CN101314735A - Hydrogenation method for reducing aromatic hydrocarbon content of diesel oil cut fraction and improving its cetane number - Google Patents
Hydrogenation method for reducing aromatic hydrocarbon content of diesel oil cut fraction and improving its cetane number Download PDFInfo
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Abstract
A hydrogenation method for reducing arene content and improving cetane number of diesel distillate comprises the following steps: cutting a diesel material into a light component and a heavy component at a cutting temperature of 280 to 340 DEG C; circulating the heavy component and hydrogen in converse direction, and passing through a hydrogenation and modification catalyst bed in a first hydrogenation reaction zone to carry out deep dearomatization and arene ring-opening reaction; circulating the light component and hydrogen in the same direction, and passing through a hydrorefining catalyst bed in a second hydrogenation reaction zone to carry out hydrorefining reaction; and mixing the reaction effluents in the two reaction zones, cooling, separating, and distilling to obtain naphtha distillate and diesel product. The method can process diesel distillate with high sulfur content, high nitrogen content and high final boiling end under a moderate operation condition with low pressure and high air speed to obtain clean diesel product with low sulfur content, low arene content and high cetane number, and the product can meet the EuroIV emission standard.
Description
Technical field
The invention belongs to a kind ofly in the method that has under the situation of hydrogen refining hydrocarbon ils, more particularly, is a kind of method of hydrotreating of producing low aromatic hydrocarbons high hexadecane value clean diesel.
Background technology
In recent years, along with developing of automobile industry, the increase of automobile pollution, Economic development to many countries, irreplaceable effect has all been played in the raising of people's living standard, but also brought problems, particularly motor vehicle exhaust huge simultaneously, HUMAN HEALTH and environment for human survival have been constituted a serious threat to the multiple amount of pollutants in the atmosphere.The production of clean fuel is to reduce the effective measure that vehicle exhaust pollutes atmosphere.The clean fuel standards of increasingly stringent is formulated for this reason and issued and implemented in countries in the world, aromaticity content and cetane value for diesel oil in these standards have also all proposed strict more requirement, for example European Union requires diesel cetane-number to be not less than 51 in the European III automobile emissions standards that began to carry out in 2000, and polycyclic aromatic hydrocarbon content is not more than 11 volume %.In Europe IV number and the European V automobile emissions standards same requirement is arranged also.In recent years, China also begins to implement gradually the fuel standard in Europe.Come into effect Europe III emission standard in 2005 in cities such as Beijing, Shanghai, planned in 2008 and carried out the diesel oil index of Europe IV, Euro V emissions in 2010 respectively.
Except that Fischer-Tropsch combined diesel oil and hydrocracking diesel oil, catalytic diesel oil, coker gas oil and visbreaking diesel oil all can not satisfy the requirement of clean diesel sulphur content, aromaticity content and cetane value, even straight-run diesel oil also has quite a few to be difficult to satisfy Europe IV specification requirement.Therefore, when producing clean diesel, all diesel oil blending components all must deep hydrodesulfurizationof and/or deeply hydrodearomatized.
The technological difficulties of producing clean diesel are particularly catalytic diesel oil and coker gas oil components of all diesel components, should deep desulfuration again deeply de-aromatizing improve cetane value, also need investment and the production cost all can not be too high.
Produce low-sulfur, low aromatic hydrocarbons, high hexadecane value clean diesel with existing technology, must under original complete processing, improve the severity of operation.Usually the measure of taking comprises the raising temperature of reaction, improves the reactive hydrogen dividing potential drop and reduces air speed etc.But the raising temperature of reaction not only has a strong impact on catalyzer work-ing life, and the device cycle of operation is shortened, and the aromatic hydrocarbons saturated reaction is the reaction that is subjected to thermodynamics equilibrium limit, when under certain reaction pressure, along with the rising of temperature of reaction, the product aromaticity content can increase.And high hydrogen dividing potential drop has proposed more requirement to equipment, causes production cost to rise significantly; Reduce volume space velocity and mean the reduction unit capacity.Therefore, concerning prior art, improve severity and not only can bring running cost raising, operational cycle to shorten, also can bring product to take off problems such as fragrant rate reduction.
US 6042716 discloses a kind of method that adopts two-stage method production to hang down aromatic hydrocarbons, high hexadecane value diesel oil.This method comprises two hydroconversion reaction zones, adopt non-precious metal catalyst to carry out the deep desulfuration denitrification reaction at first reaction zone, the effluent of first reaction zone enters second reaction zone after through a high pressure stripping jar, and second reaction zone adopts a kind of noble metal catalyst to carry out the deeply de-aromatizing reaction.Adopt this method can obtain the very low diesel product of aromaticity content, cetane value improves 10 more than the unit.But adopted noble metal catalyst to make cost up in this method, running has a big risk, flexibility of operation descends.
US 5183556 discloses a kind of method that adopts the low aromatics diesel of two reaction zone productions.Contact with non-precious metal catalyst in the mode of concurrent and react at first reaction zone raw material and hydrogen, the gas phase effluent of first reaction zone is told afterwards, the liquid phase effluent of first reaction zone and hydrogen enter second reaction zone in the mode of reverse flow, contact with base metal or noble metal catalyst and react at second reaction zone.This method main purpose is to take off aromatic hydrocarbons, does not consider further to increase cetane value.
US 5068025 discloses a kind of method of desulfurizing and dearomatizing diesel oil deeply, this method adopts the dual catalyst bed reactive system that two kinds of different non-precious metal catalysts are housed respectively, first bed loads the strong NiW catalyzer of a kind of hydrogenation performance, mainly carries out the saturated reaction of aromatic hydrocarbons; Second bed loads the good Co of a kind of desulfurization performance and/or Ni and Mo Hydrobon catalyst, carries out deep hydrodesulfurizationof and takes off aromatic hydrocarbons.This method adopts non-precious metal catalyst to realize the purpose that deep hydrodesulfurizationof takes off aromatic hydrocarbons, but this method does not consider further to increase cetane value.
CN 1769387A discloses a kind of hydroprocessing process of diesel oil distillate, this method is lighting end and last running with the stock oil fractionation earlier, lighting end is in first reaction zone and Hydrobon catalyst contact reacts, last running is in second reaction zone and Hydrobon catalyst contact reacts, and two reaction zone liquid products are mixed into refining distillate.Wherein second reaction zone is than the severe reaction conditions of first reaction zone, and/or first reaction zone uses hydrogenation catalyst, second reaction zone with high desulfurization activity to use the hydrogenation catalyst with high hydrogenation activity.But the main purpose of this method is the sulphur content that reduces in the raw material, does not relate to Tuo Fang and improves cetane value.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of hydrotreating that reduces aromatic hydrocarbon content of diesel oil cut fraction and improve its cetane value.
Method provided by the invention comprises:
(1) diesel raw material oil is cut into light constituent and heavy constituent, and its cut point is 280～340 ℃;
(2) the catalyst for hydro-upgrading bed of first hydroconversion reaction zone is passed through in heavy constituent and hydrogen reverse flow, 260～450 ℃ of temperature of reaction, and hydrogen dividing potential drop 1.0～12.0MPa, volume space velocity 0.1～6.0h during liquid
-1, hydrogen to oil volume ratio 100～1500Nm
3/ m
3Condition under react;
(3) light constituent and hydrogen concurrent pass through the Hydrobon catalyst bed of second hydroconversion reaction zone, 250～420 ℃ of temperature of reaction, and hydrogen dividing potential drop 1.0～12.0MPa, volume space velocity 0.3～10.0h during liquid
-1, hydrogen to oil volume ratio 100～1000Nm
3/ m
3Condition under react;
Cool off after the reaction effluent of the reaction effluent of (4) first hydroconversion reaction zones and second hydroconversion reaction zone mixes and separate, separating obtained liquid phase stream enters fractionating system, obtains naphtha fraction and diesel product after fractionation.
Adopt method provided by the invention, can handle high-sulfur, high nitrogen and the high diesel oil distillate of final boiling point, can be at pressure low and air speed height so comparatively under the demulcent operational condition, obtain the clean diesel product that sulphur content is low, aromaticity content is low and cetane value is high, product index can reach Europe IV emission standard.Flow process of the present invention is simple, working pressure is low, facility investment and process cost are all lower.Since with raw material be cut into light, weigh two kinds of components, two kinds of components are adopted different treatment processs, light constituent is carried out mild hydrogenation, and carry out deeply hydrodearomatized to heavy constituent, avoided light constituent hydrogenation reaction exceedingly, reduced reactive chemistry hydrogen consumption, thereby reduced tooling cost.
Description of drawings
Accompanying drawing is reduction aromatic hydrocarbon content of diesel oil cut fraction provided by the invention and the method for hydrotreating schematic flow sheet that improves its cetane value.
Embodiment
Aromatic hydrocarbon in diesel oil also has part three rings and the above aromatic hydrocarbons of three rings mainly based on monocycle and dicyclo.Aromaticity content increases with the change of distillate is heavy, and its structure also is tending towards complicated simultaneously.Relative straight-run diesel oil, catalytic cracking diesel oil is the aromaticity content height not only, and double ring arene and the shared proportion increase of thrcylic aromatic hydrocarbon.Polycyclic aromatic hydrocarbons of the present invention also is condensed-nuclei aromatics, is meant shared respectively two aromatic hydrocarbon that adjacent carbon atom forms of two or more aromatic nucleus, as naphthalene, anthracene and phenanthrene etc.The distribution of aromatic hydrocarbons is relevant with the boiling range of distillate, and mononuclear aromatics mainly is present in the lighting end, and three rings and the above aromatic hydrocarbons of three rings mainly exist in the last running.
Aromatic hydrogenation is saturated to be a reversible thermopositive reaction, and the equilibrium constant was bigger when temperature of reaction was low, and speed of response is slower; And temperature when high the equilibrium constant less, speed of response is very fast.In the diesel oil fraction hydrogenating process, the arene engaging scraping rate has a maximum value with the temperature of reaction curve increase that raises, promptly after temperature rises to a certain numerical value, and owing to the restriction that is subjected to thermodynamic(al)equilibrium, elevated temperature again, the aromatic hydrocarbons saturation exponent can reduce.In addition, rising reaction pressure helps the aromatic hydrocarbons saturated reaction.From the saturated complexity of hydrogenation, first aromatic ring hydrogenation of condensed-nuclei aromatics is easier to, and two ring hydrogenation take second place, but the whole hydrogenation of aromatic ring are saturated very difficult.That is to say that thrcylic aromatic hydrocarbon in the raw material and the easy hydrogenation of aromatic hydrocarbons more than three rings are saturated to be two ring or mononuclear aromatics, but the number of total aromatic hydrocarbons does not reduce in the raw material.Thus, polycyclic aromatic hydrocarbon content is many more in the raw material, and the arene engaging scraping difficulty is big more.
The height of diesel cetane-number (or cetane index) has considerable influence to diesel oil at in-engine delay period, increases cetane value and can improve cold starting performance, reduces oil consumption and reduce discharging.Aromatic hydroxy compound in the diesel oil distillate is lower cetane value component, and the aromatic hydrocarbons number of rings is many more, and cetane value is low more.Aromaticity content in the reduction diesel oil can improve the cetane value of oil product.But, because the cetane value of the alkyl benzene of short-side chain and perhydronaphthalene class is not high, thus the double ring arene hydrogenation in the diesel oil distillate is saturated become naphthenic hydrocarbon after, the cetane value increasing degree of oil product is very limited.Have only naphthenic ring further to rupture, when generating the mononuclear aromatics of alkane, the single-ring naphthene that has alkyl chain or many alkyl group side chains, the cetane value of oil product just can significantly increase.Thereby in significantly improving the hydrogenation dearomatization technology of cetane value, except the aromatic hydrogenation saturated reaction should take place, also wish to take place the ring-opening reaction of naphthenic ring.
By above analysis and the understanding that diesel oil fraction hydrogenating is taken off arylation reaction, the specific embodiment of the present invention is:
(1) diesel raw material oil is cut into light constituent and heavy constituent, and its cut point is 280～340 ℃; Because the boiling range of aromatic hydrocarbons and distribution of sulphide and raw material has very big relation, the most difficult sulfide major part that removes concentrates in the heavy ends of diesel oil distillate, be that to contain the amount of dibenzothiophene of multi-substituent in the high more diesel oil distillate of boiling point many more, the content of polycyclic aromatic hydrocarbons is also many more.Therefore, different according to raw material oil properties and composition, at 280～340 ℃ raw material is cut into two kinds of components of weight, according to light constituent and heavy constituent characteristics separately and the various objectives that will reach, it is taked different treatment processs then.
(2) the catalyst for hydro-upgrading bed of first hydroconversion reaction zone is passed through in heavy constituent and hydrogen reverse flow, 260～450 ℃ of temperature of reaction, and preferred 280～420 ℃, hydrogen dividing potential drop 1.0～12.0MPa, preferred 2.0～10.0MPa, volume space velocity 0.1～6.0h during liquid
-1, preferred 0.3～5.0h
-1, hydrogen to oil volume ratio 100～1500Nm
3/ m
3, preferred 150～1000Nm
3/ m
3Condition under, react hydrogenating desulfurization, hydrodenitrification, aromatic hydrocarbons is saturated and the polycyclic aromatic hydrocarbons ring-opening reaction.
The present invention utilizes the polycyclic aromatic hydrocarbons of difficult reaction to be distributed in the characteristics of diesel oil last running, heavy constituent is separated separately carry out the open loop cracking reaction, reaches to reduce polycyclic aromatic hydrocarbon content, improve cetane value and improve the purpose of character such as boiling range, density.
Described first hydroconversion reaction zone is provided with at least one fixed bed hydrogenation reactor, and described fixed-bed reactor are reverse flow reactor, i.e. the heavy constituent of step (1) gained enter reactor by reactor top, and hydrogen enters reactor by reactor lower part.Take gas-liquid conversed stream mode at first hydroconversion reaction zone, can make reaction bed temperature more even, make the catalyzer of the upper and lower bed synchronous inactivation of trying one's best, thereby make full use of catalyzer; Can also effectively avoid the big restraining effect of the hydrogen sulfide, ammonia and the hydro carbons small molecules that in reaction process, generate reaction such as saturated and aromatic hydrocarbons open loop, thereby avoid the decline of its speed of reaction aromatic hydrocarbons.
First hydroconversion reaction zone makes and takes off aromatic hydrocarbons and be reflected under the saturated thermodynamic(al)equilibrium temperature of aromatic hydrocarbons and carry out under the reaction conditions of deeply de-aromatizing, helps removing to greatest extent aromatic hydrocarbons.Because raw material is cut, have only heavy ends through containing the composite catalyst bed of zeolite, so good reaction selectivity, the diesel product yield height has reduced the air speed of this reaction zone in addition, helps the carrying out of aromatic hydrocarbons saturated reaction.Simultaneously, reduce the saturated degree of mononuclear aromatics participation hydrogenation in the light constituent effectively, reduced reactive chemistry hydrogen consumption.
(3) light constituent and hydrogen concurrent pass through the Hydrobon catalyst bed of second hydroconversion reaction zone, 250～420 ℃ of temperature of reaction, and preferred 260～400 ℃, hydrogen dividing potential drop 1.0～12.0MPa, preferred 2.0～10.0MPa, volume space velocity 0.3～10.0h during liquid
-1, preferred 0.5～8.0h
-1, hydrogen to oil volume ratio 100～1000Nm
3/ m
3, preferred 120～800Nm
3/ m
3Condition under, carry out hydrogenating desulfurization, denitrogenation and aromatic hydrocarbons saturated reaction.
Because the sulfide in the light constituent more easily removes, the content of polycyclic aromatic hydrocarbons is also less, therefore it is carried out hydrofining, has promptly removed impurity, has avoided light constituent hydrogenation reaction exceedingly again, has reduced reactive chemistry hydrogen consumption, thereby has reduced tooling cost.
Described second hydroconversion reaction zone is provided with at least one fixed bed hydrogenation reactor, and described fixed-bed reactor are flow reactor in the same way, and promptly the light constituent and the hydrogen of step (1) gained all enter reactor by reactor head.
Cool off after the reaction effluent of the reaction effluent of (4) first hydroconversion reaction zones and second hydroconversion reaction zone mixes and separate, but separating obtained hydrogen-rich gas Returning reacting system recycles, separating obtained liquid phase stream enters fractionating system, obtains naphtha fraction and diesel product after fractionation.
In described diesel raw material grease separation catalytic cracking diesel oil, straight-run diesel oil, coker gas oil and the visbreaking diesel oil one or more, its boiling range is 180 ℃～400 ℃.
The admission space ratio of described catalyst for hydro-upgrading and Hydrobon catalyst is 4: 6～7: 3.According to the stock oil composition and property with to the different mass requirement of product, can adjust the concrete cut point of light constituent and heavy constituent, and the catalyst proportion scheme of two reaction zones.
Described catalyst for hydro-upgrading is group vib metal and/or the group VIII non-precious metal catalyst that loads on the carrier of being made up of aluminum oxide and zeolite, and wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.
Preferred described catalyst for hydro-upgrading consists of, in oxide compound and with the catalyzer total amount is benchmark, and the content of molybdenum and/or tungsten is 10～35 heavy %, content 1～15 heavy % of nickel and/or cobalt, surplus is a carrier, and the weight ratio of aluminum oxide and zeolite is 90: 10～50: 50 in the carrier.
Described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60～600 dust holes accounts for the aluminum oxide of total pore volume more than 70%.Described zeolite is to be selected from faujusite, mordenite, zeolite L, omega zeolite, ZSM-4 zeolite and the Beta zeolite one or more, and preferred y-type zeolite, particularly preferred zeolite are that total acid content is 0.02 to less than 0.5 mmole/gram.
The preferred catalyst for hydro-upgrading of the present invention has the good shape open loop ability of selecting, and can make the open loop cracking of the above cyclic aromatic compounds of dicyclo in the raw material, thereby reach the reduction polycyclic aromatic hydrocarbon content, improves the purpose of cetane value and reduction density.Studies show that, the chemical reaction of double ring arene is followed following approach: become naphthane after most of double ring arene hydrogenation is saturated, become two Yuans naphthenic hydrocarbon after the further hydrogenation of part naphthane is saturated, another part naphthane becomes mononuclear aromatics through the open loop cracking reaction, and the further more saturated single-ring naphthene that becomes of hydrogenation of the mononuclear aromatics of part.Above-mentioned reaction network, except the open loop cracking reaction of naphthane does not have the reversed reaction, all the other hydrogenation saturated reactions all have reversed reaction to take place, and therefore a corresponding chemical equilibrium is arranged.The catalyst for hydro-upgrading that the present invention uses has good open loop cracking ability, promoted that naphthane open loop cracking is the generation of mononuclear aromatics reaction, thereby broken the chemical equilibrium of entire reaction network, make entire reaction to carry out smoothly along the saturated course of repeated hydrogenation after the naphthane open loop cracking, thereby reach higher depth of conversion, reduced the polycyclic aromatic hydrocarbon content in the heavy constituent and improved cetane value.
Described Hydrobon catalyst is group vib metal and/or the group VIII non-precious metal catalyst that loads on unformed aluminum oxide and/or the silica-alumina supports, and wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.
Preferred described Hydrobon catalyst, with the catalyzer is benchmark, it consists of: nickel oxide 1～10 heavy %, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina, with the carrier is benchmark, and silica content is 2～45 heavy %, and alumina content is 55～98 heavy %; The content of further preferred silicon oxide is 5～40 heavy %, and the content of aluminum oxide is 60～95 heavy %.Described silica-alumina has the specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of preferred silica-alumina is 150～350m
2/ g, more preferably 180～300m
2/ g, the pore volume of preferred silica-alumina is 0.4～1ml/g, more preferably 0.5～0.8ml/g.
The preferred Hydrobon catalyst of the present invention, the reactive behavior height can be under demulcent reaction conditions comparatively, the sulphur in the effective elimination light constituent, nitrogen impurity, and, also help the carrying out of aromatic hydrocarbons saturated reaction because its hydrogenation performance is good.
Accompanying drawing is reduction aromatic hydrocarbon content of diesel oil cut fraction provided by the invention and the method for hydrotreating synoptic diagram that improves its cetane value.Below in conjunction with accompanying drawing method provided by the present invention is further detailed, has omitted many equipment among the figure, as pump, process furnace, interchanger, compressor etc., but this is known to those of ordinary skills.
Reduction aromatic hydrocarbon content of diesel oil cut fraction provided by the invention and the method for hydrotreating technical process that improves its cetane value are described in detail as follows: enter separation column 28 from the diesel raw material oil of pipeline 1 and carry out the cut cutting, the light constituent of gained and heavy constituent are extracted out through pipeline 3 and pipeline 2 respectively.Enter reactor 4 from the heavy constituent of pipeline 2 by the top of reactor 4, reactor 4 is first hydroconversion reaction zone, the filling catalyst for hydro-upgrading.Enter reactor 4 from the hydrogen of pipeline 20 by the bottom of reactor 4, heavy constituent and hydrogen contact on catalyst for hydro-upgrading in the mode of reverse flow and react, and finish the saturated and ring-opening reaction of hydrofining and polycyclic aromatic hydrocarbons.Extract out through pipeline 5 liquid phase effluent autoreactor 4 bottoms of first hydroconversion reaction zone, and extract out through pipeline 6 at gas phase effluent autoreactor 4 tops of first hydroconversion reaction zone, and the two mixing is after pipeline 26 extractions.Mix the back with hydrogen from pipeline 21 from the light constituent of pipeline 3 and enter reactor 7 by reactor 7 tops, reactor 7 is second hydroconversion reaction zone, the filling Hydrobon catalyst.Light constituent and hydrogen carry out hydrogenating desulfurization, denitrogenation and aromatic hydrocarbons saturated reaction in the mode of concurrent under the effect of Hydrobon catalyst.The resultant of reaction of second hydroconversion reaction zone with after resultant of reaction from first hydroconversion reaction zone of pipeline 26 mixes, enters high-pressure separator 9 through pipeline 27 and carries out gas-liquid separation after pipeline 8 is extracted out.The hydrogen-rich gas at high-pressure separator 9 tops enters circulating hydrogen compressor 23 by pipeline 22, is extracted out by pipeline 24 after circulating hydrogen compressor 23 superchargings.From the new hydrogen of pipeline 17 by new hydrogen supercharger 18 superchargings after, mix with recycle hydrogen through pipeline 19 from pipeline 24, mix hydrogen and extract out by pipeline 25.Hydrogen from pipeline 25 is divided into two-way, and one the tunnel enters reactor 4 through pipeline 20 by the bottom of reactor 4, and another road enters the top of reactor 7 through pipeline 21.The liquid phase stream of high-pressure separator 9 bottoms enters light pressure separator 11 through pipeline 10, carries out further gas-liquid separation at this, and isolated gas is extracted out through pipeline 13; The liquid of light pressure separator 11 bottoms enters separation column 14 through pipeline 12.The liquid phase stream that enters separation column 14 is after fractionation, and the naphtha fraction of gained and diesel product are extracted out through pipeline 16 and pipeline 15 respectively.
Advantage of the present invention is:
1, adopts method provided by the invention, can handle high-sulfur, high nitrogen and do high diesel oil distillate, can be at pressure low and air speed height so comparatively under the demulcent operational condition, obtain the diesel product of low-sulfur, low aromatic hydrocarbons, high hexadecane value, product index can reach Europe IV emission standard.
2, the present invention with diesel oil distillate be cut into light, weigh two kinds of components, carry out the different hydrotreatment reaction of severity at different reaction zones, and carry out the optimization of reaction conditions at two reaction zones different feed composition and reaction purposes, reach energy-conservation, reduce hydrogen consumption, and the effect that improves the economy of device.
3, method flow provided by the invention is simple, working pressure is low, facility investment and process cost are all lower, the catalyst activity height, and activity stability is good, and the device cycle of operation is long.Both can be used in new device, and also can be used for building on the plant modification.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
The trade names of the catalyst for hydro-upgrading of the first used hydroconversion reaction zone are RIC-1 among the embodiment; The trade names of the Hydrobon catalyst of second reaction zone are RS-1000, are catalyzer Chang Ling branch office of China Petrochemical Corp. and produce.
Used stock oil A is a kind of catalytic diesel oil among the embodiment, and stock oil B is a kind of catalytic diesel oil, and raw material C is a kind of straight-run diesel oil.The main character of various raw materials is as shown in table 1.
Embodiment 1
Stock oil A is cut into two components of weight at 320 ℃.Enter first reactor greater than 320 ℃ heavy constituent by the top of first reactor, hydrogen is then entered by first reactor lower part, carries out the saturated and open loop cracking reaction of hydrogenation of polycyclic aromatic hydrocarbons under the environment of gas-liquid counter current; Enter second hydrogenator less than 320 ℃ of light constituents and the back top of hydrogen mixing by second hydrogenator, under the effect of Hydrobon catalyst, react, the resultant of two reactors mixes after after cooling, separation and the fractionation, obtain naphtha fraction and diesel product.The reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3.
As can be seen from Table 3, the sulphur content of diesel product is 20 μ g/g, and polycyclic aromatic hydrocarbon content is 5.0 heavy %, and cetane index is 51.4, is the high-quality clean diesel that satisfies Europe IV emission standard.A compares with stock oil, and the total aromatic hydrocarbons of gained diesel product and the content of polycyclic aromatic hydrocarbons all descend significantly, and cetane index increases substantially, and diesel product yield can reach more than the 98.0 heavy %.
Stock oil B is cut into two components of weight at 310 ℃.Enter first reactor greater than 310 ℃ heavy constituent by the top of first reactor, hydrogen is then entered by first reactor lower part, carries out the saturated and open loop cracking reaction of hydrogenation of polycyclic aromatic hydrocarbons under the environment of gas-liquid counter current; Enter second hydrogenator less than 310 ℃ of light constituents and the back top of hydrogen mixing by second hydrogenator, under the effect of Hydrobon catalyst, react, the resultant of two reactors mixes after after cooling, separation and the fractionation, obtain naphtha fraction and diesel product.The reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3.
As can be seen from Table 3, the sulphur content of diesel product is 10 μ g/g, and polycyclic aromatic hydrocarbon content is 3.0 heavy %, and cetane index is 46.0, is the high-quality clean diesel that satisfies Europe IV emission standard.B compares with stock oil, and the total aromatic hydrocarbons of gained diesel product and the content of polycyclic aromatic hydrocarbons all descend significantly, and cetane index improves 13.8 units, and diesel product yield can reach more than the 98.0 heavy %.
Stock oil C is cut into two components of weight at 300 ℃.Enter first reactor greater than 300 ℃ heavy constituent by the top of first reactor, hydrogen is then entered by first reactor lower part, carries out the saturated and open loop cracking reaction of hydrogenation of polycyclic aromatic hydrocarbons under the environment of gas-liquid counter current; Enter second hydrogenator less than 300 ℃ of light constituents and the back top of hydrogen mixing by second hydrogenator, under the effect of Hydrobon catalyst, react, the resultant of two reactors mixes after after cooling, separation and the fractionation, obtain naphtha fraction and diesel product.The reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3.
As can be seen from Table 3, the sulphur content of diesel product is 5 μ g/g, and polycyclic aromatic hydrocarbon content is that cetane index is 61, is the high-quality clean diesel that satisfies Europe IV emission standard less than 2.0 heavy %.And diesel product yield can reach more than the 99.0 heavy %.
Table 1
| The stock oil numbering | A | B | C |
| Density (20 ℃), g/cm 3 | 0.8840 | 0.9022 | 0.8384 |
| Sulphur content, μ g/g | 12600 | 8000 | 9800 |
| Nitrogen content, μ g/g | 686 | 500 | 355 |
| Aromatic hydrocarbons, heavy % | 54.3 | 53.0 | 25.0 |
| Polycyclic aromatic hydrocarbons, heavy % | 34.8 | 23.0 | 9.0 |
| Cetane index, ASTM D-4737 | 39.4 | 32.2 | 54.9 |
| Boiling range ASTM D-1160, ℃ | |||
| IBP | 194 | 167 | 210 |
| 10％ | 235 | 219 | 234 |
| 50％ | 293 | 276 | 285 |
| 90％ | 351 | 347 | 339 |
| FBP | 363 | 363 | 356 |
Table 2
| Numbering | Embodiment 1 | |
|
| Stock oil | A | B | C |
| First hydroconversion reaction zone | |||
| The hydrogen dividing potential drop, MPa | 6.8 | 6.4 | 5.9 |
| Temperature of reaction, ℃ | 353 | 370 | 366 |
| Volume space velocity during liquid, h -1 | 1.0 | 1.0 | 2.0 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 500 | 500 | 400 |
| Second hydroconversion reaction zone | |||
| The hydrogen dividing potential drop, MPa | 6.8 | 6.4 | 5.9 |
| Temperature of reaction, ℃ | 332 | 349 | 340 |
| Volume space velocity during liquid, h -1 | 2.5 | 2.5 | 3.0 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 400 | 400 | 200 |
Table 3
| Embodiment 1 | |
|
Europe IV diesel oil index | |
| Density (20 ℃), g/cm 3 | 0.8420 | 0.8670 | 0.8174 | 0.820-0.845 |
| Sulphur content, μ g/ |
20 | 10 | 5 | ＜50 |
| Nitrogen content, μ g/ |
5 | 4 | ＜1 | - |
| Total aromatic hydrocarbons, heavy % | 14.5 | 14.0 | 13.2 | - |
| Polycyclic aromatic hydrocarbons, heavy % | 5.0 | 3.0 | ＜2.0 | ＜11 |
| Cetane index, ASTM D-4737 | 51.4 | 46.0 | 61.0 | ＞46 |
| Diesel yield, heavy % | ＞98.0 | ＞98.0 | ＞99.0 | - |
Claims (10)
1, a kind of method of hydrotreating that reduces aromatic hydrocarbon content of diesel oil cut fraction and improve its cetane value comprises:
(1) diesel raw material oil is cut into light constituent and heavy constituent, and its cut point is 280～340 ℃;
(2) the catalyst for hydro-upgrading bed of first hydroconversion reaction zone is passed through in heavy constituent and hydrogen reverse flow, 260～450 ℃ of temperature of reaction, and hydrogen dividing potential drop 1.0～12.0MPa, volume space velocity 0.1～6.0h during liquid
-1, hydrogen to oil volume ratio 100～1500Nm
3/ m
3Condition under react;
(3) light constituent and hydrogen concurrent pass through the Hydrobon catalyst bed of second hydroconversion reaction zone, 250～420 ℃ of temperature of reaction, and hydrogen dividing potential drop 1.0～12.0MPa, volume space velocity 0.3～10.0h during liquid
-1, hydrogen to oil volume ratio 100～1000Nm
3/ m
3Condition under react;
Cool off after the reaction effluent of the reaction effluent of (4) first hydroconversion reaction zones and second hydroconversion reaction zone mixes and separate, separating obtained liquid phase stream enters fractionating system, obtains naphtha fraction and diesel product after fractionation.
2, method according to claim 1 is characterized in that the reaction conditions of described first hydroconversion reaction zone is: volume space velocity 0.3～5.0h when 280～420 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～10.0MPa, liquid
-1, hydrogen to oil volume ratio 150～1000Nm
3/ m
3
3, method according to claim 1 is characterized in that the reaction conditions of described second hydroconversion reaction zone is: volume space velocity 0.5～8.0h when 260～400 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～10.0MPa, liquid
-1, hydrogen to oil volume ratio 120～800Nm
3/ m
3
4, method according to claim 1 is characterized in that in described diesel raw material grease separation catalytic cracking diesel oil, straight-run diesel oil, coker gas oil and the visbreaking diesel oil one or more.
5, method according to claim 1, it is characterized in that described catalyst for hydro-upgrading is group vib metal and/or the group VIII non-precious metal catalyst that loads on the carrier of being made up of aluminum oxide and zeolite, wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.
6, method according to claim 5, it is characterized in that described catalyst for hydro-upgrading consists of, in oxide compound and with the catalyzer total amount is benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, content 1～15 heavy % of nickel and/or cobalt, surplus is a carrier, and the weight ratio of aluminum oxide and zeolite is 90: 10～50: 50 in the carrier.
7, method according to claim 6, it is characterized in that described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60～600 dust holes accounts for the aluminum oxide of total pore volume more than 70%.
8, method according to claim 6 is characterized in that described zeolite is to be selected from faujusite, mordenite, zeolite L, omega zeolite, ZSM-4 zeolite and the Beta zeolite one or more.
9, method according to claim 1, it is characterized in that described Hydrobon catalyst is group vib metal and/or the group VIII non-precious metal catalyst that loads on unformed aluminum oxide and/or the silica-alumina supports, wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.
10, method according to claim 9, it is characterized in that described Hydrobon catalyst, with the catalyzer is benchmark, and it consists of: nickel oxide 1～10 heavy %, and molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina, is benchmark with the carrier, silica content is 2～45 heavy %, and alumina content is 55～98 heavy %.
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| CNA2007100998412A CN101314735A (en) | 2007-05-31 | 2007-05-31 | Hydrogenation method for reducing aromatic hydrocarbon content of diesel oil cut fraction and improving its cetane number |
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| CNA2007100998412A CN101314735A (en) | 2007-05-31 | 2007-05-31 | Hydrogenation method for reducing aromatic hydrocarbon content of diesel oil cut fraction and improving its cetane number |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102079985A (en) * | 2009-11-26 | 2011-06-01 | 中国石油化工股份有限公司 | Catalytic conversion method for producing high-cetane number light diesel oil |
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- 2007-05-31 CN CNA2007100998412A patent/CN101314735A/en active Pending
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| CN102079985A (en) * | 2009-11-26 | 2011-06-01 | 中国石油化工股份有限公司 | Catalytic conversion method for producing high-cetane number light diesel oil |
| CN102079985B (en) * | 2009-11-26 | 2015-01-14 | 中国石油化工股份有限公司 | Catalytic conversion method for producing high-cetane number light diesel oil |
| CN102851067A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Hydrogenation method for production of ultralow-sulfur clean diesel oil |
| CN102851067B (en) * | 2011-06-30 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation method for production of ultralow-sulfur clean diesel oil |
| CN103827268A (en) * | 2011-07-29 | 2014-05-28 | 沙特阿拉伯石油公司 | Selective middle distillate hydrotreating process |
| US9144752B2 (en) | 2011-07-29 | 2015-09-29 | Saudi Arabian Oil Company | Selective two-stage hydroprocessing system and method |
| US9145521B2 (en) | 2011-07-29 | 2015-09-29 | Saudi Arabian Oil Company | Selective two-stage hydroprocessing system and method |
| US9144753B2 (en) | 2011-07-29 | 2015-09-29 | Saudi Arabian Oil Company | Selective series-flow hydroprocessing system and method |
| CN103781880B (en) * | 2011-07-29 | 2015-11-25 | 沙特阿拉伯石油公司 | Selectivity series flow hydrotreating systems and method |
| CN103827268B (en) * | 2011-07-29 | 2016-05-18 | 沙特阿拉伯石油公司 | Selective midbarrel hydrotreating method |
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