydrogen expense in the hydrogenation unit processing charges higher, generally accounts for 60～70% of total processing charges.Therefore, be necessary prior art is optimized with the raising diesel product yield, and control the hydrogen consumption of hydrogenation process effectively, this will further promote the competitive power of hydrocracking technology.
US 4197184 discloses a kind of " parallel-flow " multistage hydrocracking process, and this technology can be used for maximum and produces diesel oil and rocket engine fuel.Its technical process can be sketched and is: raw material enters hydrofining reactor, reaction after refining generates oil and is mixed into separation system with the reaction generation oil that hydrocracking reactor comes out, obtain the different fractions product, tail oil is recycled to hydrocracking reactor and carries out cracking reaction at the bottom of the tower of separating.The entire reaction system has only a circulating hydrogen compressor, a make-up hydrogen compressor and a separation system.This patent is two sections recycle to extinction conversion process, because hydrofining is handled the diesel oil distillate obtain without hydrocracking, and directly enters separation system, therefore can improve diesel yield; Ammonia concentration is low in the atmosphere of hydrocracking reaction, helps improving the quality of products.But this flow process tail oil internal circulating load is very big, and high score, low branch, recycle compressor, separation column are loaded big, so investment cost and process cost height.
US 4713167 discloses a kind of multiple single-stage hydrocracking flow process.Promptly increase " repetition cracking " reaction zone in the hydrocracking flow process of conventional tail oil recycle to extinction, a part of intermediate oil that obtains after the generation of hydrocracking soon is separating of oil carries out cracking again, becomes lighter purpose product.Repeat cracking and generate oil and conventional oily mixing of hydrocracking generation, obtain various products through separation.But this patent maximum is produced petroleum naphtha or boat product of coal, and this flow process is owing to set up the repetition cracking case separately, and the product purpose is stronger, therefore is better than the flow process that intermediate oil loops back cracking popular response district.But need to increase a lot of equipment such as second cracking case (repetition cracking case) and corresponding interchanger, investment cost and process cost height; With the oil circulation cracking of high-quality middle runnings, make its yield low simultaneously, the hydrogen consumption is high.
WO 97/38066 discloses a kind of hydrocracking process flow process of inverted sequence.Its technical process can be summarized as follows: heavy raw oil to a hydrofining reaction district, carry out hydrogenating desulfurization and hydrodenitrification reaction, and the logistics after the hydrofining is isolated hydrogen-rich gas and liquid phase stream after cooling; Hydrogen-rich gas recycles, and liquid phase stream is isolated light-end products, at least one sideline product and bottom product to separation system; Bottom product and sideline product mix with recycle hydrogen after heating, carry out cracking reaction to a hydrocracking reaction district, and the reactant flow after the hydrocracking is directly mixed with fresh feed without separating, and handles to above-mentioned hydrofining reaction district then.Reactant flow after this flow process hydrofining is isolated hydrogen sulfide and ammonia through separator, makes that the gaseous impurities content in the reaction atmosphere of hydrocracking reactor is very low, helps the carrying out of hydrocracking reaction, and has improved the activity of cracking catalyst.But this patent hydrofining reaction district mainly carries out desulfurization and denitrification reaction, does not carry out the partial hydrogenation cracking reaction, makes that whole device tail oil internal circulating load is very big, has increased considerably high score, low branch, separation column and recycle compressor load.In addition, part sideline product (mainly being diesel oil distillate) also is recycled to the cracking reaction district and reacts, and has therefore reduced diesel yield and has improved hydrogen consumption, has also increased considerably investment and process cost.
US 5968346 discloses a kind of two-stage hydrocracking technical process that the High Temperature Gas liquid/gas separator is arranged.Its technical process can be summarized as follows: stock oil is after hydrofining, in a High Temperature Gas liquid/gas separator, carry out gas-liquid separation, liquid and recycle hydrogen are mixed into hydrocracking reactor, the hydrocracking reactor effluent mixes with High Temperature Gas liquid/gas separator top gaseous stream, its mixture obtains various products through gas-liquid separation, fractionation again, and tail oil and/or intermediate oil loop back the hydrocracking reaction district and carry out cracking reaction.The High Temperature Gas liquid/gas separator that this flow process increases can be isolated the hydrogen sulfide and the ammonia of one section generation, makes two sections hydrocracking reaction carry out in comparatively purified atmosphere, has improved cracking activity.But this patent reactive system pressure reduction increases a lot, and high score, low branch, separation column and recycle compressor load will increase considerably, and also will increase relevant device, and investment need increase considerably, and this flow process improves little to middle distillate yield.
US 5980729 has disclosed a kind of hydrocracking reactor and hydrotreating reactor is inverted, the steam stripped two-stage process flow process of high pressure-temperature.Raw material is mixed into hydrotreating reactor with the hydrocracking reactor effluent earlier, and the hydrotreatment reaction effluent is stripping in a high pressure, high-temperature separator, isolates gaseous stream and liquid phase stream.Liquid phase stream is looped back hydrocracking reactor to react; The gaseous stream that stripping is gone out enters a back end hydrogenation treatment reactor and reacts, and its resultant of reaction obtains various products through cooling, after separating.It is limited that this invention mesohigh, high-temperature separator stripping are isolated the precision of gaseous stream, and the part intermediate oil is sneaked into liquid phase stream and is circulated back in the hydrocracking reactor, has reduced the yield of intermediate oil on the contrary; Simultaneously, setting up of high pressure, high temperature stripping separator increased investment and process cost.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of low-hydrogenloss hydrogenation of high-output qulified diesel oil is provided.
Method provided by the invention comprises: stock oil mixes with the reaction effluent of hydrocracking reactor, enter hydrotreating reactor, carry out the slight hydrocracking reaction of hydrofining and heavy distillate under the effect of hydrotreating catalyst, hydrotreating catalyst is VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports; The reaction effluent of hydrotreating reactor enters high-pressure separator, light pressure separator, separation column successively after the heat exchange cooling, isolate light naphtha fraction, heavy naphtha fraction, diesel oil distillate and tail oil cut through separation column; The tail oil cut is recycled to hydrocracking reactor, in the presence of hydrogen, contact with hydrocracking catalyst, carry out hydrocracking reaction, hydrocracking catalyst is VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide and/or the Zeolite support; Enter hydrocracking reactor from isolated hydrogen-rich gas of high-pressure separator and the new hydrogen of choosing wantonly.
Method provided by the invention organically combines hydrotreatment and hydrocracking, with the mixing raw material of vacuum gas oil with the catalytic cracking diesel oil of choosing wantonly, under demulcent reaction conditions and low hydrogen consumption, but maximum is produced the fine-quality diesel oil product of low-sulfur, low nitrogen, low aromatic hydrocarbons, high hexadecane value, and this product can satisfy the Europe IV fuel specification requirement of diesel oil.
Description of drawings
Accompanying drawing is the low-hydrogenloss hydrogenation synoptic diagram of high-output qulified diesel oil provided by the invention.
Embodiment
Method provided by the invention is so concrete enforcement:
Stock oil mixes with the reaction effluent of hydrocracking reactor after heating, enter hydrotreating reactor, under the effect of hydrotreating catalyst, at hydrogen dividing potential drop 4.0～20.0MPa, preferred 6.0～15.0MPa, 280～450 ℃ of temperature of reaction, preferred 330～420 ℃, hydrogen to oil volume ratio 300～2000Nm
3/ m
3, preferred 400～1500Nm
3/ m
3, volume space velocity 0.1～10.0h
-1, preferred 0.2～3.0h
-1Condition under, carry out hydrogenating desulfurization. hydrodenitrification, alkene are saturated, part aromatic hydrocarbons saturated reaction and hydrocracking reaction to a certain extent; The reaction effluent of hydrotreating reactor enters high-pressure separator, light pressure separator, separation column successively after the heat exchange cooling, isolate naphtha fraction, diesel oil distillate and tail oil cut through separation column; The tail oil cut, contacts with hydrocracking catalyst in the presence of hydrogen, at hydrogen dividing potential drop 4.0～20.0MPa to hydrocracking reactor through the heat exchange ramp cycle, preferred 6.0～15.0MPa, 280～450 ℃ of temperature of reaction, preferred 330～420 ℃, hydrogen to oil volume ratio 300～2000Nm
3/ m
3, preferred 400～1500Nm
3/ m
3, volume space velocity 0.1～10.0h
-1, preferred 0.2～3.0h
-1Condition under carry out hydrocracking reaction; With after new hydrogen mixes, enter hydrocracking reactor from the isolated hydrogen-rich gas of high-pressure separator.
Used stock oil is vacuum gas oil and the mixture of optional catalytic cracking diesel oil among the present invention.Generally between 150～550 ℃, density is 0.85～0.93g/cm to the stock oil boiling range
3, so the present invention is applicable to the mixing raw material of almost various types of vacuum gas oils and optional catalytic cracking diesel oil.But for the inlet amount (tail oil internal circulating load) that reduces hydrocracking reactor, in the stock oil＜370 ℃ cut is preferably in more than the 30 heavy %.Because the preferred hydrocracking catalyst of the present invention has good anti-sulphur, anti-nitrogen ability, so sulphur content can be up to 5.0 heavy % in the stock oil, and nitrogen content can be up to 0.2%; In addition, mixing raw material is after hydrotreatment, and the nitrogen content of heavy distillate can be reduced to very lower concentration, can give full play to the cracking activity of cracking catalyst.In order to prolong the running period of catalyzer, the nitrogen content of stock oil preferably is controlled at ≯ 0.2 heavy %, and sulphur content preferably is controlled at 3.0 heavy %, can guarantee that like this catalyzer is not less than 6 years entire life.
The used hydrotreating catalyst of the present invention is VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.Preferred hydrotreating catalyst is a benchmark with the catalyzer, and it consists of: nickel oxide 1～5 heavy %, and Tungsten oxide 99.999 12～35 heavy %, fluorine 1～9 heavy %, surplus is an aluminum oxide.This aluminum oxide is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75: 25～50: 50, the pore volume of this aperture aluminum oxide median pore diameter＜80A accounts for total pore volume more than 95%, the pore volume of this macroporous aluminium oxide median pore diameter 60～600A accounts for total pore volume more than 70%, and described pore volume is measured with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature.Because this catalyzer has good hydrogenating desulfurization, hydrodenitrification, aromatic hydrocarbons is saturated and partial hydrogenation cracking function, so can handle the mixing oil of higher vacuum gas oil of aromaticity content and/or catalytic cracking diesel oil, can reduce product density preferably, improve diesel cetane-number, impurity such as the sulphur in the effective elimination raw material, nitrogen carry out the partial hydrogenation cracking reaction simultaneously.
The used hydrocracking catalyst of the present invention is VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide and/or the Zeolite support.Preferred hydrocracking catalyst is a benchmark with the catalyzer, and it consists of: nickel oxide 2.5～6.0 heavy %, Tungsten oxide 99.999 10～38 heavy %, fluorine are 0.5～5.0 heavy %, and surplus is a carrier, and this carrier is made up of unformed aluminum oxide and mesopore or large pore zeolite.Because this catalyzer has higher hydrogenation activity and intermediate oil selectivity, so heavy distillate obtains the fine-quality diesel oil of larger proportion after hydrocracking.Simultaneously, hydrocracking catalyst reacts in the very low reaction atmosphere of ammonia concentration, and its cracking activity increases substantially, and can turn round under higher space velocity.
Hydrotreating catalyst and hydrocracking catalyst are seated in respectively in two reactors.Hydrotreating catalyst is formed and the character adjustment according to raw material with the admission space ratio of hydrocracking catalyst, can change in 25: 75～75: 25 scope.
If stock oil character is relatively poor; as metal content, carbon residue content height; for falling, the pressure that prevents beds reaches limit value too quickly; can before hydrotreating catalyst, add a certain amount of protective material with the running of assurance device long period ground, adjust in the scope at 1: 100～30: 100 according to the volume ratio of raw material properties protective material and hydrotreating catalyst.Protective material can use one or more.
By method provided by the invention, resultant full distillate oil obtains product through fractionation and comprises light naphtha fraction, heavy naphtha fraction and diesel oil distillate.Cutting temperature can be arbitrary temperature between 55～75 ℃ between light naphtha fraction and the heavy naphtha fraction; Cutting temperature can be arbitrary temperature between 150～180 ℃ between heavy naphtha fraction and the diesel oil distillate, and the light naphtha fraction boiling range is generally C5～65 ℃, and the heavy naphtha fraction boiling range is generally 65～150 ℃, and the diesel oil distillate boiling range is generally 150～370 ℃.The light naphtha fraction yield that the present invention obtains is between 1～5 heavy %, and hydrogen richness is higher than 16 heavy %; The heavy naphtha fraction yield is between 5～20 heavy %, and sulphur, nitrogen content are lower than 0.5ppm, and virtue is dived and is higher than 45 heavy %; The diesel oil distillate yield is between 70～90 heavy %, and sulphur content is lower than 50ppm, and polycyclic aromatic hydrocarbon content is lower than 11 heavy %, and cetane value is higher than 51, satisfies European IV diesel oil standard.
The invention has the advantages that:
1, use the present invention maximum production to be met Europe IV emission request fine-quality diesel oil product.Catalytic cracking diesel oil is through after the hydrotreatment, and character improves a lot, and its sulphur, nitrogen content remove totally substantially, and density, aromaticity content also descend significantly, and diesel cetane-number also increases more; And vacuum gas oil also can obtain the good diesel product of part character through hydrotreatment, and its last running is converted into a large amount of fine-quality diesel oil products after hydrocracking.Therefore whole its character of device gained Medium diesel oil cut is quite good, can reach European IV diesel oil standard.
Compare diesel yield height of the present invention with conventional hydroeracking unit.Because in the hydrotreatment process, the part heavy distillate is converted into diesel oil distillate, and this part diesel oil distillate separated going out in separation system, having avoided entering hydrocracking reactor carries out the repetition cracking, thereby has improved the yield of diesel oil.
2, use method of the present invention, can significantly reduce the hydrogen consumption.On the one hand, the diesel oil distillate in the reaction effluent of hydrotreating reactor does not carry out hydrocracking reaction, makes hydrogen consumption reduce significantly.On the other hand, the reaction effluent of hydrocracking reactor enters hydrotreating reactor with after raw material mixes, and does not need independent recycle hydrogen; And this parallel feeding also reduced the temperature rise in the hydrotreating reactor, and required cold hydrogen amount is reduced, and therefore whole device recycle hydrogen flow reduces significantly, reduces investment outlay and process cost, thereby reduces the overall operation expense.
3, the present invention can change technological operation flexibly according to motor spirit supply/demand and market value, promptly suitably adjusts diesel oil distillate and does, and can produce different condensation point diesel products flexibly, to adapt to the needs of Various Seasonal, for oil refining enterprise is created maximum economic benefit.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is the low-hydrogenloss hydrogenation synoptic diagram of high-output qulified diesel oil provided by the invention.Some utility appliance among the figure such as process furnace, pump, interchanger etc. do not mark, but this is known to those of ordinary skills.
Flow process of the present invention is described in detail as follows: raw material boosts to reaction pressure after pipeline 1 mixes with reaction effluent from the hydrocracking reactor 24 of pipeline 25 through feedstock pump, this compound enters hydrotreating reactor 3 through pipeline 2, by contacting with hydrotreating catalyst, remove impurity such as metal in the stock oil, sulphur and nitrogen, finish the saturated of alkene and part aromatic hydrocarbons, and with the mild cracking of heavy distillate.Because contain higher aromaticity content in the raw material, the hydrotreatment process is emitted a large amount of heats, need in the middle of two beds of reactor, to introduce cold hydrogen, control reaction temperature through pipeline 22.The reaction effluent heat exchange cooling of hydrotreating reactor 3 is separated into two bursts of logistics after pipeline 4 enters high-pressure separator 5 in high-pressure separator 5, one is a gaseous stream, wherein contains hydrogen, hydrogen sulfide, ammonia and a small amount of lighter hydrocarbons; Another strand is liquid phase stream, and liquid phase stream mainly is a hydrogenated oil.Be divided into two-way through pipeline 7, recycle compressor 11, pipeline 12 after extracting out successively from the gaseous stream at high-pressure separator 5 tops, the one tunnel uses as cold hydrogen through pipeline 22; Another road enters hydrocracking reactor 24 with successively after the new hydrogen of pipeline 18, make-up hydrogen compressor 19, pipeline 20 mixes through pipeline 21.High-pressure separator 5 isolated liquid phase streams enter light pressure separator 8 through pipeline 6, extract hydrogen and the lighter hydrocarbons that remove out from light pressure separator 8 tops through pipeline 9, the liquid phase stream of light pressure separator 8 bottoms enters separation column 13 through pipeline 10, and isolated light naphtha fraction, heavy naphtha fraction, diesel oil distillate and tail oil cut are extracted out through pipeline 14,15,16,17 respectively.Behind the tail oil cut and recycle hydrogen mixing from pipeline 17 from pipeline 21, enter hydrocracking reactor 24 through pipeline 23, contact with hydrocracking catalyst at this, heavy distillate is changed into the light-end products of expectation, hydrocracking reactor 24 is introduced cold hydrogen through pipeline 22 too, prevents temperature of reaction because heat release causes temperature too high.
The following examples will give further instruction to present method, but therefore not limit present method.
The hydrotreating catalyst and the hydrocracking catalyst trade mark used among the embodiment are respectively RN-10 and RT-5, produce by Sinopec catalyzer branch office Chang Ling catalyst plant.
Embodiment 1
Stock oil A is mixed by 20 heavy % catalytic diesel oils and 80 heavy % vacuum gas oils, and its stock oil character is as shown in table 1.Stock oil with enter hydrotreating reactor after the reaction effluent of hydrocracking reactor mixes, under the effect of hydrotreating catalyst, react; The reaction effluent of hydrotreating reactor obtains each cut product after refrigerated separation, wherein the tail oil cut loops back hydrocracking reactor, carry out hydrocracking reaction, hydrotreating catalyst and hydrocracking catalyst are seated in respectively in two reactors, and the admission space ratio of hydrotreating catalyst and hydrocracking catalyst is 64: 36.Reaction conditions and product distribute and list in table 2 and table 3 respectively, by table 3 as seen, use method of the present invention, and the hydrogen consumption of stock oil A is 2.0 heavy %, less than the process raw material hydrogen consumption 2.5 heavy % of oily A of conventional hydroeracking unit; And diesel oil distillate (150～370 ℃) yield is up to 85.0 heavy %.The product property of heavy naphtha fraction, diesel oil distillate is as shown in table 4, and by table 4 as seen, it is 60 heavy % that the virtue of heavy naphtha fraction is dived, and is the fine reformer feed; Diesel oil distillate density is 0.832g/cm
3, sulphur content is less than 30ppm, and polycyclic aromatic hydrocarbon content is less than 5 heavy %, and cetane value is 54, is the quality products of low-sulfur, low aromatic hydrocarbons, high hexadecane value, can satisfy European IV diesel oil standard.
Stock oil B is a vacuum gas oil, and its stock oil character is as shown in table 1.According to the method for the present invention oily B that processes raw material, the admission space ratio of hydrotreating catalyst and hydrocracking catalyst is 60: 40, reaction conditions, product distribute and product property is listed in table 5, table 6 and table 7 respectively, by table 6 as seen, use method of the present invention, the hydrogen of stock oil B consumption is 2.1 heavy %, less than the process raw material hydrogen consumption 2.6 heavy % of oily A of conventional hydroeracking unit; And diesel oil distillate (150～370 ℃) yield is up to 80.0 heavy %.By table 7 as seen, it is 52 heavy % that the virtue of heavy naphtha fraction is dived, and is the fine reformer feed; Diesel oil distillate density is 0.825g/cm
3, sulphur content is less than 30ppm, and polycyclic aromatic hydrocarbon content is less than 3 heavy %, and cetane value is 57, is the quality products of low-sulfur, low aromatic hydrocarbons, high hexadecane value, can satisfy European IV diesel oil standard.
Table 1
| Stock oil | A | B |
| Density (20 ℃), g/cm 3 | 0.9129 | 0.9158 |
| S, heavy % | 2.2 | 2.7 |
| N，ppm | 617 | 832 |
| Boiling range (D-1160), ℃ | ||
| Initial boiling point | 188 | 261 |
| 10％ | 327 | 373 |
| 30％ | 390 | 408 |
| 50％ | 423 | 435 |
| 70％ | 448 | 456 |
| 90％ | 479 | 484 |
| Final boiling point | 540 | 540 |
Table 2
| Reaction conditions | Hydrotreating reactor | Hydrocracking reactor |
| The hydrogen dividing potential drop, MPa | 10.0 | 10.0 |
| Temperature of reaction, ℃ | 370 | 350 |
| Volume space velocity, h -1 | 1.0 * | 2.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 1000 | 1000 |
*Do not comprise hydrocracking reactor outlet logistics.
Table 3
| Hydrogen consumption (fresh feed weighs % relatively) | 2.0 |
| The main products yield, heavy % | |
| Light naphtha fraction (C 5～65℃) | 2.1 |
| Heavy naphtha fraction (65～150 ℃) | 11.3 |
| Diesel oil distillate (150～370 ℃) | 85.0 |
Table 4
| Main products character | Heavy naphtha fraction | Diesel oil distillate |
| The boiling range scope, ℃ | 65～150℃ | 150～370℃ |
| Density (20 ℃), g/cm 3 | 0.755 | 0.832 |
| S，ppm | ＜0.5 | ＜30 |
| N，ppm | ＜0.5 | ＜5 |
| Total aromaticity content, heavy % | -- | 18 |
| Polycyclic aromatic hydrocarbon content, heavy % | -- | ＜5 |
| Virtue is dived, heavy % | 60 | -- |
| Cetane value | -- | 54 |
Table 5
| Reaction conditions | Hydrotreating reactor | Hydrocracking reactor |
| The hydrogen dividing potential drop, MPa | 13.5 | 13.5 |
| Temperature of reaction, ℃ | 370 | 350 |
| Volume space velocity, h -1 | 1.0 * | 2.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 1000 | 1000 |
*Do not comprise hydrocracking reactor outlet logistics.
Table 6
| Hydrogen consumption (fresh feed weighs % relatively) | 2.1 |
| The main products yield, heavy % | |
| Light naphtha fraction (C 5～65℃) | 2.8 |
| Heavy naphtha fraction (65～150 ℃) | 15.3 |
| Diesel oil distillate (150～370 ℃) | 80.0 |
Table 7
| Main products character | Heavy naphtha fraction | Diesel oil distillate |
| The boiling range scope, ℃ | 65～150℃ | 150～370℃ |
| Density (20 ℃), g/cm 3 | 0.751 | 0.825 |
| S，ppm | ＜0.5 | ＜30 |
| N，ppm | ＜0.5 | ＜5 |
| Total aromaticity content, heavy % | -- | 14 |
| Polycyclic aromatic hydrocarbon content, heavy % | -- | ＜3 |
| Virtue is dived, heavy % | 52 | -- |
| Cetane value | -- | 57 |
Claims (7)
1, a kind of low-hydrogenloss hydrogenation of high-output qulified diesel oil comprises the following steps:
(1), stock oil mixes with the reaction effluent of hydrocracking reactor, enter hydrotreating reactor, carry out the slight hydrocracking reaction of hydrofining reaction and heavy distillate under the effect of hydrotreating catalyst, hydrotreating catalyst is VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports;
(2), the reaction effluent of hydrotreating reactor after the heat exchange cooling, enter high-pressure separator, light pressure separator, separation column successively, isolate light naphtha fraction, heavy naphtha fraction, diesel oil distillate and tail oil cut through separation column;
(3), the tail oil cut is recycled to hydrocracking reactor, in the presence of hydrogen, contact with hydrocracking catalyst, carry out hydrocracking reaction, hydrocracking catalyst is VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide and/or the Zeolite support;
(4) enter hydrocracking reactor from isolated hydrogen-rich gas of high-pressure separator and the new hydrogen of choosing wantonly.
2,, it is characterized in that described stock oil is vacuum gas oil and the mixture of optional catalytic cracking diesel oil according to the method for claim 1.
3, according to the method for claim 1, it is characterized in that the reaction conditions of described hydrotreating reactor and hydrocracking reactor is: hydrogen dividing potential drop 4.0～20.0MPa, 280～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000Nm
3/ m
3, volume space velocity 0.1～10.0h
-1
4, according to the method for claim 1 or 3, it is characterized in that the reaction conditions of described hydrotreating reactor and hydrocracking reactor is: hydrogen dividing potential drop 6.0～15.0MPa, 330～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 400～1500Nm
3/ m
3, volume space velocity 0.2～3.0h
-1
5, according to the method for claim 1, it is characterized in that described hydrotreating catalyst, be benchmark with the catalyzer, it consists of: nickel oxide 1～5 heavy %, Tungsten oxide 99.999 12～35 heavy %, fluorine 1～9 heavy %, surplus is an aluminum oxide.
6, according to the method for claim 1, it is characterized in that described hydrocracking catalyst, with the catalyzer is benchmark, it consists of: nickel oxide 2.5～6.0 heavy %, Tungsten oxide 99.999 10～38 heavy %, fluorine are 0.5～5.0 heavy %, surplus is a carrier, and this carrier is made up of unformed aluminum oxide and mesopore or large pore zeolite.
7,, it is characterized in that the admission space ratio of described hydrotreating catalyst and hydrocracking catalyst is 25: 75～75: 25 according to the method for claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101054419A CN100510022C (en) | 2005-09-28 | 2005-09-28 | Low-hydrogenloss hydrogenation of high-output qulified diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101054419A CN100510022C (en) | 2005-09-28 | 2005-09-28 | Low-hydrogenloss hydrogenation of high-output qulified diesel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1940029A true CN1940029A (en) | 2007-04-04 |
| CN100510022C CN100510022C (en) | 2009-07-08 |
Family
ID=37958556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101054419A Active CN100510022C (en) | 2005-09-28 | 2005-09-28 | Low-hydrogenloss hydrogenation of high-output qulified diesel oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100510022C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373085A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Catalytic conversion method for maximum production of high-cetane diesel oil |
| CN103102973A (en) * | 2011-11-14 | 2013-05-15 | 李清会 | Hydrogenated decomposition and separation system for intermediate composition oil of petroleum |
| CN103509599A (en) * | 2012-06-29 | 2014-01-15 | 中国石油化工股份有限公司 | Parallel-flow hydrogenation method for producing intermediate fraction oil |
| CN105745309B (en) * | 2013-11-25 | 2019-04-05 | 国际壳牌研究有限公司 | The method of micro- carbon residue content catalyzed conversion for heavy hydrocarbon feedstocks and its used in low surface area catalyst composition |
-
2005
- 2005-09-28 CN CNB2005101054419A patent/CN100510022C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373085A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Catalytic conversion method for maximum production of high-cetane diesel oil |
| CN102373085B (en) * | 2010-08-26 | 2013-12-25 | 中国石油化工股份有限公司 | Catalytic conversion method for maximum production of high-cetane diesel oil |
| CN103102973A (en) * | 2011-11-14 | 2013-05-15 | 李清会 | Hydrogenated decomposition and separation system for intermediate composition oil of petroleum |
| CN103509599A (en) * | 2012-06-29 | 2014-01-15 | 中国石油化工股份有限公司 | Parallel-flow hydrogenation method for producing intermediate fraction oil |
| CN103509599B (en) * | 2012-06-29 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of cocurrent flow type method of hydrotreating producing intermediate oil |
| CN105745309B (en) * | 2013-11-25 | 2019-04-05 | 国际壳牌研究有限公司 | The method of micro- carbon residue content catalyzed conversion for heavy hydrocarbon feedstocks and its used in low surface area catalyst composition |
| US11344865B2 (en) | 2013-11-25 | 2022-05-31 | Shell Usa, Inc. | Process for the catalytic conversion of micro carbon residue content of heavy hydrocarbon feedstocks and a low surface area catalyst composition for use therein |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100510022C (en) | 2009-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100590182C (en) | Method for producing cleaning oil from coal-tar oil | |
| CN100558863C (en) | A kind of combined method of producing cleaning oil from coal-tar oil | |
| CN1876767B (en) | Coal tar hydrocracking method | |
| CN101294107B (en) | Method for preparing fuel oil with coal oil hydrogenation | |
| CN1923972A (en) | Hydrocarbons hydrocracking method | |
| CN100510023C (en) | Production of cleaning fuel from heavy-fraction oil | |
| CN103305271B (en) | The combined technical method of a kind of residual oil/middle coalite tar lighting | |
| CN101760233A (en) | Method for hydrocracking of coked wax oil | |
| CN1854265A (en) | Production of intermediate fractional oil from Fischer-Tropsch synthetic oil | |
| CN103305269B (en) | Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar | |
| CN1854264A (en) | Integrated Fischer-Tropsch synthetic oil hydrogenation purification | |
| CN1854263A (en) | Hydrogenation cracking method of mass production of chemical materials | |
| CN100443572C (en) | Hydrogenation cracking method of high-output diesel oil from high-nitrogen content heavy raw material | |
| CN101230291A (en) | Low consumption energy method for processing fischer-tropsch synthesis | |
| CN100510022C (en) | Low-hydrogenloss hydrogenation of high-output qulified diesel oil | |
| CN1854266A (en) | Hydrogenation purifying combined process for Fischer-Tropsch synthetic substance | |
| CN1896181A (en) | Production of high-bioctyl-value diesel oil by coal liquification | |
| CN103525461A (en) | Hydrocracking method | |
| CN102311782B (en) | Method for producing diesel oil by purifying coal tar through hydrogenating | |
| CN100351346C (en) | Medium pressure hydrocracking process for preparing jet fuel | |
| CN100419044C (en) | Production of large-specific-weight aircraft liquid petroleum oil at maximum from coal liquefied oil | |
| CN1128859C (en) | Converting and combining method for hydrogenation of hydrocarbon | |
| CN1216967C (en) | Hydrogenation cracking method for maximally producing intermediate distillate | |
| CN1261544C (en) | Medium pressure hydrogenation method for maximumly producing high quality diesel fuel | |
| CN102816596A (en) | Deep processing method of non-caking coal or feebly caking coal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |