CN1197940C - Method for producing good quality diesel oil - Google Patents
Method for producing good quality diesel oil Download PDFInfo
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- CN1197940C CN1197940C CN 01133370 CN01133370A CN1197940C CN 1197940 C CN1197940 C CN 1197940C CN 01133370 CN01133370 CN 01133370 CN 01133370 A CN01133370 A CN 01133370A CN 1197940 C CN1197940 C CN 1197940C
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Abstract
The present invention discloses a method for producing diesel oil with good quality. The combined technical process of hydrogenation refining, hydrodewaxing and aromatic saturation are used, a catalyst and process conditions of each step are selected thoughtfully, and finally, units are matched well to exert a whole synergistic effect. The technical process is simple and feasible. The method is especially suitable for the processing step for producing the diesel oil with good quality, a high cetane value, low sulfur content, low condensation and low aromatic content from inferior distillate oil to satisfy a new specification requirement of a diesel oil product whose the requirement is strict gradually.
Description
1, technical field
The production method of a kind of diesel oil involved in the present invention, the method for particularly producing low-sulfur, low condensation point, low arene content, high hexadecane value fine-quality diesel oil by inferior distillate oil.
2, background technology
Entered since the eighties, countries in the world increase year by year to the diesel oil demand, from nineteen ninety to 1999 a year diesel oil demand annual increasing rate reach more than the 7.9w%.The increase of diesel oil demand, objectively requiring increases the residual oil conversion capability, adds crude resources poor qualityization day by day, causes the distillate quality constantly to descend, and sulphur, nitrogen, aromaticity content increase in the product, influence motor performance and cause environmental pollution.In addition, the most of crude oil of China belongs to paraffinic crude, and the diesel oil distillate wax content of being produced is many, condensation point is high, is unfavorable for using at northern frore area.
Along with the fast continual development of national economy, the urban atmospheric pollution problem that is on the rise has become " bottleneck " of restriction China economic growth and social progress.In recent years, countries in the world have been formulated the environmental protection new legislation one after another, and diesel oil sulphur content, cetane value especially aromaticity content have been proposed higher, stricter requirement.Though China does not also reach foreign level to the specification requirement of top grade diesel oil at present, along with China and international integrating with, China petroleum refining industry will enter the world market widely and participate in the competition.Therefore, producing the cleaning oil product becomes the task of top priority, develop and a kind ofly produces low-sulfur, low method of coagulating, hanging down aromatic hydrocarbons, high hexadecane value fine-quality diesel oil is imperative.
The common method of processing inferior distillate oil is hydrofining at present.This handicraft product yield height, technology maturation are in industrial widespread use.Hydrobon catalyst commonly used generally is with Al
2O
3Deng refractory oxide or the refractory oxide that contains auxiliary agent is carrier, is active ingredient with VI family and/or group VIII metal oxide.This technology can make oil quality improve, and can not reduce condensation point of diesel oil effectively but exist, and low coagulates to produce, the limitation of high hexadecane value fine-quality diesel oil, and the arene engaging scraping rate also is nowhere near.
U.S. Pat 4,436,614 have introduced a kind of method by low lubricant base with fixed attention of distillate production or intermediate oil, this method adopts the technical process of desulfurization dewaxing one-stage serial, in same reactor, the upper bed layer of reactor carries out desulphurization reaction, feeds inert dilution gas to reduce the dividing potential drop of hydrocarbon gas in reactor, the reaction catalyst system therefor is a desulfurization catalyst, and the hydrocarbon gas dividing potential drop of reaction is 0.2MPa; In the reaction that dewaxes of the lower floor of reactor, the reaction catalyst system therefor is the non-hydro-dewaxing molecular sieve catalyst then, and the hydrocarbon gas dividing potential drop of reaction is no more than 0.2MPa.Because the dewaxing reaction of reactor lower floor belongs to the non-hydro-dewaxing reaction, there is not hydrogen to exist, do not contain hydrogenation component in the catalyzer, can not alkene in the product and nonhydrocarbon hydrogenation is saturated, can cause oil product to darken, it is poor not only to obtain the product stability, and has a large amount of cokes to generate in non-hydrogen catalysis, and shortened the running period of catalyzer greatly.
U.S. Pat .5,114,562 have introduced the processing method that a kind of two-stage method is handled middle runnings, to produce the product of low-sulfur, low aromatic hydrocarbons.This method is a desulfurization section for first section, adopts Hydrobon catalyst (base metal); Second section is the hydrotreatment section, adopts noble metal hydrogenation catalyst so that aromatic hydrocarbons is saturated.The method that this technology provided is owing to adopted noble metal catalyst can make the aromatic hydrocarbons degree of depth saturated to satisfy the environmental protection new legislation, and condensation point of diesel oil is effective to be reduced to satisfy the severe cold area demand but can not make.
3, summary of the invention
The objective of the invention is the problem that exists in the above-mentioned technology, that develops a kind of simple possible produces high hexadecane value, low-sulfur, low coagulating and the fine-quality diesel oil method of low arene content by inferior distillate oil, to satisfy strict day by day diesel product new spec requirement.
Main design of the present invention is a kind of hydrofining of exploitation, hydrodewaxing, the saturated process integration of aromatic hydrocarbons.But these three kinds of technologies can not directly be cascaded simply, and are especially saturated in order to realize the aromatic hydrocarbons degree of depth, need to use noble metal hydrogenation catalyst, and this just requires the H with hydrofining section desulfurization generation
2S, NH
3Remove.In addition, in order to make processing method processing ease of the present invention, process simplification can select preferably that suitable hydrogenation is refining, hydrodewaxing and saturated processing condition and the catalyzer of aromatic hydrocarbons, makes and mates better between them.Therefore, for the pour point depression catalyzer, require it preferably to have suitable acid matter, to improve anti-NH
3And H
2The S performance; Concerning catalyst for refining, preferably require it to have stronger anti-coking performance, to satisfy the requirement of temperature raising.Between hydrofining section and hydrodewaxing section, need not heat exchange like this and remove the H that dereaction generates
2S and NH
3Hydrobon catalyst and Hydrodewaxing catalyst both can be to be seated in two independent reactors, also they superimposedly can be used in two beds of a reactor, realize associating with the saturated noble metal catalyst of next section aromatic hydrocarbons with two-stage method technology again, saved plant investment like this and simplified processing step.
Based on above design, the inventive method comprises:
(1) mixture of stock oil and hydrogen at first contacts with Hydrobon catalyst, and main purpose is to carry out a series of hydrogenation reactions such as hydrogenating desulfurization, denitrogenation;
(2) reacting rear material contact with Hydrodewaxing catalyst again (1) step, mainly selects the shape scission reaction, removes content of wax component, reduces condensation point, and the while further removes impurity such as S, N;
(3) enter Separate System of Water-jet through (2) step post reaction mixture material, wherein H
2S, NH
3Remove;
(1) through (3) step separation removal H
2S, NH
3After liquid phase material under the condition that hydrogen exists, contact with precious metal aromatic hydrocarbon saturation catalyst, carry out degree of depth aromatic hydrocarbons saturated reaction with the reduction aromaticity content;
(5) logistics behind (4) step aromatic hydrocarbons hydrocarbon saturated reaction enters separation system, separates obtaining hydrogen-rich gas and liquid-phase product.
The inventive method is applicable to that the boiling range scope of raw material is 120-390 ℃ a content of wax diesel oil distillate oil.Specifically, the operational condition of control hydrofining, hydrodewaxing process is: 300～430 ℃ of temperature of reaction, and better in 320～400 ℃ of scopes, best in 370～400 ℃ of scopes; Hydrogen dividing potential drop 2.0～8.0MPa, better in 3.0～9.0MPa scope, best in 4.0～8.0MPa scope; Hydrogen to oil volume ratio 200～1000, better in 300～900 scopes, better in 400～800 scopes; Volume space velocity 0.5～5.0h
-1, at 1.0～4.0h
-1Better in the scope, at 1.5～3.0h
-1Best in the scope.The operational condition of control aromatic hydrocarbons degree of depth saturation history is: 200～400 ℃ of temperature of reaction, and better in 240～370 ℃ of scopes, best in 280～350 ℃ of scopes; Hydrogen dividing potential drop 2.0～15.0MPa, better in 3.0～10.0MPa scope, best in 4.0～8.0MPa scope; Hydrogen to oil volume ratio 200～1800, better in 500～1500 scopes, best in 800～1200 scopes; Volume space velocity 0.2～10.0h
-1, at 0.5～5.0h
-1Better in the scope, at 1.0～3.0h
-1Best in the scope.
Processing method of the present invention both can be that hydrofining, hydrodewaxing is superimposed in two beds of a reactor, removed H after the reaction
2S and NH
3Deng impurity, carry out aromatics saturation process again, take two-stage method technology to realize; Also can carry out unifining process earlier, reacted material need not to separate H
2S and NH
3Deng impurity, directly carry out the hydrodewaxing reaction, wherein hydrofining is contained in the different reactors with Hydrodewaxing catalyst, and the two-stage method technology of carrying out aromatics saturation process again is to realize; The catalyzer that can certainly be above-mentioned three processes is seated in respectively in the different reactors, and wherein the reactant behind the unifining process is earlier with H
2S and NH
3Behind impurity removal, carry out the hydrodewaxing process again, also need earlier then H in the reaction mass
2S and NH
3Behind impurity removal, carry out the three-stage process technology of aromatic hydrocarbons saturated reaction process again.
Rich H in the aforesaid method after (5) described separation of step
2Gas generally can partly or entirely circulate as the hydrogen feed of hydrofining and hydrodewaxing part.
The employed Hydrobon catalyst of technological process of the present invention can be any suitable catalyzer that comprises prior art, generally is with Al
2O
3Deng refractory oxide or the refractory oxide that contains a little auxiliary is carrier, and the catalyst activity component is group vib component and/or the group VIII component in the periodic table of elements, and the most frequently used is with W (or Mo) and Ni is active metal component.In order to make processing method processing ease of the present invention, reach best effect, Hydrobon catalyst of the present invention preferably can satisfy following requirement: with γ-Al
2O
3Being carrier, is the hydrogenation activity component to be selected from metal component W of VI family in the periodic table of elements and/or Mo and group VIII metal component Ni, is benchmark with the weight percent of catalyzer, WO
3And/or MoO
3Content account for 10～30%, NiO accounts for 8%～15%; This catalyzer pore volume is 0.3～0.6ml/g preferably, and specific surface is 200～650m preferably
2/ g.
The described hydrodewaxing section of processing method of the present invention catalyzer can be any suitable catalyst that comprises prior art, generally is with mesopore sub-sieve and Al such as ZSM type, SAPO
2O
3Jointly as carrier, the hydrogenation active metals component is group VIII metal component and/or a VI family metal component in the periodic table of elements Deng refractory oxide or the refractory oxide that contains a little auxiliary, general commonly used be that Ni and/or Co are as active metal component.In order to give full play to the characteristics of processing method of the present invention, especially need not separate H when between described hydrofining unit and the hydrodewaxing unit
2S and NH
3Deng impurity, and under the direct placed in-line situation, described Hydrodewaxing catalyst preferably can satisfy following requirement:
With catalyst weight per-cent is benchmark, and NiO and/or Co content should be 1.0%～3.0%, and the ZSM-5 molecular sieve content is 60～90%, and the catalyzer pore volume is 0.15～0.40ml/g, 200～800m in the specific surface
2/ g.The NH of catalyzer
3-TPD acid distributes and is preferably:
160℃：0.150～0.185mmol/g；
250℃：0.115～0.145mmol/g；
350℃：0.060～0.105mmol/g；
450℃：0.045～0.065mmol/g；
530℃：0.005～0.020mmol/g。
Aromatic hydrocarbon saturation catalyst of the present invention can be to comprise any suitable catalyzer of prior art, such catalyzer generally is as the saturated active ingredient of hydrogenation with group VIII noble metals and/or base metal, as carrier, also can add molecular sieve component with refractory oxides such as aluminum oxide, silicon oxide.
The preferential hydrogenation arenes catalytic agent of recommending of the present invention preferably can be satisfied following requirement: with the Pd in the group VIII noble metals and/or Pt as active ingredient, with modification γ type molecular sieve and γ-Al
2O
3As carrier, be benchmark with the catalyst weight jointly, the total metal contents in soil of Pd and/or Pt is 0.2～2.0w%, and the content of modified zeolite of Y-type is 40%～90%, γ-Al
2O
3Content is 10%～60%.Wherein said modified zeolite of Y-type unit cell parameters is preferably 2.435～2.455nm, SiO
2/ Al
2O
3Value is preferably 5～70, Na
2The O weight content is preferably less than 0.20%.This catalyzer pore volume is preferably: 0.20～0.50ml/g, specific surface is preferably 600～1000m
2/ g.Certainly processing method of the present invention also can be used and comprise precious metal and non-noble metal aromatic hydrocarbon saturation catalyst simultaneously.
Compared with prior art, advantage of the inventive method and characteristics are:
1, inferior distillate oil has removed impurity such as most of sulphur, nitrogen and has made part aromatic hydrocarbons saturated after hydrofining, has improved the fed downstream quality, has relaxed operational condition, helps prolonging the life cycle of catalyzer.
2, when handling inferior distillate oil, the hydrofining section needs higher temperature of reaction, usually used Hydrobon catalyst.Ni content lower (being about 3～5%), the high temperature anti-coking performance is relatively poor.And among the present invention institute's special recommendation be the higher Hydrobon catalyst of Ni content, so easily within it portion form part Ni-Al spinel, it at high temperature will absorb H
2, make catalyzer have stronger anti-coking performance, so this catalyzer still have good activity under higher temperature, be convenient to the temperature raising of hydrofining section to satisfy the temperature raising needs of hydrodewaxing section.
3, the hydrodewaxing section effectively reduces the distillate condensation point to the distillate shape slective cracking, and Hydrodewaxing catalyst also has certain refining effectiveness, objectively helps to alleviate first section hydrofining section load.
4, the present invention also proposes in the hydrodewaxing process, and catalyzer preferably will have specific acid matter, thereby possesses good anti-ammonia and antiacid performance, need not to remove wherein NH to satisfy reaction mass preferably before entering the hydrodewaxing bed
3And H
2The purpose of S also can guarantee to need not heat exchange between two sections of the hydrofining of the first string and the hydrodewaxing in addition, can make two sections heats reach good coupling, thereby realize hydrofining-hydrodewaxing one-stage serial.
5, that distillate is carried out degree of depth aromatic hydrocarbons is saturated for saturated section of the aromatic hydrocarbons high reactivity that utilizes noble metal catalyst, effectively reduces aromaticity content in the distillate, has compensated the part cetane value of losing owing to the hydrodewaxing shape slective cracking simultaneously.
6, the used carrier of catalyzer of the present invention is acid moderate Y zeolite, because the acidity of carrier is too strong, can cause excessive fragmentation, influence diesel yield, and acidity can cause catalyst tolerates sulphur, anti-nitrogen ability drop a little less than too, so the modified molecular screen acidity that the present invention selects for use is moderate, can make catalyzer have stronger anti-sulphur, anti-nitrogen ability, can guarantee high diesel yield again.
4, embodiment
The present invention is described in detail below in conjunction with specific embodiment and comparative example.
The used stock oil of embodiment and comparative example is wax-containing distillate, and its character sees Table 1.Embodying the technical process that embodiments of the invention adopted is: the mixture of stock oil and hydrogen at first contacts with Hydrobon catalyst, main purpose is to carry out a series of hydrogenation reactions such as hydrogenating desulfurization, denitrogenation, the reaction effluent material contacts with Hydrodewaxing catalyst again, mainly select the shape scission reaction, remove content of wax component, reduce condensation point, further remove impurity such as S, N simultaneously, the post reaction mixture material enters Separate System of Water-jet, wherein H
2S, NH
3Remove separation removal H
2S, NH
3After liquid phase material under the condition that hydrogen exists, contact with precious metal aromatic hydrocarbon saturation catalyst, carry out degree of depth aromatic hydrocarbons saturated reaction to reduce aromaticity content, the logistics behind the aromatic hydrocarbons hydrocarbon saturated reaction enters separation system, separation obtains hydrogen-rich gas and liquid-phase product.The technical process that comparative example 1 is adopted is: the mixture of stock oil and hydrogen at first contacts with Hydrobon catalyst, and main purpose is to carry out a series of hydrogenation reactions such as hydrogenating desulfurization, denitrogenation, and the post reaction mixture material enters Separate System of Water-jet, wherein H
2S, NH
3Remove separation removal H
2S, NH
3After liquid phase material under the condition that hydrogen exists, contact with precious metal aromatic hydrocarbon saturation catalyst, carry out degree of depth aromatic hydrocarbons saturated reaction to reduce aromaticity content, the logistics behind the aromatic hydrocarbons hydrocarbon saturated reaction enters separation system, separation obtains hydrogen-rich gas and liquid-phase product.And the technical process that comparative example 2 is adopted is: the mixture of stock oil and hydrogen at first contacts with Hydrobon catalyst, main purpose is to carry out a series of hydrogenation reactions such as hydrogenating desulfurization, denitrogenation, the reaction effluent material contacts with Hydrodewaxing catalyst again, mainly select the shape scission reaction, remove content of wax component, reduce condensation point, further remove impurity such as S, N simultaneously, reacted logistics enters separation system, separates to obtain hydrogen-rich gas and liquid-phase product.
The character of test catalyst system therefor is listed in table 2, tests used processing condition and test-results and lists in table 3 and table 4.
Table 1 test stock oil character
| Analysis project | Stock oil |
| Density (20 ℃), kg/m 3Boiling range, ℃ IP/10% 30%/50% 70%/90% 95%/EP sulphur, μ g/g nitrogen, μ g/g flash-point, ℃ aniline point, ℃ 20 ℃ of viscosity, mm 2/ s condensation point, ℃ cetane value aromaticity content, w% | 882.4 185/253 278/305 328/353 364/373 7720 1020 73 58 6.550 7 36.0 49.6 |
Table 2 test catalyst property
| Catalyst type | Hydrofining | Hydrodewaxing | Aromatic hydrocarbons is saturated | |||
| The catalyzer numbering | HT-1 | HT-2 | HDW-1 | HDW-2 | HDA-1 | HDA-2 |
| Catalyzer is formed w% NiO WO 3Pt Pd ZSM-5 molecular sieve Y zeolite Al 2O 3Pore volume, ml/g specific surface, m 2/ g bulk density; G/ml profile TPD acid distributes 160 ℃ of 250 ℃ of 350 ℃ of 450 ℃ 530 ℃ Y zeolite character a of Mm/g0，nm SiO 2/Al 2O 3 Na 2O，w％ | 8 28 surpluses, 0.34 242 1.02 clover | 10 26 surpluses, 0.36 250 1.03 clover | 1.8 75 surpluses, 0.29 302 0.76 clover 0.183 0.135 0.100 0.062 0.016 | 2.2 80 surpluses, 0.20 289 0.74 clover 0.179 0.126 0.092 0.058 0.012 | 0.98 78.8 surpluses, 0.45 598 0.59 clover 2.439 21.3 0.03 | 0.31 0.78 79.0 surplus, 0.47 617 0.57 clover 2.447 7.30 0.08 |
Table 3 test technology condition
| Example | Embodiment | Comparative example | ||||||
| Test number | 1 | 2 | 3 | 4 | 5 | 6 | 1 | 2 |
| Hydrofining section hydrogen dividing potential drop, Mpa hydrogen to oil volume ratio volume space velocity, h -1Temperature of reaction, ℃ catalyzer numbering | 6.5 500 1.0 340 HT-1 | 6.5 800 2.0 355 HT-2 | 8.0 600 1.5 365 HT-1 | 4.0 500 1.0 360 HT-2 | 9.0 1200 3.0 385 HT-1 | 8.0 800 2.0 380 HT-2 | 6.5 800 2.0 355 HT-2 | 6.5 800 2.0 355 HT-2 |
| Hydrodewaxing section hydrogen dividing potential drop, Mpa hydrogen to oil volume ratio volume space velocity, h -1Temperature of reaction, ℃ catalyzer numbering | 6.5 500 1.0 340 HDW-1 | 6.5 800 2.0 355 HDW-2 | 8.0 600 1.5 365 HDW-1 | 4.0 500 1.0 360 HDW-2 | 9.0 1200 3.0 385 HDW-1 | 8.0 800 2.0 380 HDW-2 | 6.5 800 2.0 355 HDW-2 | |
| Saturated section hydrogen dividing potential drop of aromatic hydrocarbons, Mpa hydrogen to oil volume ratio volume space velocity, h -1Temperature of reaction, ℃ catalyzer numbering | 6.5 500 1.0 310 HAD-1 | 6.5 800 1.0 308 HDA-1 | 8.0 600 1.5 310 HDA-2 | 4.0 500 1.0 320 HDA-2 | 9.0 1200 3.0 340 HDA-1 | 8.0 800 2.0 330 HDA-2 | 6.5 800 1.0 308 HDA-1 | |
Table 4 combination process test-results
| Test number | Embodiment-1 | Embodiment-2 | Embodiment-3 | Embodiment-4 | Embodiment-5 | Embodiment-6 | Comparative example-1 | Comparative example-2 |
| Diesel yield, w% density (20 ℃), kg/m 3Sulphur content, μ g/g nitrogen content, μ g/g aromaticity content, w% cetane value 90% boiling range, ℃ condensation point, ℃ cold filter clogging temperature, ℃ | 93.1 835.0 15.0 1.0 14.5 55.3 339 -30 -20 | 92.9 835.9 16.1 1.0 14.8 55.0 338 -28 -17 | 91.7 830.0 5.2 1.0 5.8 58.0 339 -41 -30 | 90.4 839.0 52.0 12.2 24.9 53.5 338 -30 -19 | 87.9 822.0 2.0 1.0 24.5 53.0 337 -39 -21 | 89.2 828.0 5.8 1.0 20.4 53.9 338 -39 -29 | 95.0 835.2 15.2 1.0 14.0 55.2 340 7 16 | 93.1 842.0 159.5 30.0 38.0 43.8 339 -32 -19 |
Embodiment 1-6 is a particular embodiment of the present invention, and wherein comparative example 1 is to adopt the saturated two-stage method of hydrofining/aromatic hydrocarbons to produce the example of diesel oil, and comparative example 2 is to adopt hydrofining-hydrodewaxing one-stage serial method to produce the example of diesel oil.From the listed test conditions of table 3 and table 4 and test-results as can be seen, adopt the embodiment 1-6 of the inventive method all can produce the low high-grade low-freezing diesel oil of aromaticity content, and other quality of diesel oil that the method that adopts comparative example 1 is produced is good, but can not reduce the condensation point of diesel oil; The condensation point of diesel oil that adopts the method for comparative example 2 to produce is low, but other of diesel oil is of poor quality, this shows advance of the present invention.
Claims (7)
1. the production method of a fine-quality diesel oil comprises:
(1) content of wax diesel oil distillate oil at first contacts with Hydrobon catalyst with the mixture of hydrogen, mainly carries out hydrogenating desulfurization, denitrification reaction;
(2) reacting rear material contact with Hydrodewaxing catalyst again (1) step, mainly selects the shape scission reaction, removes content of wax component, reduces condensation point, and the while further removes impurity such as S, N;
(3) enter Separate System of Water-jet through (2) step post reaction mixture material, wherein H
2S, NH
3Remove;
(4) through (3) step separation removal H
2S, NH
3After liquid phase material under the condition that hydrogen exists, contact with precious metal aromatic hydrocarbon saturation catalyst, carry out degree of depth aromatic hydrocarbons saturated reaction with the reduction aromaticity content;
(5) logistics behind (4) step aromatic hydrocarbons hydrocarbon saturated reaction enters separation system, separates obtaining hydrogen-rich gas and liquid-phase product;
The operational condition of wherein said hydrofining and hydrodewaxing process is: 300～430 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～8.0MPa, hydrogen to oil volume ratio 200～1000, volume space velocity 0.5～5.0h during liquid
-1The operational condition of described aromatic hydrocarbons degree of depth saturation history is: 200～400 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～15.0MPa, hydrogen to oil volume ratio 200～1800, volume space velocity 0.2～10.0h during liquid
-1Described aromatic hydrocarbon saturation catalyst is as active ingredient, with Modified Zeolite Y and γ-Al with the Pd in the group VIII noble metals and/or Pt
2O
3As carrier, be benchmark with catalyst weight per-cent jointly, the total metal contents in soil of Pd and/or Pt is 0.2%～2.0%, and the content of modified zeolite of Y-type is 40%～90%, and surplus is γ-Al
2O
3The modified zeolite of Y-type unit cell parameters is 2.435～2.455nm, SiO
2/ Al
2O
3Value is 5～70, Na
2The O weight content is less than 0.20%.
2, according to the described fine-quality diesel oil production method of claim 1, it is characterized in that described Hydrobon catalyst is is carrier with refractory oxide or the refractory oxide that contains a little auxiliary, the catalyst activity component is group vib component and/or the group VIII component in the periodic table of elements.
3, according to the described fine-quality diesel oil production method of claim 1, it is characterized in that described hydrodewaxing section catalyzer be with in the mesopore sub-sieve with refractory oxide or the refractory oxide that contains a little auxiliary jointly as carrier, the hydrogenation active metals component is group VIII metal component and/or a VI family metal component in the periodic table of elements.
4,, it is characterized in that described Hydrobon catalyst is with γ-Al according to the described fine-quality diesel oil production method of claim 1
2O
3Being carrier, is the hydrogenation activity component to be selected from metal component W of VI family in the periodic table of elements and/or Mo and group VIII metal component Ni, is benchmark, wherein WO with the weight percent of catalyzer
3And/or MoO
3Content account for 10%～30%, NiO accounts for 8%～15%.
5, according to the described fine-quality diesel oil production method of claim 1, it is characterized in that described Hydrodewaxing catalyst is is the hydrogenation activity component with Ni and/or Co, with ZSM-5 molecular sieve and aluminum oxide is carrier, with catalyst weight per-cent is benchmark, the content of ZSM-5 molecular sieve is 60～90%, and NiO and/or CoO content should be 1.0%～3.0%.
6, according to the described fine-quality diesel oil production method of claim 1, it is characterized in that described Hydrobon catalyst pore volume is 0.3～0.6ml/g, specific surface is 200～650m
2/ g.
7, according to the described fine-quality diesel oil production method of claim 1, it is characterized in that described Hydrodewaxing catalyst pore volume is 0.15～0.40ml/g, specific surface area is 200～800m
2/ g, the NH of catalyzer
3-TPD acid is distributed as:
160℃：0.150～0.185mmol/g；
250℃：0.115～0.145mmol/g；
350℃：0.060～0.105mmol/g；
450℃：0.045～0.065mmol/g；
530℃：0.005～0.020mmol/g。
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|---|---|---|---|
| CN 01133370 CN1197940C (en) | 2001-10-30 | 2001-10-30 | Method for producing good quality diesel oil |
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|---|---|---|---|
| CN 01133370 CN1197940C (en) | 2001-10-30 | 2001-10-30 | Method for producing good quality diesel oil |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323140C (en) * | 2004-08-31 | 2007-06-27 | 中国石油化工股份有限公司 | Two-step super-depth method for removing arenes from natural gas synthetic oil |
| CN1323139C (en) * | 2004-08-31 | 2007-06-27 | 中国石油化工股份有限公司 | One-step super-depth method for removing arenes from natural gas synthetic oil |
| CN100340642C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Method for producing high grade low condensation diesel oil from distillate oil |
| CN100352896C (en) * | 2005-10-19 | 2007-12-05 | 长春惠工催化剂有限责任公司 | Diesel oil hydroforming pourpoint depressing catalyst and preparing process thereof |
| CN102051217B (en) * | 2009-10-30 | 2014-07-30 | 中国石油化工股份有限公司 | Hydrogenation method for producing ultra-low sulfur clean diesel |
| CN101880603A (en) * | 2010-07-01 | 2010-11-10 | 云南铭惠石化有限公司 | Method for preparing low condensation point biodiesel from high acid value oil |
| CN103059934B (en) * | 2011-10-19 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of hydro-upgrading pour-point depressing method taking into account diesel product quality |
| CN104971732B (en) * | 2014-04-09 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its application |
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