CN102453531A - Hydrodewaxing method for diesel fraction - Google Patents
Hydrodewaxing method for diesel fraction Download PDFInfo
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Abstract
The invention discloses a hydrodewaxing method for diesel fraction. The method is as follows: a raw material of wax-containing diesel oil sequentially passes through alternatively cascaded hydrodewaxing catalyst beds and hydrofining catalyst beds, and a finally obtained hydrofining product is subjected to separation so as to obtain a product of diesel oil. The method enables average reaction temperature of the hydrodewaxing catalyst beds to be increased, thereby improving the utilization rate of a hydrodewaxing catalyst, prolonging the on-stream period of an apparatus and enhancing yield of the target product.
Description
Technical field
The present invention relates to a kind of method of hydrotreating of diesel oil, particularly the hydrogenating and pour point depressing method of content of wax diesel oil.
Background technology
Diesel product is mainly derived from straight-run diesel oil and secondary processing diesel oil.Not only contain impurity such as sulphur, nitrogen in the raw material, but also contain the wax component.Common process for dewaxing is to adopt the hydrogenating and pour point depressing technology, and is low because of its less investment, process cost, strong and operational condition relaxes, condensation point reduces advantages such as amplitude is big and receives much concern to adaptability to raw material.
Diesel hydro-pour-reducing is meant that under the situation that hydrogen exists the diesel raw material of the content of wax reduces wax molecule content wherein on the appropriate catalyst surface.Its dewaxing principle is under certain operational condition; Raw material is mixed with hydrogen to be contacted with Hydrodewaxing catalyst; Paraffinic hydrocarbons in the raw material, band short-side chain alkane, the naphthenic hydrocarbon of belt length side chain and the component such as condensation point such as height such as aromatic hydrocarbons grade of belt length side chain optionally are cracked into small molecules; And other component does not change basically, finally reaches the purpose of the condensation point that reduces oil product.United States Patent(USP) No. 3,894,438,3,894,439,4,173,148,4,181,598 and 4,437,975 have described the catalytic dewaxing process of oil product.
Hydrodewaxing catalyst is a dual-function catalyst, and metal component provides and adds the dehydrogenation activity center, and ZSM-5 equimolecular sieve provides proper pore structure and acid sites.If but the acid site of molecular sieve is a lot, acidity is very strong again, then can cause the over-drastic scission reaction; Generate a large amount of gases; Make purpose product-diesel oil distillate yield losses, reduce economy, something must be done to is controlled at a suitable scope with the acid site and the strength of acid of catalyzer.The present method that reduces catalyst acidity has multiple, like the molecular sieve of employing high silica alumina ratio, with methods such as steam-treated, high-temperature roastings.Above treatment process can not be regulated acidity in molecular sieve surface acidity and the hole selectively, causes raising selectivity of catalyst and activity to receive very big restriction.And, when improving catalyst selectivity, exist activity but to reduce usually, so the employing aforesaid method receives very big restriction when improving catalyst selectivity.
CN 85100324A discloses a kind of distillate Hydrodewaxing catalyst and preparation method thereof; This catalyzer is that the direct synthetic ZSM-5 of employing non-amine method zeolite molecular sieve is a matrix, through s.t., adds the tackiness agent kneading and compacting; Add metal component, process through water vapor thermal treatment again.This method employing steam-treated has not only reduced the acidity of HZSM-5 molecular sieve outer surface, and also reduction significantly of the acidity in the duct, and the raising of catalyst activity is restricted like this.
Adopt the no amine type high silica alumina ratio ZSM-5 of little crystal grain in the disclosed Hydrodewaxing catalyst of CN1219571A, tackiness agent is selected carbon dioxide process synthetic aluminum oxide for use.Because the silica alumina ratio of selected ZSM-5 molecular sieve is high, causes the acid site number few, will certainly influence activity of such catalysts, and present method do not do any improvement with regard to the pore structure aspect of molecular sieve, and the selectivity of its purpose product also can further improve.
The disclosed Hydrodewaxing catalyst of CN1352231A is to adopt non-amine method synthetic high silica alumina ratio ZSM-5, contains nickel oxide 1.0%～6.0% and Tungsten oxide 99.999 0～15%.This method adopts the method for high-temperature roasting support of the catalyst to reduce the acidity of catalyzer; Its main deficiency is can not remove selectively in the high-temperature roasting dealumination process aluminium atom of molecular sieve outer surface; Thereby influence the raising of selectivity of catalyst; And the dealuminzation degree also can cause caving in of framework of molecular sieve when dark, and its selectivity to paraffinic hydrocarbons is reduced.
CN1257107A has introduced a kind of method of being produced high-grade low-freezing diesel oil by distillate.This method adopts unifining and hydrogenating and pour point depressing one-stage serial flow process, and comprising Hydrobon catalyst and two beds of Hydrodewaxing catalyst, hydrogenating and pour point depressing adopts the Ni/ZSM-5 catalyzer.This method is bigger at the temperature drop of Hydrodewaxing catalyst bed, and the raising of the yield of diesel oil distillate and pour point depression effect receives certain limitation, has reduced the work-ing life of Hydrodewaxing catalyst.
Summary of the invention
To deficiency of the prior art, the present invention proposes a kind of liquid receive high, the diesel oil distillate yield is high, pour point depression is effective, the method for the diesel hydro-pour-reducing of catalyzer long service life.
The method of diesel hydro-pour-reducing of the present invention; Comprise at least two Hydrodewaxing catalyst beds and at least two Hydrobon catalyst beds; Content of wax diesel raw material is Hydrodewaxing catalyst bed and the Hydrobon catalyst bed through alternately connecting and load successively; The hydrotreated product of final gained obtains diesel product through separating.
In the method for diesel hydro-pour-reducing of the present invention, the volume ratio of adjacent Hydrodewaxing catalyst bed and Hydrobon catalyst bed is 20～40: 4～10.
Described Hydrodewaxing catalyst can adopt and contain the shape slective cracking sieve catalyst, is carrier with shape slective cracking molecular sieve and tackiness agent promptly, is the hydrogenation active metals component with group vib and/or group VIII metal.Described shape slective cracking molecular sieve is a Hydrogen shape slective cracking molecular sieve, is selected among ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and the ZSM-38 one or more, preferred ZSM-5; The silica alumina ratio of said shape slective cracking molecular sieve is 10～150, is preferably 20～120.Described group vib metal is one or more among Mo, the W, and described group VIII metal is one or more among Co, the Ni.Weight with catalyzer is benchmark, and the hydrogenation active metals component is 1%～16% in the weight content of oxide compound, and the weight content of shape slective cracking molecular sieve is 50%～85%, and the weight content of tackiness agent is 10%～40%.
Preferably select the Hydrodewaxing catalyst of carrier in the inventive method for use through modification; Wherein carrier comprises shape slective cracking molecular sieve and tackiness agent; Also contain silicon dioxide meter finishing coat and metal promoter oxide compound; Described metal promoter is one or more in IIA, IB, IIB and the IIIB family metal, is preferably in IIA and the IIB family metal one or more.The composition of this catalyzer is following: the weight with catalyzer is benchmark; The content of shape slective cracking molecular sieve is 50%～85%, and the weight content of active metal oxide is 1%～16%, and the weight content of described silicon dioxide meter finishing coat is 1%～10%; Be preferably 2%～8%; The weight content of metal promoter oxide compound is 0.1%～8.0%, is preferably 0.5%～6.5%, and the weight content of tackiness agent is 10%～40%.In the described metal promoter; Described IIA family metal is preferably one or more in magnesium and the calcium; Described IB family metal is preferably copper, and described IIB family metal is preferably zinc, and described IIIB family metal is preferably one or more in scandium, yttrium and the lanthanide series metal.Described lanthanide series metal is preferably lanthanum.Active metal component is the conventional used active metal component of Hydrodewaxing catalyst, is generally in group vib and/or the group VIII metal one or more, and described group vib metal is Mo and/or W, and the group VIII metal is Ni and/or Co.The present invention is preferably following: the weight with catalyzer is benchmark, and the content of group vib MOX is 2.0%～15.0%, and the content of group VIII MOX is 0.1%～5.0%.Described active metal component is preferably Ni and W or Ni and Mo.Tackiness agent can adopt conventional binder ingredients, such as in aluminum oxide, the siliceous aluminum oxide one or more, is preferably aluminum oxide.The titanium dioxide surface silicon coating that contains in the said carrier is guided on the carrier by silicone oil, and described silicone oil is one or more in hydroxy silicon oil, methyl-silicone oil, ethyl silicon oil, dimethyl silicone oil and the polymethylphenyl siloxane fluid.The character of this Hydrodewaxing catalyst is following: pore volume is 0.30～0.50cm
3/ g, specific surface area is 180～400m
2/ g, 350～390 ℃ acidity is 0.085～0.190mmol/g, is preferably 0.100～0.180mmol/g.
Among the present invention, specific surface area and pore volume adopt the low temperature liquid nitrogen determination of adsorption method, and acidity adopts NH
3The temperature programmed desorption(TPD) method is measured.
The preparation method of the preferred Hydrodewaxing catalyst of the present invention; Comprise: will select type cracking molecular sieve and tackiness agent mix pinch, moulding, process carrier through dry and roasting, more successively through metal promoter modification and silicon modification; Obtain the carrier after metal promoter and silicon modification, again the supported active metal component; Wherein the process through metal promoter and silicon modification is following successively for carrier:
(1) with the solution impregnating carrier of containing metal auxiliary agent, after drying, obtains carrier through the metal promoter modification;
(2) silicone oil and organic solvent being made into the silicon oxide weight concentration is 5%～40%, is preferably 10%～25% silicone oil organic liquid mixture;
(3) with the carrier through the metal promoter modification of silicone oil organic liquid mixture impregnation steps (1) gained of step (2) gained,, obtain the carrier after metal promoter and silicon modification then through drying and roasting.
The aqueous solution of the described containing metal auxiliary agent of step (1) is soluble in water the obtaining of compound of adopting the containing metal auxiliary agent, and weight concentration counts 0.5%～10.0% with the metal promoter oxide compound.The compound of containing metal auxiliary agent can be water-soluble compounds such as nitrate salt, muriate.Behind the dipping, described drying conditions is following: temperature is 40～200 ℃, and the time is 1～20h.
The described organic solvent of step (2) is one or more in hexanaphthene, industrial naptha, coking lightnaphtha, mononuclear aromatics compounds and the Vegetable oil lipoprotein.Described Vegetable oil lipoprotein is one or more in soya-bean oil, peanut oil, rapeseed oil, the til.
In the described steeping process of step (3), the silicone oil organic mixture is 0.5: 1～3: 1 with volume ratio through the carrier of metal promoter modification, and time of immersion was generally 1～10 hour.Behind the dipping, described drying conditions is following: 40～280 ℃ of temperature, time of drying 1～20h; Described roasting condition is following: 360～600 ℃ of temperature, roasting time 2～10h.The described steeping process of step (3) can adopt single-steeping, also can adopt repeatedly dipping, behind each dipping, preferably adopts after the above-mentioned drying and calcination steps, floods next time again.
In the inventive method, after the carrier moulding, condition dry and roasting is following: 50～150 ℃ of dryings of warp 2～15 hours, processed carrier in 1～6 hour through 300～600 ℃ of roastings.In the extruded moulding process, can add extrusion aid.Described extrusion aid is meant the material that helps extrusion molding, and like sesbania powder, carbon black, Graphite Powder 99, Hydrocerol A etc., the consumption of extrusion aid accounts for total 1wt%～5wt% that pinches the material butt that mixes.
In the inventive method, carrier loaded active metal component can adopt conventional pickling process.Flooding the used active metallic compound that contains is water-soluble cpds, is generally in nitrate salt, vitriol, ammonium salt and the muriate one or more.Wherein, Tungstenic compound is preferably ammonium metawolframate, and nickel compound containing is preferably nickelous nitrate, and cobalt compound is preferably Xiao Suangu, and molybdate compound is an ammonium molybdate.Described dipping method preferably adopts the supersaturation dipping method.Behind the dipping active metal component, 40～130 ℃ of dryings of warp 2～8 hours through 450～600 ℃ of roastings 2～10 hours, are processed Hydrodewaxing catalyst of the present invention.
Described Hydrobon catalyst is a carrier with aluminum oxide or siliceous aluminum oxide usually, and the hydrogenation active metals component is group vib and the group VIII metal in the periodic table of elements, and preferred or Mo and Co are the hydrogenation active metals component.Described Hydrobon catalyst is preferably formed as follows: the weight with catalyzer is benchmark, preferred MoO
3Content account for 15%～30%, the content of CoO accounts for 4%～12%, the pore volume of this catalyzer is 0.3～0.6ml/g, specific surface area is 200～650m
2/ g.
In the inventive method, the hydrogenating and pour point depressing condition of Hydrodewaxing catalyst bed is: 300～420 ℃ of temperature of reaction, optimum range are 340～390 ℃; Hydrogen dividing potential drop 2.0～8.0MPa, optimum range is 3.0～6.0MPa; Hydrogen to oil volume ratio 200～800, optimum range are 400～600; Volume space velocity 0.2～4.0h during liquid
-1, optimum range is 0.9～3.0h
-1The unifining condition of Hydrobon catalyst bed is: 300～420 ℃ of temperature of reaction, optimum range are 330～400 ℃; Hydrogen dividing potential drop 2.0～8.0MPa, optimum range is 3.0～6.0MPa; Hydrogen to oil volume ratio 200～800, optimum range are 400～600; Volume space velocity 3.0～10.0h during liquid
-1, optimum range is 5.0～8.0h
-1
In the inventive method; Foreign matter contents such as sulphur and nitrogen are higher in the described content of wax diesel raw material, can load Hydrobon catalyst before first Hydrodewaxing catalyst bed and make waxy feeds carry out the hydrogenation pre-refining earlier, remove impurity such as sulphur and nitrogen wherein; In order to avoid impurity such as the alkali nitrogen in the shape slective cracking sieve catalyst absorption oil product and inactivation; Wherein used Hydrobon catalyst can be the Hydrobon catalyst of routine, is carrier with aluminum oxide or siliceous aluminum oxide usually, and the hydrogenation active metals component is group vib and the group VIII metal in the periodic table of elements; Preferred W of group vib and/or Mo, preferred Ni of group VIII metal and/or Co.Hydrogenation pre-refining operational condition is following: 300～420 ℃ of temperature of reaction, optimum range are 320～380 ℃; Hydrogen dividing potential drop 2.0～8.0MPa, optimum range is 3.0～6.0MPa; Hydrogen to oil volume ratio 200～800, optimum range are 400～600; Volume space velocity 0.5～4.0h during liquid
-1, optimum range is 0.8～3.0h
-1
The inventive method adopts the alternately series connection filling of Hydrodewaxing catalyst bed and Hydrobon catalyst bed; Have following advantage: content of wax diesel raw material contacts with Hydrodewaxing catalyst earlier carries out the Hydrodewaxing reaction; This reaction is thermo-negative reaction; Simultaneously also can by-product alkene, the Hydrodewaxing product of gained gets into the Hydrobon catalyst bed and carries out hydrogenation reaction, mainly be carry out that alkene is saturated, impurity and aromatic hydrocarbons saturated reactions such as desulfurization and nitrogen; This reaction is thermopositive reaction, and the temperature of reactant flow is raise.Comparatively high temps, the reactant flow that foreign matter content is lower get into another Hydrodewaxing catalyst bed; Improved the average reaction temperature of Hydrodewaxing catalyst bed this moment greatly; This not only makes the utilization ratio of Hydrodewaxing catalyst improve; Prolong the on-stream time of device, and improved the yield of title product.The Hydrodewaxing product of gained gets into another Hydrobon catalyst bed and carries out hydrogenation reaction, for next Hydrodewaxing catalyst bed provides the reactant flow that foreign matter content is lower, temperature is higher, also can get into separation system and go out product.
It is the carrier that adopts through metal promoter and silicon modification that the inventive method adopts preferred Hydrodewaxing catalyst, at first uses the metal promoter modification, improves the performance of carrier; Especially modify shape slective cracking molecular sieve pore passage internal surface, and then with silicon oil modified, because the molecule of silicone oil is bigger; Can not enter in the duct of shape slective cracking molecular sieve, so finally form silica coating, the particularly outside surface of shape slective cracking molecular sieve and aperture at carrier surface; Mainly be the acidity and the orifice shapes of regulating molecular sieve outer surface, and keep the duct internal surface of modifying by metal promoter, and through optimizing the content of metal promoter and silica coating; Make the shape slective cracking molecular sieve have suitable pore structure and duct internal surface character, help carrying out the shape slective cracking reaction in the duct that the wax quasi-molecule is diffused into molecular sieve; Have advantages of high catalytic activity and purpose product selectivity; Again since the acidity of molecular sieve outer surface a little less than, cracking ability is low, has reduced side reaction.
The present invention adopts preferred L o-Co Hydrobon catalyst; This catalyzer has the saturated and lower lytic activity of stronger alkene; Can well cooperate with Hydrodewaxing catalyst, help improving the activity and the selectivity of Hydrodewaxing catalyst, and the running period of extension fixture; Especially match best results with preferred Hydrodewaxing catalyst.
Embodiment
Below embodiment will further explain and set forth with regard to method provided by the invention, but do not limit the present invention.Among the present invention, wt% representes massfraction.
Embodiment 1
Will be by little porous aluminum oxide (specific surface 238m
2G
-1, pore volume 0.48mLg
-1) tackiness agent processed is added to HZSM-5 molecular sieve (butt 97wt%, manufacturer: Tianjin Catalyst Factory, Nankai Univ, SiO
2/ Al
2O
3Mol ratio 38) in, mix, through extruded moulding, again through 130 ℃ of dryings 4 hours, 580 ℃ of roastings 4 hours obtain carrier.
With above-mentioned carrier be added to the zinc oxide weight content be in 6% zinc nitrate aqueous solution by incipient impregnation, time of immersion is 5 hours, after the filtration, the solid phase of gained obtains the zinc modification carrier through 120 ℃ of dryings 4 hours.
In dimethyl silicone oil, add hexanaphthene, obtain the silicon oxide weight concentration and be 15% silicone oil organic liquid mixture, then the zinc modification carrier is added in the above-mentioned silicone oil organic liquid mixture by incipient impregnation, time of immersion is 3 hours.100 ℃ of dryings 4 hours, 580 ℃ of roastings 4 hours obtained the carrier S 1 through zinc and silicon modification after filtering, and wherein the zinc oxide weight content is 2.0%, and the silicon oxide surface coating levels is 5.0wt%.
The carrier S 1 of gained is dipped in the aqueous solution of nickeliferous and tungsten, and then through 120 ℃ of dryings 5 hours, 600 ℃ of roastings 3 hours obtain Hydrodewaxing catalyst N1.
Embodiment 2
Will be by little porous aluminum oxide (specific surface 238m
2G
-1, pore volume 0.48mLg
-1) tackiness agent processed is added in the HZSM-5 molecular sieve (with embodiment 1), mixes, through extruded moulding, again through 130 ℃ of dryings 4 hours, 580 ℃ of roastings 4 hours obtain carrier.
It is that 3wt% cupric nitrate and content of magnesia are to be 1: 1.5 dipping by volume in the aqueous solution of magnesium nitrate of 3wt% that above-mentioned carrier is added to cupric oxide content; Time of immersion is 4 hours; After the filtration, 120 ℃ of dryings of the solid phase of gained warp 5 hours obtain copper and magnesium-modified carrier.
In ethyl silicon oil, add industrial naptha, obtain the silicon oxide weight concentration and be 20% silicone oil organic liquid mixture, then copper and magnesium-modified carrier being added in the above-mentioned silicone oil organic liquid mixture is 1: 1.5 dipping by volume, and time of immersion is 3 hours.Filter after the back 100 ℃ of dryings 6 hours, 550 ℃ of roastings 6 hours obtain the carrier S 2 through copper, magnesium and silicon modification, and wherein the cupric oxide weight content is 1.5%, and the Natural manganese dioxide weight content is 2.0%, and the silicon oxide surface coating levels is 6.0wt%.
The carrier S 2 of gained is dipped in the aqueous solution of nickeliferous and tungsten, and then through 120 ℃ of dryings 5 hours, 560 ℃ of roastings 5 hours obtain Hydrodewaxing catalyst N2.
Embodiment 3
Will be by little porous aluminum oxide (specific surface 238m
2G
-1, pore volume 0.48mLg
-1) tackiness agent processed is added in the HZSM-5 molecular sieve (with embodiment 1), mixes, through extruded moulding, again through 130 ℃ of dryings 4 hours, 580 ℃ of roastings 4 hours obtain carrier.
It is 1: 1.5 dipping by volume that above-mentioned carrier is added in the aqueous solution that lanthanum trioxide content is the 9wt% Lanthanum trinitrate, and time of immersion is 4 hours, and after the filtration, the solid phase of gained obtains the carrier of lanthanum modification through 120 ℃ of dryings 5 hours.
In ethyl silicon oil, add industrial naptha, obtain the silicon oxide weight concentration and be 20% silicone oil organic liquid mixture, then the carrier of lanthanum modification being added in the above-mentioned silicone oil organic liquid mixture is 1: 1.5 dipping by volume, and time of immersion is 3 hours.Filter after the back 120 ℃ of dryings 4 hours, 500 ℃ of roastings 8 hours obtain the carrier S 3 through lanthanum and silicon modification, and wherein the lanthanum trioxide weight content is 5.5%, and the silicon oxide surface coating levels is 6.0wt%.
The carrier S 3 of gained is dipped in the aqueous solution of nickeliferous and tungsten, and then through 120 ℃ of dryings 5 hours, 550 ℃ of roastings 6 hours obtain Hydrodewaxing catalyst N3.
Embodiment 4
The preparation of carrier is with embodiment 1.
With above-mentioned carrier be added to the zinc oxide weight content be 5% with the quicklime weight content be in 5% the calcium nitrate aqueous solution by incipient impregnation, time of immersion is 5 hours, after the filtration, the solid phase of gained obtains the carrier of zinc and calcium modification through 120 ℃ of dryings 4 hours.
In polymethylphenyl siloxane fluid, add YLENE, obtain the silicon oxide weight concentration and be 18% silicone oil organic liquid mixture, then the carrier of zinc and calcium modification being added in the above-mentioned silicone oil organic liquid mixture is 1: 2 dipping by volume, and time of immersion is 3 hours.Filter after the back 140 ℃ of dryings 4 hours, 560 ℃ of roastings 6 hours obtain the carrier S 4 through zinc, calcium and silicon modification, and wherein the zinc oxide weight content is 2.0%, and the weight content of quicklime is 2.0%, and the silicon oxide surface coating levels is 5.0wt%.
The carrier S 4 of gained is dipped in the aqueous solution of nickeliferous and tungsten, and then through 120 ℃ of dryings 5 hours, 580 ℃ of roastings 3 hours obtain Hydrodewaxing catalyst N4.
Embodiment 5
The preparation of carrier is with embodiment 1.
With above-mentioned carrier be added to the zinc oxide weight content be 5% with the lanthanum trioxide weight content be in 4% the lanthanum nitrate aqueous solution by incipient impregnation, time of immersion is 5 hours, after the filtration, the solid phase of gained obtains the carrier of zinc and lanthanum modification through 120 ℃ of dryings 4 hours.
In hydroxy silicon oil, add soya-bean oil, obtain the silicon oxide weight concentration and be 18% silicone oil organic liquid mixture, then the carrier of zinc and lanthanum modification being added in the above-mentioned silicone oil organic liquid mixture is 1: 2 dipping by volume, and time of immersion is 3 hours.Filter after the back 120 ℃ of dryings 4 hours, 580 ℃ of roastings 4 hours obtain the carrier S 5 through zinc, lanthanum and silicon modification, and wherein the zinc oxide weight content is 2.0%, and the lanthanum trioxide weight content is 1.5%, and the silicon oxide surface coating levels is 7.0wt%.
Carrier S 5 is dipped in the aqueous solution of nickeliferous and molybdenum, and then through 120 ℃ of dryings 5 hours, and 560 ℃ of roastings 5 hours obtain Hydrodewaxing catalyst N5.
Embodiment 6
Compare with embodiment 3, with lanthanum trioxide content be the aqueous solution of 9wt% Lanthanum trinitrate to replace with the Natural manganese dioxide weight content be 5% magnesium nitrate aqueous solution, obtain Hydrodewaxing catalyst N6.
Embodiment 7
The preparation of carrier is with embodiment 1.
Carrier is dipped in the nickeliferous aqueous solution, and then through 120 ℃ of dryings 5 hours, 600 ℃ of roastings 3 hours obtain Hydrodewaxing catalyst N7.
The composition and the character of table 1 embodiment of the invention gained catalyzer
| The catalyzer numbering | N1 | N2 | N3 | N4 | N5 | N6 | N7 |
| Catalyzer is formed, wt% | |||||||
| NiO | 1.5 | 2.5 | 2.0 | 1.5 | 2.2 | 2.0 | 2.2 |
| MoO 3 | - | - | - | 10.0 | 8.6 | - | - |
| WO 3 | 3.5 | 11.4 | 8.0 | - | - | 8.0 | - |
| Molecular sieve | 75 | 65 | 80 | 55 | 78 | 80 | 85 |
| Tackiness agent | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Catalyst property | |||||||
| Specific surface area, m 2/g | 320 | 252 | 358 | 260 | 310 | 365 | 290 |
| Pore volume, ml/g | 0.43 | 0.38 | 0.46 | 0.36 | 0.34 | 0.42 | 0.40 |
| 350～390 ℃ of acidity, mmol/g | 0.146 | 0.155 | 0.166 | 0.105 | 0.140 | 0.152 | 0.108 |
Embodiment 8
The hydrogenation pre-refining catalyzer that embodiment selects for use is FH-98, is produced by Sinopec catalyst Co. Fushun branch office.The composition of the Hydrobon catalyst A that selects for use is following: MoO
3Weight content be 24.0%, the weight content of CoO is 6.2%, surplus is an aluminum oxide; The character of this catalyzer is following: pore volume is 0.34ml/g, and specific surface area is 251m
2/ g.
With the MDO Medium diesel oil is raw material (character is seen table 2); Contact with hydrogenation pre-refining catalyzer FH-98 earlier and carry out hydrofining reaction; The hydrotreated product of gained contacts with Hydrobon catalyst with the Hydrodewaxing catalyst of alternately series connection filling again; Wherein Hydrodewaxing catalyst N1 and Hydrobon catalyst A load three beds respectively, and along liquid phase reaction logistics direction, the volume ratio of each layer catalyzer is 21: 4: 29: 6: 29: 9.The processing condition that adopted are seen table 3, and the character of gained diesel product is seen table 3.
Embodiment 9-14
Adopt Hydrodewaxing catalyst N2-N7 to replace the N1 among the embodiment 8 respectively, the processing condition that adopted are seen table 3, and gained diesel product character is seen table 3.
Comparative Examples 1
With the MDO Medium diesel oil is raw material (character is seen table 2); Contact with hydrogenation pre-refining catalyzer FH-98 earlier and carry out hydrofining reaction; The hydrogenation pre-refining product of gained contacts with Hydrobon catalyst A with Hydrodewaxing catalyst more successively; Wherein the volume ratio of Hydrodewaxing catalyst N7 and Hydrobon catalyst A is 81: 19, and the processing condition that adopted are seen table 3, and the character of gained diesel product is seen table 3.
Table 2 raw oil character
| Character | Mixing raw material |
| Blending ratio | Solar oil: heavy gas oil |
| Density/kg.m -3 | 904.0 |
| Boiling range/℃ | |
| IBP/10％ | 163/239 |
| 30％/50％ | 272/300 |
| 70％/90％ | 325/348 |
| 95％/EBP | 360/369 |
| Condensation point/℃ | 5 |
| Sulphur/μ g.g-1 | 1603 |
| Nitrogen/μ g.g-1 | 1555 |
| Mass spectrum is formed, wt% | |
| Paraffinic hydrocarbons | 27.9 |
| Naphthenic hydrocarbon | 13.2 |
| Total aromatic hydrocarbons | 58.3 |
| Colloid | 0.6 |
Table 3 main technique condition
* annotate: the summation of volume space velocity when volume space velocity is meant the liquid of three Hydrodewaxing catalyst beds during total liquid in the hydrogenating and pour point depressing condition; Average reaction temperature is meant the MV of the temperature of reaction of three Hydrodewaxing catalyst beds;
* annotates: the summation of volume space velocity when volume space velocity is meant the liquid of three Hydrobon catalyst beds during total liquid in the unifining condition; Average reaction temperature is meant the MV of the temperature of reaction of three Hydrobon catalyst beds.
Table 4 diesel product main character
Visible by table 3, compare with Comparative Examples 1, under the condition of TV air speed unanimity; When processing same raw oil and producing low-coagulation diesel oil; The temperature of reaction of the hydrogenation pre-refining section of the inventive method is lower, has given full play to the pour point depression characteristic of Hydrodewaxing catalyst, has prolonged the on-stream time of device; And the yield of purpose low-coagulation diesel oil product increases substantially, and reached good reaction effect.
Claims (17)
1. the method for a diesel hydro-pour-reducing; Comprise at least two Hydrodewaxing catalyst beds and at least two Hydrobon catalyst beds; Content of wax diesel raw material is Hydrodewaxing catalyst bed and the Hydrobon catalyst bed through alternately connecting and load successively; The hydrotreated product of final gained obtains diesel product through separating.
2. according to the described method of claim 1, it is characterized in that the volume ratio of adjacent Hydrodewaxing catalyst bed and Hydrobon catalyst bed is 20～40: 4～10.
3. according to the described method of claim 1, it is characterized in that described Hydrodewaxing catalyst is a carrier with shape slective cracking molecular sieve and tackiness agent, is the hydrogenation active metals component with group vib and/or group VIII metal.
4. according to the described method of claim 3, it is characterized in that described shape slective cracking molecular sieve is a Hydrogen shape slective cracking molecular sieve, be selected among ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and the ZSM-38 one or more; Described group vib metal is one or more among Mo, the W, and described group VIII metal is one or more among Co, the Ni.
5. according to claim 3 or 4 described methods; It is characterized in that described Hydrodewaxing catalyst; Weight with catalyzer is benchmark; The hydrogenation active metals component is 1%～16% in the weight content of oxide compound, and the weight content of shape slective cracking molecular sieve is 50%～85%, and the weight content of tackiness agent is 10%～40%.
6. according to claim 3 or 4 described methods; It is characterized in that described Hydrodewaxing catalyst selects the Hydrodewaxing catalyst of carrier through modification for use; Wherein carrier comprises shape slective cracking molecular sieve and tackiness agent; Also contain silicon dioxide meter finishing coat and metal promoter oxide compound, described metal promoter is one or more in IIA, IB, IIB and the IIIB family metal; The composition of this catalyzer is following: the weight with catalyzer is benchmark; The content of shape slective cracking molecular sieve is 50%～85%; The weight content of active metal oxide is 1%～16%; The weight content of described silicon dioxide meter finishing coat is 1%～10%, and the weight content of metal promoter oxide compound is 0.1%～8.0%, and the weight content of tackiness agent is 10%～40%.
7. according to the described method of claim 6, it is characterized in that in the described Hydrodewaxing catalyst that the weight content of silicon dioxide meter finishing coat is 2%～8%, the weight content of metal promoter oxide compound is 0.5%～6.5%.
8. according to the described method of claim 6; It is characterized in that in the described metal promoter that described IIA family metal is one or more in magnesium and the calcium, described IB family metal is a copper; Described IIB family metal is a zinc, and described IIIB family metal is one or more in scandium, yttrium and the lanthanum.
9. according to the described method of claim 6, it is characterized in that described active metal component Ni and W or Ni and Mo, is benchmark with the weight of catalyzer, and the content of Tungsten oxide 99.999 and/or molybdenum oxide is 2.0%～15.0%, and the content of nickel oxide is 0.1%～5.0%.
10. according to the described method of claim 6; It is characterized in that the silicon dioxide meter finishing coat that contains in the said carrier guided on the carrier by silicone oil, described silicone oil is one or more in hydroxy silicon oil, methyl-silicone oil, ethyl silicon oil, dimethyl silicone oil and the polymethylphenyl siloxane fluid.
11. according to the described method of claim 6, it is characterized in that the character of said Hydrodewaxing catalyst is following: pore volume is 0.30～0.50cm
3/ g, specific surface area is 180～400m
2/ g, 350～390 ℃ acidity is 0.085～0.190mmol/g.
12. according to the described method of claim 1, it is characterized in that the composition of described Hydrobon catalyst is following: the weight with catalyzer is benchmark, MoO
3Content account for 15%～30%, the content of CoO accounts for 4%～12%, the pore volume of this catalyzer is 0.3～0.6ml/g, specific surface area is 200～650m
2/ g.
13., it is characterized in that the hydrogenating and pour point depressing condition is according to the described method of claim 1: 300～420 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～8.0MPa, hydrogen to oil volume ratio 200～800, volume space velocity 0.2～4.0h during liquid
-1The unifining condition is: 300～420 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～8.0MPa, hydrogen to oil volume ratio 200～800, volume space velocity 3.0～10.0h during liquid
-1
14., it is characterized in that the hydrogenating and pour point depressing condition is according to the described method of claim 1: temperature of reaction is 340～390 ℃; The hydrogen dividing potential drop is 3.0～6.0MPa; Hydrogen to oil volume ratio is 400～600; Volume space velocity is 0.9～3.0h during liquid
-1The unifining condition is: temperature of reaction is 330～400 ℃; The hydrogen dividing potential drop is 3.0～6.0MPa; Hydrogen to oil volume ratio is 400～600; Volume space velocity is 5.0～8.0h during liquid
-1
15., it is characterized in that according to the described method of claim 1, before first Hydrodewaxing catalyst bed, load Hydrobon catalyst and make content of wax diesel raw material carry out the hydrogenation pre-refining earlier, mainly remove wherein sulfur impurity and nitrogen.
16., it is characterized in that hydrogenation pre-refining condition is following according to the described method of claim 15: 300～420 ℃ of temperature of reaction; Hydrogen dividing potential drop 2.0～8.0MPa; Hydrogen to oil volume ratio 200～800; Volume space velocity 0.5～4.0h during liquid
-1
17., it is characterized in that hydrogenation pre-refining condition is following according to the described method of claim 15: 320～380 ℃ of temperature of reaction; Hydrogen dividing potential drop 3.0～6.0MPa; Hydrogen to oil volume ratio 400～600; Volume space velocity 0.8～3.0h during liquid
-1
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| CN103805237A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
| CN103805268A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing clean diesel oil with low condensation point by treating inferior diesel oil |
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| CN105087063B (en) * | 2014-05-06 | 2017-01-18 | 中国石油化工股份有限公司 | Hydroisomerization pour-point-depressing deep-coupling process for producing low-pour-point diesel oil |
| CN114479924A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrodewaxing method |
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| CN103805237A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
| CN103805268A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing clean diesel oil with low condensation point by treating inferior diesel oil |
| CN103805238A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low condensation point by gradation technology |
| CN103805238B (en) * | 2012-11-07 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of grating technology produces the method for hydrogenation low-coagulation diesel oil |
| CN103805237B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of method utilizing catalyzer grating technology to produce low-coagulation diesel oil |
| CN103805268B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of poor ignition quality fuel that processes produces the method cleaning low-coagulation diesel oil |
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| CN104611027B (en) * | 2013-11-05 | 2017-02-08 | 中国石油化工股份有限公司 | Low freezing point diesel fuel production method |
| CN105087063B (en) * | 2014-05-06 | 2017-01-18 | 中国石油化工股份有限公司 | Hydroisomerization pour-point-depressing deep-coupling process for producing low-pour-point diesel oil |
| CN114479924A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrodewaxing method |
| CN114479924B (en) * | 2020-10-27 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrodewaxing method |
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