CN105087064A - Method for producing clean low freezing point diesel oil by treating high nitrogen diesel oil - Google Patents
Method for producing clean low freezing point diesel oil by treating high nitrogen diesel oil Download PDFInfo
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Abstract
The invention discloses a method for producing clean low freezing point diesel oil by treating high nitrogen diesel oil. The method comprises: after mixing a diesel oil raw material with hydrogen, sequentially feeding the mixture through at least two serial hydrogenation reaction regions, wherein each of the hydrogenation reaction regions according a material flowing direction sequentially comprises a hydrogenation refining catalyst bed layer and a compound catalyst bed layer mixed and filled with a hydrodewaxing catalyst and a hydrogenation modified isomerization-visbreaking catalyst; and separating and fractionating a reaction effluent obtained in the last hydrogenation reaction region to obtain the low freezing point diesel oil. According to the method disclosed by the invention, temperature rise in a modified depressing process and temperature drop in a hydrodewaxing process are reasonably utilized,so that the yield and cetane number of the diesel oil are improved while the low freezing point diesel oil is produced, and therefore, the hot-spot temperature is reduced and the operating period is prolonged. In addition, the consumption of cold hydrogen or the gas loss of a heating furance is reduced, and the operating cost is further lowered.
Description
Technical field
The present invention relates to a kind of poor ignition quality fuel that processes and produce the processing method of low-coagulation diesel oil, especially a kind of by catalyzer grating technology and compound filling technology, be used for producing the method for hydrotreating of clean low-coagulation diesel oil.
Background technology
Diesel oil is as the fuel of self-igniton engine, irreplaceable effect is played as Nonrenewable resources in modern productive life process, launch vehicle or other mechanical fuel such as automobile, tank, aircraft, tractor, rail vehicle can be used as, also can be used to generating, heating etc.The difference of industry and environment is used according to it, user also has very large difference for the specification of quality of diesel product, for the people at extremely frigid zones or life in winter, the demand of low freezing point diesel fuel remains high always, and traditional shape slective cracking technique can process the heavy gas oil cut of the content of wax, and pour point depression amplitude can reach 20 ~ 50 DEG C, while obtaining low freezing point diesel fuel, also can widen diesel oil distillate scope, improve productive rate, be the very useful and advanced technology solving low freezing point diesel fuel production problem.
The situation of China is also similar, particularly in recent years, along with improving constantly of the national economic development and environmental consciousness, requirement for diesel quality is more and more higher, and the popularity rate of diesel refining rises year by year, this external northern cold area, except the requirement to diesel oil regular refiner character, condensation point becomes and requisitely requires one of index, therefore, it is possible to improve the seed output and quality of low-coagulation diesel oil, the major issue becoming and pay close attention to Han Qu oil refining enterprise of meeting the need of market.And shape slective cracking and combination process thereof are as one of Main Means reducing condensation point of diesel oil, can be used for producing low-sulfur low-coagulation diesel oil, be conducive to the economic benefit improving oil refining enterprise.
Diesel oil shape slective cracking technology, also known as hydrodewaxing, refers in the presence of hydrogen, and the diesel raw material of the content of wax by the dual-function catalyst surface containing active metal and molecular sieve, thus reduces wax molecule content wherein.Its dewaxing principle is under certain operating conditions, raw material is mixed with hydrogen contact with Hydrodewaxing catalyst, be cracked into small molecules paraffinic hydrocarbons in raw material, band short-side chain alkane, the naphthenic hydrocarbon of belt length side chain and the contour condensation point compositional selecting of aromatic hydrocarbons of belt length side chain, and other component does not change substantially, finally reach the object of the condensation point reducing oil product.Because it has that lower, the adaptability to raw material of reaction process hydrogen consumption is strong, energy consumption is lower, technical process is simple, can form the plurality of advantages such as process integration or independence use with other hydrogenation process, be therefore widely used.The a lot of oil refining enterprise of current northern China Han Qu all have employed this technology and produces low-coagulation diesel oil.
CN1257107A describes a kind of method of being produced high-grade low-freezing diesel oil by distillate.The method adopts hydrofining and hydrodewaxing one-stage serial flow process, and comprising Hydrobon catalyst and Hydrodewaxing catalyst two beds, hydrodewaxing adopts Ni/ZSM-5 catalyzer.The method is comparatively large at the temperature drop of Hydrodewaxing catalyst bed, and the yield of diesel oil distillate and the raising of depression effeCt are subject to a definite limitation, reduce the work-ing life of Hydrodewaxing catalyst.
CN102051232A describes a kind of method of diesel oil hydrogenation pour point depression, the method be by adjust catalyzer character thus make diesel oil depression effeCt good, the feature that diesel oil distillate yield is high, but owing to still adopting the combination process of hydrofining and hydrodewaxing series connection, the contradiction between depression effeCt and diesel oil distillate yield still exists.
CN102453531A describes a kind of method of diesel hydro-pour-reducing, although improve the average reaction temperature of Hydrodewaxing catalyst, utilize the temperature rise of finishing agent, increase the utilization ratio of pour point depression catalyzer, but the temperature of reaction of each bed outlet is still relatively high, and the cycle receives certain restriction.
CN1289931A the present invention discloses a kind of method of being produced high-quality low-coagulation diesel oil with high hexadecane value by distillate: by hydrodewaxing and hydrofining, hydro-upgrading is directly connected, realize hydrofining-hydro-upgrading-hydrodewaxing-section serial flow, what adopt is Hydrobon catalyst that anti-coking performance is strong and has stronger anti-ammonia, the hydro-upgrading of capacity antacid and Hydrodewaxing catalyst, thus refining/depression effeCt is good to make this technique have, diesel yield is high, adaptability to raw material is strong, diesel cetane-number is high, simple and the products scheme feature flexibly of technical process.
CN1417298A mono-kind produces the combined hydrogenation method of high hexadecane value, low-coagulation diesel oil, that stock oil, hydrogen are first contacted with catalyst for hydro-upgrading or hydrocracking catalyst, reaction effluent then contacts with Hydrodewaxing catalyst without separation, reaction effluent enters high-pressure separator through cooling, isolated product liquid enters fractionating system, and the gas circulation being rich in hydrogen returns reactor.The method can improve diesel-fuel cetane number simultaneously and reduce the condensation point of diesel oil in same set of device, and the cetane value of diesel product comparatively stock oil improves more than 6 units.
Summary of the invention
For prior art Problems existing, the invention provides a kind of compound production method of high quality low-coagulation diesel oil.The mixed catalyst that first the inventive method adopts high-performance Hydrobon catalyst and the hydrodewaxing containing mesoporous molecular sieve and the hydro-upgrading pour point depression compound containing large pore molecular sieve to load carries out grating, Appropriate application is carried out in temperature rise in the temperature drop of hydrodewaxing process and hydro-upgrading isomerization-visbreaking process, realize bed isothermal operation, reduce the hot(test)-spot temperature of device, extend running period, save process cost, reduce device comprehensive energy consumption, reduce condensation point of diesel oil and the quality that improve diesel oil to greatest extent simultaneously.
Provided by the inventionly a kind ofly process the method that high nitrogen diesel production cleans low-coagulation diesel oil, comprise following content:
After diesel raw material mixes with hydrogen, successively by the hydroconversion reaction zone of at least two series connection, according to Flow of Goods and Materials direction, each described hydroconversion reaction zone comprises by simple Hydrobon catalyst bed and the composite catalyst bed that loaded by Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyst mix successively, last hydroconversion reaction zone gained reaction effluent is after separation and fractionation, obtain clean low freezing point diesel fuel product, and a small amount of light naphthar and liquefied gas product.
According to method of the present invention, wherein in each described hydroconversion reaction zone, first diesel raw material and hydrogen pass through Hydrobon catalyst bed, and it is saturated to carry out hydrogenating desulfurization, hydrodenitrification, olefin saturated and polycyclic aromatic hydrocarbons; And then by the composite catalyst bed that Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyst mix are loaded, carry out the saturated open loop of polycyclic aromatic hydrocarbons, cracking and normal paraffin isomerization reaction.
According to method of the present invention, described diesel raw material is conventional pour point depression raw material and high freezing point diesel fuel, and condensation point is generally all more than 0 DEG C, and preferred condensation point is more than 5 DEG C.The nitrogen content of described diesel raw material, at 2000 below μ g/g, is generally 200 ~ 1500 μ g/g, most preferably is 300 ~ 1200 μ g/g.The diesel oil distillate etc. of the various straight run that described diesel raw material can obtain for processing naphthenic base crude, intermediate base crude oil or paraffinic crude or secondary processing, preferably processes the said components that paraffinic crude obtains.Doing of diesel raw material is generally 350 ~ 440 DEG C, preferably 370 ~ 400 DEG C.
Described Hydrobon catalyst can be diesel oil hydrofining catalyst, also can be hydrocracking pre-refining catalyzer, the highly effective hydrogenation catalyst for refining of the high metal content that body phase legal system also can be used standby.Described Hydrobon catalyst mainly comprises hydrogenation active metals and modified aluminium oxide supports component etc.General Hydrobon catalyst is made up of hydrogenation active metals component and various modified aluminium oxide supports etc. such as Wo, Mo, Co, Ni, Fe, and with the weight of catalyzer for benchmark, the content of hydrogenation component is 15% ~ 80%.Being exclusively used in Hydrobon catalyst of the present invention is comprise WO by weight
3(or MoO
3) 12 ~ 60wt%, NiO (or CoO) 3 ~ 20wt%, aluminum oxide 5 ~ 80wt%.Wherein aluminum oxide is generally the gamma-alumina of additive modification, and adjuvant component can be one in F, Si, P, B, Zr and Zn and/or several.Conventional hydro catalyst for refining can select existing various commercial catalysts, FHUDS diesel oil hydrofining catalyst series, FF hydrocracking pre-refining catalyst series and FTX body phase method highly effective hydrogenation that such as FRIPP develops refine catalyst series, and the UF series hydrofining catalyzer of the UOP of offshore company, the hydrocracking such as diesel oil hydrofining catalyst or KF848, KF860 and KF868 pre-refining catalyzer such as Albemarle Corporation KF757.Also can be prepare the close Hydrobon catalyst of selectivity by the general knowledge of this area as required.
The operational condition of described Hydrobon catalyst bed is: reaction pressure 6.0 ~ 20.0MPa, hydrogen to oil volume ratio 100:1 ~ 800:1, and volume space velocity is 0.1 ~ 10.0h
-1, temperature of reaction 260 DEG C ~ 425 DEG C; Preferred operations condition is: reaction pressure 6.0 ~ 15.0MPa, hydrogen to oil volume ratio 200:1 ~ 600:1, volume space velocity 0.3 ~ 8.0h
-1, temperature of reaction 300 DEG C ~ 390 DEG C.
Described Hydrodewaxing catalyst adopts the catalyzer containing shape slective cracking molecular sieve, comprises the metal component of carrier and institute's load.Described catalyzer generally with shape slective cracking molecular sieve and tackiness agent for carrier, with group VIB and/or group VIII metal for hydrogenation active metals component.Described shape slective cracking molecular sieve is hydrogen type molecular sieve, described molecular sieve can be selected from Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve one or more, preferred ZSM-5 molecular sieve; The silica alumina ratio of described shape slective cracking molecular sieve is generally 10 ~ 150, is preferably 20 ~ 120.
Described group VIB metal is Mo and/or W, and described group VIII metal is Co and/or Ni.With the weight of catalyzer for benchmark, hydrogenation active metals component is with the content of oxide basis for 1% ~ 16%, and the content of shape slective cracking molecular sieve is 50% ~ 85%, and the content of tackiness agent is 10% ~ 40%.The bulk density of Hydrodewaxing catalyst is generally 0.65 ~ 0.75gcm
-3, its normal use temperature scope is 380 DEG C ~ 400 DEG C.Described Hydrodewaxing catalyst can select existing various commercial catalysts, the Hydrodewaxing catalysts such as FDW-1, FDW-3 that such as Fushun Petrochemical Research Institute (FRIPP) develops; Also can be prepared by the general knowledge of this area as required, such as, can prepare satisfactory Hydrodewaxing catalyst with reference to content disclosed in CN1952074A, CN1352231A, CN101143333A, CN102451748A.
Hydro-upgrading isomerization-visbreaking catalyzer described in the present invention is the hydroisomerization catalyst containing the strong twelve-ring large pore molecular sieve of isomery performance, referring to a kind of hydrogenation catalyst being exclusively used in diesel modifying isomerization-visbreaking, is the conventional hydro conversion catalyst in this area.Described hydro-upgrading isomerization-visbreaking catalyzer is a kind of dual function hydrogenation catalyst, with aluminum oxide, amorphous aluminum silicide and modified molecular screen for carrier, containing at least one VI B race's metal and at least one VIII race metal, it is characterized in that support of the catalyst consists of aluminum oxide 10w% ~ 80w%, amorphous aluminum silicide 0w% ~ 40w%, molecular sieve 5w% ~ 40w%, wherein modified molecular screen can be the modified product of beta molecule, P type molecular sieve, X-type molecular sieve and A type molecular sieve, wherein preferred modified beta molecular sieve, the SiO of modified beta molecular sieve
2/ Al
2o
3weight ratio is 50 ~ 90, and average grain size is 0.1 ~ 0.5 micron, and infrared acidity is that the secondary pore pore volume of 0.1 ~ 0.4mmol/g, 2 ~ 10nm accounts for 30% ~ 60% of total pore volume; Pore volume is 0.20 ~ 0.52mL/g, and specific surface area is 550 ~ 900m
2/ g.
The macroporous aluminium oxide of to be a kind of crystalline phase the be pseudo-boehmite of the aluminum oxide contained by described hydro-upgrading isomerization-visbreaking catalyzer, its pore volume is generally 0.30 ~ 1.5mL/g, specific surface 150 ~ 600m
2/ g, content is 10w% ~ 80w%.Macroporous aluminium oxide content (taking carrier as benchmark) is generally 5w% ~ 80w%, preferred 10w% ~ 40w%; The pore volume of described macroporous aluminium oxide is 1.0 ~ 1.5mL/g, is preferably >1.2 ~ 1.5mL/g(and is greater than 1.2 to 1.5mL/g); Specific surface area is 200 ~ 550m
2/ g, is preferably 300 ~ 500m
2/ g.The sieve and silica-sesquioxide weight ratio 1:2 ~ 2:1 of contained amorphous silicon aluminium in carrier, pore volume 0.40 ~ 1.0mL/g, specific surface 150 ~ 500m
2/ g, content is generally 0w% ~ 40w%, is preferably 10w% ~ 30w%.
In method of the present invention, selected hydro-upgrading isomerization-visbreaking catalyzer, when its catalyst/support is shaping, selects suitable sour peptizing techniques especially, join in moulding process by mineral acid and organic acid mixing acid, to strengthen the character such as specific surface area, intensity of catalyzer; Simplify the Production Flow Chart of catalyzer in addition, reduce production cost, also can ensure the stability of macroporous aluminium oxide simultaneously, make the pore volume that prepared catalyst/support keeps higher.This technology can be that gained is prepared in the modification when shaping of current industry-wide catalyzer.Adopt catalyzer prepared by this technology, also on catalyzer face shaping, be also optimized process simultaneously, be preferably prepared into tooth ball shape catalyst, be convenient to transport, filling and Homogeneous phase mixing.
Recited above through modified hydro-upgrading isomerization-visbreaking catalyzer, due to the change of carrying alumina volume property, when reaching the same reaction degree of depth, its activity will be weaker than about 10 DEG C conventional of hydro-upgrading isomerization-visbreaking catalyzer, and the normal use temperature scope of catalyzer is elevated to 380 DEG C ~ 400 DEG C.This modified catalyst is compared with above-mentioned Hydrodewaxing catalyst, and in mixing process, the difference of two kinds of catalyst bulk densitys is generally less than 0.05gcm
-3.
Described hydrogenation metal can be the combination of at least one VI B family metal oxide or sulfide and at least one VIII family metal oxide or sulfide, VI B race metal can be Mo or W, preferably select W, content 10w% ~ 30w%, VIII race's metal can be Ni or Co, preferably select Ni, content 2w% ~ 15w%.Conventional hydro upgrading isomerization-visbreaking catalyzer can select existing various commercial catalysts, such as FRIPP develop 3901, catalyzer or the modified catalyst such as FC-16, FC-14, FC-20.Also specific hydro-upgrading isomerization-visbreaking catalyzer can be prepared by the general knowledge of this area as required, such as, satisfactory hydro-upgrading isomery (conversion) catalyzer can be prepared with reference to content disclosed in CN1184843A, CN1178238A.
According to method of the present invention, wherein in each hydroconversion reaction zone, the admission space ratio of the described pour point depression modifying catalyst composite bed loaded with hydro-upgrading isomerization-visbreaking catalyzer compound by Hydrobon catalyst bed and Hydrodewaxing catalyst is 1:10 ~ 10:1, preferred 1:5 ~ 5:1.
The operational condition of the composite catalyst bed that described hydrodewaxing and hydro-upgrading isomerization-visbreaking catalyzer form is: reaction pressure 6.0 ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 1500:1, volume space velocity is 0.1 ~ 10.0h
-1, temperature of reaction 270 DEG C ~ 460 DEG C; Preferred operations condition is reaction pressure 6.0 ~ 15.0MPa, hydrogen to oil volume ratio 300:1 ~ 1000:1, volume space velocity 0.3 ~ 8.0h
-1, temperature of reaction 315 DEG C ~ 427 DEG C.
In described hydrodewaxing and hydro-upgrading isomerization-visbreaking catalyzer composite bed, Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyzer compound/mixed packing, admission space is than being 1:10 ~ 10:1, preferred 1:5 ~ 5:1.
For described at least two hydroconversion reaction zones, wherein said simple Hydrobon catalyst bed and hydro-upgrading pour point depression catalyzer composite bed, can be separately positioned in the two or more bed of a reactor; Or can be separately positioned in the hydrogenator of two or more series connection.
Compared with prior art, the inventive method has the following advantages:
1, in the inventive method, in each hydroconversion reaction zone, first stock oil be the reactions such as hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation, alkene and aromatic saturation by the principal reaction of hydrofining bed, and heat effect shows as stronger thermopositive reaction, and technological process bed produces temperature rise; Stock oil is after refining, again through the bed of Homogeneous phase mixing hydrodewaxing and hydro-upgrading isomerization-visbreaking catalyzer, due to Hydrodewaxing catalyst preferred ten-ring modified mesoporous molecular sieve, mainly select type cracking and isomerization reaction, to the paraffinic hydrocarbons of high condensation point, there is good selective splitting performance, significantly can reduce the zero pour of diesel oil, and the heat effect of reaction shows as stronger thermo-negative reaction, technological process produces bed temperature drop; The modified macroporous molecular sieve of the preferred twelve-ring of hydro-upgrading isomerization-visbreaking catalyzer, not only to paraffinic hydrocarbons, there is good isomery performance, also to polycyclic aromatic hydrocarbons, there is the effect that good hydrotreated lube base oil and open loop transform, not only can reduce diesel product condensation point further, can also significantly promote diesel product quality, principal reaction is the reactions such as aromatic saturation, cyclic hydrocarbon open loop, paraffinic hydrocarbons isomery and hydrocarbon cracking, and heat effect shows as stronger thermopositive reaction, and technological process bed produces temperature rise; And these two kinds of catalyzer are carried out grating mixed packing, its respective heat release and thermo-negative reaction feature can be made full use of, the comprehensive utilization of the heat of realization response process, obvious temperature rise and temperature drop effect can not be produced, and affect depression effeCt, thus make the reaction of composite catalyst bed can realize the reaction process of isothermal, obtain desirable reaction effect, both can ensure the yield of diesel oil, also achieve better depression effeCt, be more conducive to the long-term operation of device; From the angle of catalyzed reaction, the strong isomate process of hydrodewaxing reaction and hydro-upgrading isomerization-visbreaking react selects hydrocarbon molecule dissimilar in raw material to react respectively, reduce the zero pour of diesel product to greatest extent, taken into account quality product lifting simultaneously, obtain best reaction effect.First deviate to affect the organic impurity of the performance of molecular sieve activity through simple Hydrobon catalyst bed, simultaneously by the temperature needed for the temperature increase of reaction mass to isomerization reaction, then enter hydrodewaxing and hydro-upgrading isomerization-visbreaking mixed catalyst bed, be conducive to saving energy and reduce the cost.
2, at process aspect, in each hydroconversion reaction zone, substantially identical effect is all shown.Thus at least two hydroconversion reaction zones of series connection, described hydrogenation reaction shows as comprehensive cumulative effect of optimization.Compared with prior art, the present invention is on the basis of not changing device flow process, load by means of only the grading composition of catalyzer and Homogeneous phase mixing, from local by the high temperature dot of device and the effective Appropriate application of low warm spot, reduce the hot(test)-spot temperature of device, reasonably decrease the bulk temperature gradient of device, give full play of the catalytic performance of catalyzer the best, extend the work-ing life of catalyzer.In addition this combination is compared with the hydrodewaxing combination process of routine, heat due to reaction process obtains and more reasonably utilizes, can beat less between two reaction zones or not liquid hydrogen injection, therefore consumption and the process furnace load of cold hydrogen is also reduced, save process cost, reduce device comprehensive energy consumption.
3, in the present invention special select suitable catalyzer and technique with the use of, there is good adaptability and advantage.During by hydro-upgrading isomerization-visbreaking catalyzer and Hydrodewaxing catalyst mixed packing, can reach more excellent and load in mixture effect, avoid because density variation is excessive, out-of-shape and cause catalyst mix filling time, the problem of size distribution inequality.The reactive behavior reducing upgrading and pour point reducing heterogeneous catalyst that modification is simultaneously also suitable, better can mate with Hydrodewaxing catalyst like this, make the two quite active, to play the effect that it is maximum separately in same temperature ranges stated, while reduction product condensation point, can also improve the quality of products.
Accompanying drawing explanation
Fig. 1 is the grading loading schematic diagram of a kind of embodiment of the inventive method.
Embodiment
Below in conjunction with accompanying drawing, method of the present invention is described in detail.
As shown in Figure 1, it is as follows that the high nitrogen diesel production of one process of the present invention cleans low-coagulation diesel oil production method flow process: stock oil 1 enters reactor 3-1 with hydrogen 2 after reactor inlet mixes, Hydrobon catalyst bed 4 from top to bottom successively by connecting step by step, the composite catalyst bed 5 of hydrodewaxing and hydro-upgrading isomerization-visbreaking mixed packing, then reactor 3-2 is entered, material is successively by Hydrobon catalyst bed 6, and the composite catalyst bed 7 of hydrodewaxing and hydro-upgrading isomerization-visbreaking mixed packing, obtain reaction effluent 8 and after interchanger 9, enter into high-pressure separator 10 from reactor bottom discharge, high-pressure separator 10 top obtains gas 11 by circulating hydrogen compressor 12, hydrogen or cold hydrogen use as a supplement to obtain recycle hydrogen 14 after mixing with new hydrogen 13, the liquid phase that high-pressure separator 10 middle and lower part obtains enters light pressure separator 17, and light pressure separator 17 top is discharged low point of gas 18 and gone subsequent disposal, and light pressure separator 17 middle and lower part obtains liquid phase 20 and enters subsequent fractionation system, the sour water 15 of discharging bottom high-pressure separator 10 mixes rear disacidify water treatment device with the sour water 19 of discharging bottom light pressure separator 17 and carries out following process.
Next by specific embodiment, method of the present invention is further described.The character of used catalyst is listed in table 1.
The main physico-chemical property of table 1 catalyzer and active contrast
| Catalyzer | FC-14 | FC-14G | FDW-3 |
| Catalyst type | Hydro-upgrading | Hydro-upgrading | Hydrodewaxing |
| Wherein macroporous aluminium oxide, % | 10 | 35 | — |
| Pore volume, cm 3/g | 0.7 | 1.3 | — |
| Specific surface area, m 2/g | 360 | 345 | — |
| Catalyst physical properties | |||
| Shape | Tooth ball | Tooth ball | Tooth ball |
| Diameter, mm | 2.5 | 2.5 | 2.5 |
| Physical strength, N/cm | ≮150 | ≮130 | ≮100 |
| Active ingredient | W-Ni | W-Ni | Ni |
| Metal content, % | 29 | 23 | 2 |
| Nature packing density, t/m 3 | 0.76～0.86 | 0.65～0.75 | 0.65～0.75 |
| Mean pore size/nm | 5.34 | 7.65 | — |
| Temperature when reaching the same reaction degree of depth/DEG C | 375 | 384 | — |
| Normal use temperature (just-latter stage)/DEG C | 370～390 | 380～400 | 380～400 |
Comparative example 1
Comparative example 1 is the device adopting hydrofining, hydrodewaxing and hydro-upgrading isomerization-visbreaking one-stage serial flow process to produce clean low freezing point diesel fuel.Comparative example 1 comprises two reaction zones, each reaction zone includes the pour point depression beds loaded by Hydrobon catalyst bed and hydro-upgrading isomerization-visbreaking catalyzer and Hydrodewaxing catalyst layering, the catalyst loading ratio of two reaction zones is identical, the catalyzer of single reaction zone consists of, and the volume ratio of hydro-upgrading isomerization-visbreaking catalyzer and Hydrodewaxing catalyst is 1:2.Comparative example 1 produces the low-coagulation diesel oil of the identical trade mark with embodiment 1.The catalyzer used, stock oil and diesel product condensation point are all identical with embodiment 1.Operation result lists in table 3.
Comparative example 2
Comparative example 2 is the device adopting hydrofining, hydrodewaxing and hydro-upgrading isomerization-visbreaking catalyzer one-stage serial flow process to produce low freezing point diesel fuel.Control substantially identical diesel yield with embodiment 1, produce the low-coagulation diesel oil of the different trade mark.The catalyzer that comparative example uses, stock oil and diesel product yield are all identical with embodiment 1, and catalyst loading is with comparative example 1.Operation result lists in table 3.
Embodiment 1
Adopt the technical process shown in Fig. 1, utilize grating to connect and load in mixture flow process and produce low freezing point diesel fuel.Embodiment 1 comprises the hydroconversion reaction zone of two series connection, and in the pour point depression catalyzer composite bed of each reaction zone, Hydrodewaxing catalyst is 1:2 with the mixed volume ratio of hydro-upgrading isomerization-visbreaking catalyzer.The Hydrobon catalyst agent used in embodiment 1 is FF-36 catalyzer, hydro-upgrading isomerization-visbreaking catalyzer is FC-14 catalyzer, Hydrodewaxing catalyst is FDW-3 catalyzer, and described catalyzer is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operational condition and test-results list in table 3.
Embodiment 2
Adopt the technical process shown in Fig. 1, utilize grating to connect and load in mixture flow process and produce low freezing point diesel fuel.Embodiment 1 comprises the hydroconversion reaction zone of two series connection, in the compound pour point depression beds of each reaction zone, Hydrodewaxing catalyst is 1:2 with the mixed volume ratio of hydro-upgrading isomerization-visbreaking catalyzer, and the total consumption of catalyzer is all identical with comparative example 2 with comparative example 1.The hydro-upgrading isomerization-visbreaking catalyzer used in embodiment 2 is FC-14G catalyzer, and Hydrodewaxing catalyst is FDW-3 catalyzer, and described catalyzer is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operational condition and test-results list in table 3.
Table 2 stock oil property list.
| Project | Stock oil |
| Source | Normal two, three lines+catalytic diesel oil |
| Ratio | 1:1 |
| Density (20 DEG C)/gcm -3 | 0.8912 |
| Boiling range scope/DEG C | 157～392 |
| Nitrogen/μ gg -1 | 859 |
| Sulphur/μ gg -1 | 2116 |
| Condensation point/DEG C | 5 |
| Cetane index | 34 |
Table 3 process conditions and result.
| Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | |
| Catalyzer forms | FF-36/(FDW-3/FC-14) | FF-36/(FDW-3/FC-14) | FF-36/(FDW-3+FC-14) | FF-36/(FDW-3/FC-14G) |
| Reaction pressure/MPa | 9.0 | 9.0 | 9.0 | 9.0 |
| Average reaction temperature/DEG C | 370/375*/375/380* | 360/370*/370/375* | 370/375*/375/3*80 | 370/376*/375/381* |
| LHSV/h -1 | 5.0**/6.0/5.0**/6.0 | 5.0**/6.0/5.0**/6.0 | 5.0**/6.0/5.0**/6.0 | 5.0**/6.0/5.0**/6.0 |
| Entrance hydrogen to oil volume ratio | 600:1 | 600:1 | 600:1 | 600:1 |
| Diesel product condensation point/DEG C | -36 | -22 | -41 | -42 |
| Diesel yield, wt% | 73.5 | 80.2 | 79.8 | 79.6 |
| Bed top temperature/DEG C | 391 | 389 | 389 | 385 |
| Cold hydrogen consumption/benchmark | 1.1 | 0.9 | 1.0 | 0.97 |
| Diesel oil density/gcm -3 | 0.8367 | 0.8414 | 0.8346 | 0.8340 |
| Diesel fuel cetane index | 48 | 46 | 51 | 52 |
| Diesel oil sulphur content/μ gg -1 | 21 | 24 | 10 | 10 |
* average reaction temperature is the weighted mean temperature of compound pour point depression beds;
* volume space velocity is the volume space velocity of compound pour point depression beds.
As can be seen from above embodiment, the maximum feature of the inventive method is, producing low solidifying product for processing diesel raw material, product cetane value can be improved, the condensation point of raw material can be reduced simultaneously when ensureing certain diesel yield to greatest extent; In addition also to have hot(test)-spot temperature low for the inventive method, and running period is long, the feature that cold hydrogen consumption is low; For enterprise, while completing quality products production task, human and material resources and energy consumption have very large advantage.
Claims (14)
1. one kind processes the method that high nitrogen diesel production cleans low-coagulation diesel oil, comprise following content: after diesel raw material mixes with hydrogen, successively by the hydroconversion reaction zone of at least two series connection, by Flow of Goods and Materials direction, the composite catalyst bed that each described hydroconversion reaction zone comprises simple Hydrobon catalyst bed successively and loaded by Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyst mix; Last hydroconversion reaction zone gained reaction effluent is through being separated and after fractionation, obtaining low freezing point diesel fuel product.
2. in accordance with the method for claim 1, it is characterized in that, the condensation point of described diesel raw material more than 0 DEG C, preferably more than 5 DEG C; Nitrogen content, at 2000 below μ g/g, is preferably 20 ~ 1500 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that, doing of described diesel raw material is 350 ~ 440 DEG C, preferably 370 ~ 400 DEG C.
4. in accordance with the method for claim 1, it is characterized in that, in each described hydroconversion reaction zone, Hydrobon catalyst bed is 1:10 ~ 10:1 with the admission space ratio of the composite catalyst bed loaded by Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyst mix.
5. in accordance with the method for claim 1, it is characterized in that, in described composite catalyst bed, Hydrodewaxing catalyst is 1:10 ~ 10:1 with the admission space ratio of hydroisomerizing upgrading and pour point reducing catalyzer.
6. in accordance with the method for claim 1, it is characterized in that, the operational condition of described Hydrobon catalyst bed is: reaction pressure 6.0 ~ 20.0MPa, hydrogen to oil volume ratio 100:1 ~ 800:1, and volume space velocity is 0.1 ~ 10.0h
-1, temperature of reaction 260 DEG C ~ 425 DEG C; The operational condition of described composite catalyst bed is: reaction pressure 6.0 ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 1500:1, and volume space velocity is 0.1 ~ 10.0h
-1, temperature of reaction 270 DEG C ~ 460 DEG C.
7. in accordance with the method for claim 1, it is characterized in that, described Hydrodewaxing catalyst with shape slective cracking molecular sieve and tackiness agent for carrier, with group VIB and/or group VIII metal for hydrogenation active metals component; With the weight of catalyzer for benchmark, hydrogenation active metals is with the content of oxide basis for 1% ~ 16%, and the content of shape slective cracking molecular sieve is 50% ~ 85%, and the content of tackiness agent is 10% ~ 40%.
8. in accordance with the method for claim 1, it is characterized in that, described hydro-upgrading isomerization-visbreaking is urged with aluminum oxide, amorphous aluminum silicide and modified molecular screen as carrier, containing at least one VI B race's metal and at least one VIII race metal, support of the catalyst consists of aluminum oxide 10w% ~ 80w%, amorphous aluminum silicide 0w% ~ 40w%, molecular sieve 5w% ~ 40w%.
9. in accordance with the method for claim 8, it is characterized in that, described aluminum oxide is macroporous aluminium oxide, take carrier as benchmark, and the pore volume of macroporous aluminium oxide is 1.0 ~ 1.5mL/g, is preferably >1.2 ~ 1.5mL/g.
10. according to the method described in claim 8 or 9, it is characterized in that, the sieve and silica-sesquioxide weight ratio 1:2 ~ 2:1 of described amorphous silicon aluminium, pore volume 0.40 ~ 1.0mL/g, specific surface 150 ~ 500m
2/ g, content is 10w% ~ 30w%.
11., according to the method described in claim 8 or 9, is characterized in that, described molecular sieve is the SiO of modified beta molecular sieve, modified beta molecular sieve
2/ Al
2o
3weight ratio is 50 ~ 90, and average grain size is 0.1 ~ 0.5 micron, and infrared acidity is that the secondary pore pore volume of 0.1 ~ 0.4mmol/g, 2 ~ 10nm accounts for 30% ~ 60% of total pore volume; Pore volume is 0.20 ~ 0.52mL/g, and specific surface area is 550 ~ 900m
2/ g.
12. in accordance with the method for claim 1, it is characterized in that, the bulk density of described Hydrodewaxing catalyst is 0.65 ~ 0.75gcm
-3.
13. in accordance with the method for claim 12, it is characterized in that, the described bulk density of hydro-upgrading isomerization-visbreaking catalyzer and the difference of the bulk density of Hydrodewaxing catalyst are less than 0.05gcm
-3.
14. in accordance with the method for claim 9, it is characterized in that, the specific surface area of described macroporous aluminium oxide is 200 ~ 550m
2/ g.
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| CN109988598A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible diesel oil hydrogenation modification technique |
| CN111097513A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for restoring activity of low-activity pour point depressing catalyst |
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| CN1221639C (en) * | 2002-12-19 | 2005-10-05 | 中国石油化工股份有限公司 | Method for producing low-freezing diesel oil from fractional oil |
| CN1331989C (en) * | 2004-07-06 | 2007-08-15 | 中国石油化工股份有限公司 | Method of hydro up grading isomerizing pour point depression to produce diesel oil |
| CN102051232B (en) * | 2009-10-27 | 2013-08-28 | 中国石油化工股份有限公司 | Diesel oil hydrogenation pour point depressing method |
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| CN109988598A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible diesel oil hydrogenation modification technique |
| CN111097513A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for restoring activity of low-activity pour point depressing catalyst |
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