CN101003750A - Method for producing high grade of diesel oil from charking full distillate oil - Google Patents
Method for producing high grade of diesel oil from charking full distillate oil Download PDFInfo
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- CN101003750A CN101003750A CN 200610045708 CN200610045708A CN101003750A CN 101003750 A CN101003750 A CN 101003750A CN 200610045708 CN200610045708 CN 200610045708 CN 200610045708 A CN200610045708 A CN 200610045708A CN 101003750 A CN101003750 A CN 101003750A
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- 239000002283 diesel fuel Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000004939 coking Methods 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 43
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000002994 raw material Substances 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 9
- 238000005194 fractionation Methods 0.000 claims description 8
- 238000004523 catalytic cracking Methods 0.000 claims description 6
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
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- 238000012986 modification Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000003502 gasoline Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
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- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000003223 protective agent Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 102100030310 5,6-dihydroxyindole-2-carboxylic acid oxidase Human genes 0.000 description 3
- 101000773083 Homo sapiens 5,6-dihydroxyindole-2-carboxylic acid oxidase Proteins 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
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- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 239000002808 molecular sieve Substances 0.000 description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- -1 hydrocarbons compounds Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910001723 mesolite Inorganic materials 0.000 description 2
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- 238000011017 operating method Methods 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
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Abstract
This invention discloses a method for producing high-quality diesel oil from whole fraction oil of coking. The method comprises: separating whole fraction of coking into light fraction oil of coking (containing part of light diesel oil fraction) and heavy fraction oil of coking (containing heavy diesel oil fraction), hydrogenation-modifying heavy fraction oil of coking in the presence of beta-zeolite-containing hydrogenation catalyst, mixing the modification product with light fraction oil of coking, and hydrogenation-refining. The method can obtain high-quality clean diesel oil and high-quality naphtha, and has such advantages as simple process and low energy consumption.
Description
Technical field
The present invention relates to a kind of method for processing whole fraction oil of coking, particularly adopt the method for hydrogenation combination technique processing charking full distillate oil, be used to produce the fine-quality diesel oil product, diesel product sulphur, the nitrogen content produced are low, the cetane value height, condensation point is low, and stability in storage is good, and the heavy naphtha of gained can be used as the fine catalytic reforming raw material.
Background technology
At present the trend that heaviness and poor qualityization accelerate has appearred in the world and domestic crude oil, the oil field scope that relates to also more and more widely, the increasingly stringent of the sustainable development of world economy and environmental regulation in addition, need to produce a large amount of light clean fuels, these all require existing oil Refining Technologies is improved, and produce satisfactory product with minimum cost.Coking is the residual oil lighting means that generally adopt, coking is to be that raw material at high temperature carries out degree of depth thermally splitting with residual oil, a kind of secondary processing process of obtain fraction oil and refinery coke, wherein most of delayed coking process that adopts, its advantage is to process various poor residuums, process is simple, investment and process cost are low, its shortcoming is a unsaturated hydrocarbons content height in coker gasoline and the coker gas oil (being called for short coking gasoline and diesel among the present invention), and the content of non-hydrocarbons compounds such as sulfur-bearing, nitrogen is also high, needs further processing treatment.
The article that " oil Refining Technologies and engineering " 1994 the 5th phases the 39th～42 page of Sun Guang delivers " is used FH-5 catalyzer hydrofining coking gasoline and diesel under low pressure ", adopt a cover hydro-refining unit, coker gasoline and coker gas oil are carried out hydrofining, the concrete mode that adopts feed switched, after promptly processing a collection of coker gasoline, switch the coker gas oil raw material.This mode can only be applicable to small-scale coker, needs continuous switching in the production process, and operational condition needs frequent variations, makes troubles to operation, and catalyst performance is had considerable influence.
The another kind of working method of coking gasoline and diesel is that the coking gasoline and diesel mixed hydrogenation is handled, its process is with after hydrogen mixes with the coking gasoline and diesel raw material, carry out hydrofining by the Hydrobon catalyst bed, the hydrogenated oil that obtains carries out fractionation, obtain naphtha fraction and diesel oil distillate etc., naphtha fraction wherein is as catalytic reforming raw material, and diesel oil distillate is as blend component." oil Business " 1997 the 4th phases article of the 57th～59 page " utilizes hydrofining coking gasoline and diesel device to produce No. 200 solvent oils ", coking gasoline and diesel by hydrofining after, can obtain＜140 ℃ petroleum naphtha, 140～200 ℃ solvent oil, diesel oil more than 200 ℃, wherein the diesel oil of gained still can not satisfy specification requirement, can only be as diesel oil blending component, and the commercial value of solvent oil is more much lower than the price of gasoline or diesel oil, so from economic benefit, the processing scheme of coking gasoline and diesel awaits further to optimize, and increases economic efficiency." petrochemical technology and application " 2004 the 3rd phases article of the 173rd～176 page " research of coking gasoline and diesel HYDROGENATED JET FUEL " has been introduced deep hydrofinishing has been carried out in the coking gasoline and diesel mixing, fractionates out gasoline, kerosene and diesel oil etc. then.This method is only carried out deep refining with the full cut of coking, then kerosene(oil)fraction is wherein separated, and fraction of coker gas oil only is difficult to obtain the diesel product of high standard through hydrofining.
CN 1478867A discloses a kind of method of producing rocket engine fuel from coking distillate.This method be the coking distillate raw material is contacted with hydrogenation catalyst and without intermediate section from, reacted effluent is through refrigerated separation, rich hydrogenous gas circulation is used, and product liquid enters fractionating system and is separated into naphtha fraction, rocket engine fuel cut and diesel oil distillate.Preferably load a kind of Hydrobon catalyst after hydrogenation catalyst, the main purpose of this catalyzer is that the small amounts of olefins that reaction generates is carried out hydrogenation is saturated, removes mercaptan sulfur simultaneously.This method is that coking distillate is all carried out hydrocracking, yield to diesel oil has bigger influence, in the full cut of coking simultaneously, particularly in cut, contain more alkene and diolefine, when under comparatively high temps, carrying out hydrocracking, these components are easy to coking, influence the steady running of production equipment.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of method for processing whole fraction oil of coking, this method is used to produce the fine-quality diesel oil product, diesel product sulphur, nitrogen content are low, the cetane value height, condensation point is low, and stability in storage is good, is the clean diesel product that meets environmental regulation and quality product requirement.
The present invention is comprised the steps: by the method for producing high grade of diesel oil by charking full distillate oil
A, charking full distillate oil carry out fractionation, obtain coking light distillate and coking heavy distillate, and its cut point is 200～350 ℃, are preferably 240～320 ℃; The final boiling point of coking heavy distillate is 380～460 ℃;
The coking heavy distillate of b, step a gained enters the hydro-upgrading reaction zone, contacts with catalyst for hydro-upgrading;
The hydrogenation products of c, step b gained with enter the hydrofining reaction district after the coking light distillate of step a gained mixes, in the presence of Hydrobon catalyst, carry out hydrogenating desulfurization, denitrogenation and hydrogenation saturated reaction;
The hydrotreated product of d, step c gained enters separator and carries out gas-liquid separation, and the liquid phase of gained enters fractionating system, obtains petroleum naphtha, heavy naphtha and diesel product.
Wherein said catalyst for hydro-upgrading is the catalyst for hydro-upgrading that contains the β zeolite.β zeolite 0.5～40.0wt% preferably contains β zeolite 1.0～19.0wt%.β zeolite General N a
2The O weight content is less than 0.15wt%, preferably less than 0.10wt%, and SiO
2/ Al
2O
3Mol ratio 30～300, preferred 70～170, infrared acidity 0.05～0.8mmol/g, preferred 0.1～0.4mmol/g.Other carrier component can be one or more in the various inorganic refractory oxides such as mixture of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, zirconium white, Y molecular sieve, ZSM molecular sieve and above several materials, one or more that commonly used is in aluminum oxide, Y molecular sieve and the amorphous silicon aluminium.The hydrogenation metal component can be selected from one or more in group vib and the group VIII base metal, and one or more that commonly used is among W, Mo, Ni, the Co are generally 15.0～40.0wt% in the oxide compound metal content, preferred 20.0～35.0wt%.Usually contain group vib metal and group VIII metal simultaneously, as contain W and/or Mo15.0～30.0wt% in oxide compound, preferred 18.0～26.0wt% contains Ni and/or Co3.0～9.0wt% in oxide compound, preferred 5.0～7.0wt%.Zeolite component in the modifying catalyst has acid sites, it is the main active centre of reactions such as cracking hydrocarbon and isomerization, metal component in the modifying catalyst is a hydrogenation sites, can finish hydrogenation and take off reactions such as impurity, and promptly catalyst for hydro-upgrading is a dual-function catalyst.
In the full distillate oil of coker gained, except the present invention used coking light distillate and capable of circulation time coker of the wax slop cut the coking heavy distillate, not only can dilute coking raw material, increase the yield of coking gasoline and diesel, reduce coking, and combine with the inventive method, do not need to increase the device of other processing wax tailings.Certainly this coking wax slop also can adopt other technological process further to process, as catalytic cracking, hydrocracking, hydrotreatment etc. one or more.
The present invention is that charking full distillate oil is fractionated into two components is coking light distillate and coking heavy distillate, and wherein coking last running is earlier through hydro-upgrading, and the hydro-upgrading product of gained mixes with coking light distillate and carries out hydrofining.In the distillate of coker gained, the final boiling point of the coking light distillate that the present invention is used is higher than conventional coker gasoline, coking heavy distillate final boiling point also is higher than conventional coker gas oil, gas yield in the time of can reducing the coking heavy distillate thus and carry out hydrocracking, improve liquid-phase product yield, the particularly yield of high quality heavy naphtha fraction.Can improve simultaneously the processing power of hydro-upgrading unit, reduce energy expenditure.Coking light distillate and coking heavy distillate hydro-upgrading product are mixed into the hydrofining reaction district, need not coking light distillate is heated, the heat that coking heavy distillate hydro-upgrading product brings, be enough to the heat that guarantees that hydrofining reaction is required, not only heat-exchange equipment of Jie Shenging or heating installation, thereby reduce cost, but also fully utilized the energy that produces in the reaction process, saved energy consumption.The content of diolefine is higher in the coking light distillate, by with the mixing of hydro-upgrading product, not only diluted the concentration of the unsaturated materials in the coking light distillate, and made full use of thermal source, avoid coking light distillate coking in extra heating and heat transfer process, help prolonging the production run cycle.
The hydro-upgrading process that the present invention adopts is taken all factors into consideration the many index requirement of clean diesel, coking heavy distillate raw material inferior can be processed as the fine-quality diesel oil product.The inventive method can remove the impurity such as sulfide, nitride, oxide compound, organic acid, phenol, alkene and aromatic hydrocarbons in the raw material, the open loop of part naphthenic hydrocarbon can also be reduced viscosity, density by a relatively large margin; The cracking of heavy component appropriateness in the raw material, can make the final boiling point reach, reduce T95, the inventive method makes the condensation point of diesel product reduce greatly because used the suitable modifying catalyst of performance, can produce the cleaning low-coagulation diesel oil, and it is but less to the diesel yield influence, need not separate tail oil, with coking heavy distillate maximum be converted into high-quality diesel product, and greatly reduce the energy consumption in the product fractionation operation process.
Description of drawings
Fig. 1 is the synoptic diagram of flow process that the embodiment of the invention adopts.
Embodiment
The specific implementation process of the inventive method is as follows:
Coking heavy distillate and hydrogen enter the hydro-upgrading reaction zone, contact with catalyst for hydro-upgrading and to carry out hydrogenation reaction, wherein the operational condition of hydro-upgrading reaction zone is as follows: hydrogen dividing potential drop 3.0～20.0MPa, hydrogen to oil volume ratio 200～3000, volume space velocity 0.2～10.0h during liquid
-1, 340～430 ℃ of temperature of reaction.Preferred operational condition is as follows: hydrogen dividing potential drop 5.0～16.0MPa, hydrogen to oil volume ratio 400～1500, volume space velocity 0.5～4.0h during liquid
-1, 360～410 ℃ of temperature of reaction.The hydro-upgrading product mixes the back and enters the hydrofining reaction district with hydrogen-rich gas with coking light distillate, contact with Hydrobon catalyst and to carry out hydrogenating desulfurization, hydrodenitrification and hydrogenation saturated reaction, wherein the operational condition in hydrofining reaction district is as follows: the hydrogen dividing potential drop is 3.0MPa～20.0MPa, preferably 5.0MPa～16.0MPa; Average reaction temperature is 280 ℃～400 ℃, best 300 ℃～370 ℃; Volume space velocity 0.1h during liquid
-1～10.0h
-1, best 0.4h
-1～5.0h
-1Hydrogen to oil volume ratio is 100: 1～3000: 1, best 200: 1～1500: 1.
In addition, in the charking full distillate oil course of processing of the present invention, can be according to practical situation, the raw material that adds other source, as in coking light distillate, adding the light ends oil that the catalytic cracking process process obtains, can add the heavy ends wet goods that the catalytic cracking process process obtains in the coking heavy distillate, for the inventive method, add-on is arbitrarily.
Hydro-upgrading of the present invention and hydrofining can be adopted method well known to those skilled in the art.As in the hydro-upgrading process, according to the raw material properties that enters the hydro-upgrading reaction zone, especially index such as nitrogen content is determined suitable operating method.If nitrogen content is higher, the pretreatment reaction district can be set, before the hydro-upgrading reaction zone to remove to the deleterious impurity of catalyst for hydro-upgrading.Hydrotreating catalyst well known to those skilled in the art or Hydrobon catalyst can load in the pretreatment reaction district.Described hydrogenation pretreatment reaction district and hydro-upgrading reaction zone can be arranged in the same reactor, also can be arranged in the different reactors.The operational condition in hydrogenation pretreatment reaction district is as follows: 250～500 ℃ of temperature of reaction, optimum range are 330～420 ℃; Hydrogen dividing potential drop 3.0～20.0MPa, optimum range is 5.0～16.0MPa, hydrogen to oil volume ratio 300～3000, optimum range are 400～2000; Volume space velocity 0.1～10.0h during liquid
-1, optimum range 0.2～5h
-1Certainly, those skilled in the art know, even nitrogen content is higher in the raw material, also hydrogenation pretreatment reaction district can be set, and only use catalyst for hydro-upgrading, particularly can use catalyst for hydro-upgrading with higher anti-nitrogen performance (as reducing β zeolite content in the modifying catalyst, or selecting the β zeolite etc. of high silica alumina ratio more for use), also can adopt the catalyst for hydro-upgrading of higher anti-nitrogen performance and common catalyst for hydro-upgrading to be used.When only using catalyst for hydro-upgrading, organonitrogen in the raw material is poisoned by the acid sites of the partial hydrogenation modifying catalyst mesolite that at first contacts with raw material or part is poisoned, but still can have an effect in the hydrogenation center of catalyst for hydro-upgrading, carry out the hydrodenitrification reaction, carrying out along with reaction, nitrogen content in the raw material reduces, and the acid sites performance catalytic activity of modifying catalyst mesolite is carried out respective reaction.This moment has only mainly been brought into play single function (hydrogenating function) in the difunctional effect that is catalyst for hydro-upgrading, but does not influence realization the object of the invention.Because the cost of catalyst for hydro-upgrading is higher than Hydrobon catalyst (pretreatment catalyst), so, when the raw material nitrogen content is higher, hydrogenation pretreatment reaction district is set preferably still.
Described catalyst for hydro-upgrading can prepare by known method, also can select commercial catalyst.The development of commercial catalyst such as Fushun Petrochemical Research Institute 3901, FC-14, FC-16, FC-20 catalyzer etc.
The used Hydrobon catalyst in the described hydrofining reaction of step c district can be identical with the used Hydrobon catalyst before the hydro-upgrading reaction zone, also can select different catalyzer in conjunction with raw material properties.The used Hydrobon catalyst of step c is made up of carrier and the hydrogenation metal that is loaded in above it, with the weight percent is benchmark, hydrogenation component comprises group vib active metal component (preferred tungsten and/or molybdenum), counts 10%～35% with metal oxide, and 15～25% is better; Group VIII active metal component (preferred nickel and/or cobalt) counts 1%～7% with metal oxide, and 1.5%～6% is better, and carrier is aluminum oxide or siliceous aluminum oxide etc.Can prepare Hydrobon catalyst by known method, also can select commercial Hydrobon catalyst.FH-5, FH-5A, FH-98, FDS-4, FDS-4A, FH-DS, FH-UDS, 481-3 or the like of commercial Hydrobon catalyst such as Fushun Petrochemical Research Institute's development.
Described hydrogenation pretreatment catalyst is made up of carrier and the hydrogenation metal that is loaded in above it, with the weight percent is benchmark, hydrogenation metal is a base metal, comprise group vib active metal component in the periodic table of elements, preferred tungsten and/or molybdenum, count 10～35% with metal oxide, 15～30% is better; And the group VIII reactive metal, preferred nickel and/or cobalt count 1%～15% with metal oxide, and 1.5%～10% is better.The carrier of hydrogenation pretreatment catalyst is an inorganic refractory oxide, as in aluminum oxide, amorphous silicon aluminium, silicon oxide, the titanium oxide etc. one or more.Hydrogenation pretreatment catalyst can prepare by known method, also can select commercial hydrogenation pretreatment catalyst.Have as commercial hydrogenation pretreatment catalyst: the KF-847 and the KF-848 of the TK-555 of the HC-K of Uop Inc., HC-T and HC-P, Topsor company and TK-565 catalyzer, AKZO company.Fushun Petrochemical Research Institute development 3936,3996, FF-16, FF-26 or the like.
In actually operating; can be according to the impurities in raw materials situation; use an amount of protective material before at Primary Catalysts (Hydrobon catalyst, hydrogenation pretreatment catalyst, catalyst for hydro-upgrading),, guarantee the work-ing life of Primary Catalysts to remove partial impurities wherein.Usually, protectant admission space accounts for 1%～30% of Primary Catalysts volume.Protective material generally all is to be carrier with porous refractory inorganic oxide such as aluminum oxide; the oxide compound of group vib and/or group VIII metal such as W, Mo, Co, Ni etc. is an active ingredient, optionally adds the catalyzer of other various auxiliary agents such as P, Si, elements such as F, B.Described protective material can adopt the known method preparation, also can select the commodity protective material for use.The FZC series protective material of producing by Fushun Petrochemical Research Institute pilot scale base for example.
Below in conjunction with accompanying drawing flow process of the present invention is described in detail.
The charking full distillate oil raw material obtains coking light distillate 2 and coking heavy distillate 1 through fractionation.Coking heavy distillate 1 enters hydro-upgrading reactor 4 with hydrogen-rich gas 3 and carries out the hydro-upgrading reaction; obtain hydro-upgrading and generate oil 8; wherein hydro-upgrading reactor 4 internal upper parts are hydrogenation protecting agent bed, and the middle part is the hydrogenation pretreatment catalyst bed, and the bottom is the catalyst for hydro-upgrading bed.Hydro-upgrading generates oil 5, coking lighting end 2 and enters hydrofining reactor 6 after hydrogen-rich gas 3 mixes and carries out hydrogenating desulfurization, hydrodenitrification and hydrogenation saturated reaction, the hydrofining that obtains generates oil 7 and enters gas-liquid separator 8, obtain gas 9 and liquid 10, wherein gas is hydrogen-rich gas, after removing hydrogen sulfide and ammonia, turn back to hydro-upgrading reactor and hydrofining reactor and recycle.Liquid 10 enters fractionating system 11, obtains petroleum naphtha 12, heavy naphtha 13 and diesel oil 14.
The present invention is described in more detail below in conjunction with embodiment, but technical solution of the present invention is not limited by following examples.
Embodiment 1-4 and comparative example 1
The schema of embodiment 1～4 is seen Fig. 1; comparative example is that the coking gasoline and diesel raw material is directly entered the hydrofining reaction district without fractionation; loaded the hydrogenation protecting agent before the Hydrobon catalyst, its admission space is 20% of a Hydrobon catalyst volume, the same Fig. 1 of subsequent process.
The FH-98 (FH-98 is the catalyzer trade mark) that used Hydrobon catalyst is produced for Wenzhou catalyst plant in each embodiment and comparative example; 3996 (3996 is the catalyzer trade mark) that hydrogenation pretreatment catalyst is produced for the Fushun Petrochemical Company catalyst plant; the hydrogenation protecting agent is the FZC-102 (FZC-102 is the catalyzer trade mark) that Fushun Petrochemical Research Institute pilot scale base produces; wherein the hydrogenation protecting agent is seated in before the hydrogenation pretreatment catalyst, and its admission space is 20% of a hydrogenation pretreatment catalyst volume.Table 1 is by being used the raw material oil properties in the embodiment of the invention and the comparative example.
Table 1 raw material oil properties
| The stock oil numbering | Raw material-1 | Raw material-2 | ||
| The coking lighting end | Coking heavy gas oil | The coking lighting end | Coking heavy gas oil | |
| Density (20 ℃), g/cm 3 | 0.7810 | 0.8800 | 0.7640 | 0.8700 |
| Sulphur, μ g/g | 7600 | 15000 | 3200 | 13400 |
| Nitrogen, μ g/g | 900 | 1870 | 400 | 1520 |
| The bromine valency, gBr/100g | 60 | 18 | 46 | 15 |
| Cetane index | 41 | 39 | ||
| The boiling range scope, ℃ | ||||
| Initial boiling point/10% | 47/91 | 300/324 | 50/89 | 230/265 |
| 30％/50％ | 135/175 | 345/381 | 135/165 | 287/311 |
| 70％/90％ | 208/245 | 405/420 | 200/225 | 355/394 |
| Do (final boiling point) | 310 | 435 | 245 | 410 |
Used catalyst for hydro-upgrading CATA and CATB are Chinese patent CN 1054153C embodiment 1 and implement 2 catalyzer that obtain, see Table 2. Embodiment 1 and 3 catalyst for hydro-upgrading CATA, embodiment 2 and 4 catalyst for hydro-upgrading CATB.
The physico-chemical property of table 2 catalyst for hydro-upgrading
| Catalyzer | CATA | CATB |
| Form wt% | ||
| WO 3(MoO 3) | 23.8 | 23.4 |
| NiO | 7.4 | 6.7 |
| The |
10 | 15 |
| Physical properties: | ||
| Pore volume, mL/g | 0.322 | 0.329 |
| Specific surface, m 2/g | 264 | 268 |
The main operational condition of table 3 hydro-upgrading
| Project | Embodiment 1 | |
|
Embodiment 4 |
| Raw material | |
|
|
|
| The hydrogen dividing potential drop, MPa | 6.0 | 14.0 | 6.0 | 14.0 |
| Hydrogen to oil volume ratio | 600∶1 | 1500∶1 | 600∶1 | 1500∶1 |
| Volume space velocity during liquid (pre-treatment/hydrocracking), h -1 | 3.0/2.0 | 6.0/4.0 | 8.0/5.0 | 1.0/1.0 |
| Temperature of reaction, ℃ | 375 | 390 | 385 | 360 |
The operating procedure condition that table 4 hydrofining reactor is main
| Project | Embodiment 1 | |
|
Embodiment 4 | Comparative example 1 |
| Raw material | Crackate and |
Crackate and |
Crackate and |
Crackate and |
Coking gasoline and diesel mixing |
| The hydrogen dividing potential drop, MPa | 5.6 | 13.6 | 5.6 | 13.6 | 8.0 |
| Hydrogen to oil volume ratio | 1000∶1 | 1800∶1 | 1000∶1 | 1800∶1 | 600∶1 |
| Volume space velocity during liquid, h -1 | 8.0 | 1.0 | 4.0 | 5.0 | 3.0 |
| Temperature of reaction, ℃ | 350 | 250 | 280 | 265 | 290 |
The character of table 5 embodiment products obtained therefrom
| Product | Petroleum naphtha | Heavy naphtha | |
| Embodiment | |||
| 1 | |||
| Density (20 ℃), g/cm 3 | 0.6480 | 0.7440 | 0.8210 |
| Sulphur, μ g/g | ＜5 | ＜5 | ＜60 |
| Nitrogen, μ g/g | ＜2 | ＜2 | ＜30 |
| T 95The point | - | - | 380 |
| Condensation point, ℃ | - | - | -10 |
| Cetane index (ASTM D4737) | - | - | 52 |
| Yield, wt% | 2.3 | 21.3 | 72.5 |
| |
|||
| Density (20 ℃), g/cm 3 | 0.6465 | 0.7415 | 0.8160 |
| Sulphur, μ g/g | ＜5 | ＜5 | ＜30 |
| Nitrogen, μ g/g | ＜2 | ＜2 | ＜10 |
| T 95The point | - | - | 372 |
| Condensation point, ℃ | - | - | -16 |
| Cetane index (ASTM D4737) | - | - | 54 |
| Yield, wt% | 2.5 | 23.1 | 70.0 |
| |
|||
| Density (20 ℃), g/cm 3 | 0.6475 | 0.7425 | 0.8190 |
| Sulphur, μ g/g | ＜5 | ＜5 | ＜30 |
| Nitrogen, μ g/g | ＜2 | ＜2 | ＜10 |
| T 95The point | 378 | ||
| Condensation point, ℃ | - | 50 | -12 |
| Cetane index (ASTM D4737) | - | - | 52 |
| Yield, wt% | 2.4 | 22.5 | 71.0 |
| Embodiment 4 | |||
| Density (20 ℃), g/cm 3 | 0.6470 | 0.7420 | 0.8165 |
| Sulphur, μ g/g | ＜5 | ＜5 | ＜30 |
| Nitrogen, μ g/g | ＜2 | ＜2 | ＜10 |
| T 95The point | - | - | 365 |
| Condensation point, ℃ | - | - | -25 |
| Cetane index (ASTM D4737) | - | - | 54 |
| Yield, wt% | 3.5 | 24.9 | 67.0 |
The character of table 6 comparative example products obtained therefrom
| Product | Petroleum naphtha | Heavy naphtha | Diesel oil |
| Comparative example 1 | |||
| Density (20 ℃), g/cm 3 | 0.6510 | 0.7414 | 0.8430 |
| Boiling range (ASTM D86), ℃ | 26～70 | 71～176 | 177～385 |
| Sulphur, μ g/g | ＜30 | ＜50 | 200 |
| Nitrogen, μ g/g | ＜20 | ＜30 | 100 |
| Virtue is dived, wt% | - | 50 | - |
| Cetane index (ASTM D4737) | - | - | 49 |
| T 95The point, ℃ | 399 | ||
| Condensation point, ℃ | - | - | 4 |
| Yield *, wt% | 1.1 | 10.8 | 60.0 |
* diesel oil distillate is done and is cut to 385 ℃, still has part (about 25wt%) last running, can not need to adopt vacuum still to separate as diesel oil distillate.
By table 5 and table 6 as seen, adopt the inventive method can obtain the more heavy naphtha and the diesel product of high quality and Geng Gao yield, all last running are the high-quality diesel component.And adopt the direct hydrorefined method of coking gasoline and diesel, its quality product to need further to improve, and the yield of heavy naphtha and diesel oil is lower, still some heavy ends can not be as the component of diesel oil, need fractionation to come out, so required equipment increases in the fractionation process, energy consumption is bigger.
Claims (13)
1, a kind of method by producing high grade of diesel oil by charking full distillate oil comprises the steps:
A, charking full distillate oil carry out fractionation, obtain coking light distillate and coking heavy distillate, and its cut point is 200～350 ℃; The final boiling point of coking heavy distillate is 380～460 ℃;
The coking heavy distillate of b, step a gained enters the hydro-upgrading reaction zone, contacts with catalyst for hydro-upgrading; Wherein catalyst for hydro-upgrading is the catalyst for hydro-upgrading that contains the β zeolite;
The hydrogenation products of c, step b gained with enter the hydrofining reaction district after the coking light distillate of step a gained mixes, in the presence of Hydrobon catalyst, carry out hydrogenating desulfurization, denitrogenation and hydrogenation saturated reaction;
The hydrotreated product of d, step c gained enters separator and carries out gas-liquid separation, and the liquid phase of gained enters fractionating system, obtains petroleum naphtha, heavy naphtha and diesel product.
2, in accordance with the method for claim 1, it is characterized in that the cut point of coking light distillate and coking heavy distillate is 240～320 ℃ in the step (a).
3, in accordance with the method for claim 1, it is characterized in that the operational condition of the described hydro-upgrading reaction zone of step (b) is as follows: hydrogen dividing potential drop 3.0～20.0MPa, hydrogen to oil volume ratio 200～3000, volume space velocity 0.2～10.0h during liquid
-1, 340～430 ℃ of temperature of reaction.
4, in accordance with the method for claim 1, it is characterized in that the operational condition of the described hydro-upgrading reaction zone of step (b) is: hydrogen dividing potential drop 5.0～16.0MPa, hydrogen to oil volume ratio 400～1500, volume space velocity 0.5～4.0h during liquid
-1, 360～410 ℃ of temperature of reaction.
5, in accordance with the method for claim 1, it is characterized in that containing β zeolite 0.5wt%～40.0wt% in the described catalyst for hydro-upgrading of step (b), β zeolite Na
2The O weight content is less than 0.15wt%, SiO
2/ Al
2O
3Mol ratio 30～300.
6, in accordance with the method for claim 1, it is characterized in that containing β zeolite 1.0wt%～19.0wt% in the described catalyst for hydro-upgrading of step (b), β zeolite SiO
2/ Al
2O
3Mol ratio 70～170.
7, in accordance with the method for claim 1, it is characterized in that in the charking full distillate oil described in the step (a), wax slop cut except that described coking light distillate and coking heavy distillate loops back coker, or as the raw material of catalytic cracking, hydrocracking, one or more devices of hydrotreatment.
8, according to the described method of claim 1, it is characterized in that the operational condition in the described hydrofining reaction of step (c) district is as follows: the hydrogen dividing potential drop is 3.0MPa～20.0MPa, and average reaction temperature is 280 ℃～400 ℃, volume space velocity 0.1h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is 100: 1～3000: 1.
9, in accordance with the method for claim 1, it is characterized in that the operational condition in the described hydrofining reaction of step (c) district is as follows: the hydrogen dividing potential drop is 5.0MPa～16.0MPa, and average reaction temperature is 300 ℃～370 ℃, volume space velocity 0.4h during liquid
-1～5.0h
-1, hydrogen to oil volume ratio is 200: 1～1500: 1.
10, in accordance with the method for claim 1, it is characterized in that to add the light ends oil that the catalytic cracking process process obtains in the coking light distillate, in the coking heavy distillate, can add the heavy distillate that the catalytic cracking process process obtains.
11, in accordance with the method for claim 1, it is characterized in that before the described hydro-upgrading reaction zone of step (b) hydrogenation pretreatment reaction district being set.
12, in accordance with the method for claim 11, it is characterized in that described hydrogenation pretreatment reaction district filling hydrotreating catalyst or Hydrobon catalyst; The operational condition in hydrogenation pretreatment reaction district is as follows: 250～500 ℃ of temperature of reaction, hydrogen dividing potential drop 3.0～20.0MPa, hydrogen to oil volume ratio 300～3000, volume space velocity 0.1～10.0h during liquid
-1
13, in accordance with the method for claim 11, it is characterized in that the operational condition in described hydrogenation pretreatment reaction district is: 330～420 ℃ of temperature of reaction, hydrogen dividing potential drop 5.0～16.0MPa, hydrogen to oil volume ratio 400～2000, volume space velocity 0.2～5h during liquid
-1
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| KR1020070005622A KR20070077092A (en) | 2006-01-19 | 2007-01-18 | Lower Distillate Processing Method |
| MYPI20070089A MY145830A (en) | 2006-01-19 | 2007-01-18 | Method for processing inferior distillate oil |
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| CN101993724A (en) * | 2009-08-25 | 2011-03-30 | 中国石油化工股份有限公司抚顺石油化工研究院 | Hydrogenation combination method for flexibly producing high-quality diesel |
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