CN103059977A - Method for producing high-quality low-freezing diesel oil - Google Patents
Method for producing high-quality low-freezing diesel oil Download PDFInfo
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Abstract
The invention relates to a method for producing a high-quality low-freezing diesel oil, which is characterized in that a diesel oil raw material is contacted with a Hydrobon catalyst in a first hydrogenation reaction zone for reaction, an effluent is directly introduced in a second reaction zone without separating, and is contacted with a hydrogenation modified pour point depression catalyst for a pour point depression reaction, an effluent in the second reaction zone is introduced in the separating system and the fractionation system, the heavy diesel fuel fraction at the bottom of a fractionate tower is circularly introduced in an inlet of the second reaction zone. According to the invention, the hydrogenation modified pour point depression catalyst is employed for obviously reducing the condensation point of the diesel oil fraction, the heavy diesel fuel component with high condensation point is circularly introduced in the second reaction zone for remodifying the pour point depression reaction, and the target product yield can be increased.
Description
Technical field
The present invention relates to a kind of hydro carbons in the situation that hydrogen exists, make with extra care the process with upgrading.More particularly, be a kind of method of producing high-grade low-freezing diesel oil.
Background technology
Along with the sustained and rapid development of Chinese national economy and the day by day raising of living standards of the people, the demand of vehicle fuel is constantly increased, especially market, the north in winter is very fast to the demand growth of low-coagulation diesel oil.On the other hand, along with the continuous quickening of diesel quality upgrading paces, the diesel product specification of quality is more and more stricter, and low-coagulation diesel oil also has strict demand to sulphur content, polycyclic aromatic hydrocarbon content, cetane value etc. except condensation point, cold filter clogging temperature etc. are proposed the special requirement.
The Chinese Crude Oils of northern China belongs to paraffinic base or content of wax intermediate base mostly, and the diesel product condensation point of its production is higher.In actual production, can produce a small amount of low-coagulation diesel oil by adding pour point depressant, but exist the pour point depression amplitude limited, the high in cost of production shortcoming.
In order to improve the low temperature flowability of oil product, usually adopt hydrodewaxing technology or isomerization-visbreaking technology.The hydrodewaxing technology adopts the molecular sieve with shape slective cracking function as the pour point depression active ingredient, and a small amount of metal of load, can be micromolecular product with the contour condensation point component of the long-chain n-praaffin in diesel oil distillate shape slective cracking, thereby reach the purpose of pour point depression.Therefore, the product of hydrodewaxing is except low-coagulation diesel oil, and the light constituents such as while by-product gasoline and liquefied gas are so the diesel yield of hydrodewaxing technology is lower; On the other hand, because the generation of cracking reaction, the utilising efficiency of hydrogen reduces, the process economy reduction.The isomerization-visbreaking technology generally adopts the noble metal catalyst of loading type, and the two-stage process flow process by special pore passage structure and the acidity of molecular sieve, tautomerizes to branched paraffin with long chain alkane and reaches the purpose that reduces condensation point.But this technical matters flow process is complicated, and the catalyzer of application is expensive, invest high, and the easy poisoning and deactivation of noble metal catalyst.
CN101942335A discloses a kind of gasoline and Combined hydrogenation process for diesel oil.Gasoline stocks mixes with hydrogen and carries out hydrofining reaction, mainly carry out the reaction of deolefination and partial desulfurization, reaction effluent mixes with diesel raw material and carries out hydrogenation aromatics-removing and react, and product further carries out deep desulfuration and reacts, the hydrogenating desulfurization product is after gas-liquid separation, and liquid phase is carried out isomerization-visbreaking.Three refining reaction districts of this technique adopt three kinds of different catalyst for refining.
CN101724459A discloses a kind of method of hydrotreating that reduces condensation point of diesel oil, diesel raw material and hydrogen are blended in the first hydroconversion reaction zone and carry out hydrogenation of total effluent, its reaction effluent carries out flash distillation in high pressure hot separator, component lighter in the diesel oil is flashed off from high pressure hot separator, the liquid phase stream that high pressure hot separator obtains is that the diesel oil restructuring divides, itself and hydrogen are mixed into the second hydroconversion reaction zone and rear refining reaction district and carry out the hydrodewaxing reaction, the gaseous stream of the high pressure hot separator of gained with separate and fractionation after the reaction effluent of the second hydroconversion reaction zone mixes.This technique belongs to hydrodewaxing technique, and the freezing point reduction amplitude is less, and the product diesel-fuel cetane number is lower.
CN1718683A discloses the method that a kind of hydro-upgrading isomerization-visbreaking is produced diesel oil.The method adopts single hop or single hop series process flow, first by the Hydrobon catalyst bed, then by containing the catalyst for hydro-upgrading bed of beta-molecular sieve, obtains diesel product after product separation and the fractionation after distillate and hydrogen mix.
CN100340642C discloses a kind of method of being produced high-grade low-freezing diesel oil by distillate, comprises hydrofining reaction district and hydrodewaxing reaction zone, and wherein hydrodewaxing reaction zone top is provided with flash zone, and the bottom is provided with the hydrodewaxing section.Stock oil and hydrogen are mixed into the hydrofining reaction district, contact with Hydrobon catalyst and to carry out hydrogenation reaction, products therefrom enters flash zone, the gained liquid phase enters the hydrodewaxing section after the flash distillation, in the presence of Hydrodewaxing catalyst, select the shape scission reaction with reverse contact of hot hydrogen, the gas-phase product of gained goes separation system to obtain the low-coagulation diesel oil product of high-quality after the product of gained and the flash distillation.
Summary of the invention
The objective of the invention is to provide a kind of method of producing low-coagulation diesel oil.
Method provided by the invention comprises:
(1) diesel raw material contacts the hydrogenation saturated reaction that carries out hydrogenating desulfurization, hydrodenitrification reaction and alkene and aromatic hydrocarbons with after hydrogen mixes with Hydrobon catalyst at the first hydroconversion reaction zone,
The reaction effluent of (2) first hydroconversion reaction zones directly enters second reaction zone without separation and contacts with hydro-upgrading pour point depression catalyzer, carries out the pour point depression reaction,
(3) the second reaction zone effluent enters separation system and fractionating system, and the heavy gas oil cut circulation of separation column bottom enters the second reaction zone entrance.
The boiling range of described heavy gas oil cut is 280～390 ℃, preferred 300～380 ℃.
Described hydro-upgrading pour point depression catalyzer contains porous support and loads on group vib metal and group VIII metal on this porous support, in oxide compound, take the total amount of this catalyzer as benchmark, the content of described group vib metal is 10～40 % by weight, the content of described group VIII metal is 2～10 % by weight, and the content of described porous support is 50～88 % by weight.
Diesel oil flowing property at low temperatures, can not only be related to fuel supply system for diesel engine system at low temperatures normal fuel injection, and with operations such as at low temperatures storage of diesel oil, transportations substantial connection be arranged normally.The low-temperature fluidity of diesel oil is relevant with its chemical constitution, and wherein the content of normal paraffin is higher, and then low temperature flowability is poorer.The index of China's evaluation research of cold flow properties of diesel fuel is condensation point and cold filter clogging temperature.Not only condensation point, cold filter clogging temperature etc. are proposed outside the special requirement in China's low-coagulation diesel oil standard, and sulphur, nitrogen, aromaticity content, cetane value etc. are also had strict demand.In addition, crude oil has entered Waste Era of Oil, and the crude oil import amount in China every year surpasses 50%, and oil refining enterprise wishes to improve the purpose product yield, reduces the running costs such as hydrogen consumption.
What affect condensation point of diesel oil and cold filter clogging temperature mainly is long-chain n-praaffin.If long-chain n-praaffin is tautomerized to branched paraffin, then not only reduced condensation point of diesel oil but also improved the low-coagulation diesel oil product yield.In addition, adopt the catalyzer of high hydrogenation activity, can not only reduce the foreign matter contents such as sulphur, nitrogen, satisfy the needs of diesel quality upgrading, and can also reduce the particularly content of polycyclic aromatic hydrocarbons of aromatic hydrocarbons, improve cetane value.
The component of high condensation point is generally macromolecular long-chain n-praaffin in the diesel oil distillate, and molecular weight is larger, and boiling range is heavier, and condensation point is also higher, so high condensation point component mainly concentrates in the high boiling fraction in the diesel oil distillate.A kind of true boiling point boiling range of Daqing crude oil is respectively 180～330 ℃, 180～350 ℃, 180～370 ℃ and 180～390 ℃, its condensation point be respectively-12 ℃ ,-5 ℃ ,+3 ℃ and+8 ℃, as seen do rising, namely high boiling fraction increases, condensation point raises.In addition, a kind of catalytic cracking diesel oil, initial boiling point are 151 ℃, and 70% to distillate be 291 ℃ a little, and doing is 361 ℃, and condensation point is-1 ℃, with its carry out true boiling point be cut into＜290 ℃ and＞290 ℃, condensation point is respectively-45 and 14 ℃.Therefore, the key of reduction condensation point of diesel oil is to reduce the condensation point of the high boiling fraction section in the diesel oil distillate.
Diesel raw material of the present invention can be diesel oil distillate, also can be the mixing oil of diesel oil distillate and gasoline fraction.Wherein diesel oil distillate can be one or more of straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil and other diesel oil distillates, and wherein the condensation point of diesel oil distillate is between 30～-35 ℃, and cold filter clogging temperature is between 20～-20 ℃.Gasoline fraction can be one or more of coker gasoline, catalytic gasoline and other gasoline fractions.
The first reaction zone and second reaction zone can be in reactors, also can be respectively in two different reactors.If the first reaction zone and second reaction zone are in same reactor, Fractionator Bottom heavy gas oil cut can be circulated to the first reaction zone entrance.The cut point of heavy gas oil cut can be according to the specification of quality control of low-coagulation diesel oil product.
In step (1), diesel oil or diesel oil mixing raw material carry out hydrogenation of total effluent at the first reaction zone, carry out the hydrogenation saturated reaction of hydrogenating desulfurization, hydrodenitrification, alkene and aromatic hydrocarbons.Hydrogenating desulfurization and hydrodenitrification reaction can reduce the foreign matter contents such as sulphur nitrogen in the raw material.The hydrogenation saturated reaction of alkene and aromatic hydrocarbons can improve product storage stability, improves the product diesel-fuel cetane number.
The reaction conditions of described the first reaction zone is: hydrogen dividing potential drop 3.0～15.0MPa, preferred 6.4～12.0MPa; 250～450 ℃ of temperature of reaction, preferred 300～420 ℃; Hydrogen to oil volume ratio 200～2000Nm
3/ m
3, preferred 500～1500Nm
3/ m
3Volume space velocity 0.5～10h during liquid
-1, preferred 0.8～3.0h
-1
In step (2), the reaction effluent of the first reaction zone directly enters second reaction zone, contacts with hydro-upgrading pour point depression catalyzer, and long chain alkane carries out the isocracking reaction at this reaction zone, significantly reduces the condensation point that the diesel oil restructuring divides.
The reaction conditions of described second reaction zone is: hydrogen dividing potential drop 3.0～15.0MPa, preferred 6.4～12.0MPa; 280～450 ℃ of temperature of reaction, preferred 300～420 ℃; Hydrogen to oil volume ratio 200～2000
Nm
3/ m
3, preferred 500～1500Nm
3/ m
3Volume space velocity 0.5～10h during liquid
-1, preferred 0.8～5.0h
-1
In step (3), the reaction effluent of second reaction zone enters separation system and fractionating system, isolates hydrogen sulfide, ammonia, dry gas, liquefied gas, petroleum naphtha, low-coagulation diesel oil and heavy gas oil cut; The some or all of second reaction zone entrance that is circulated to of described heavy gas oil cut carries out isomery and cracking reaction again, further reduces condensation point and cold filter clogging temperature.Take heavy gas oil cut integral body as benchmark, the weight fraction that enters second reaction zone is 30%～100%.
The admission space ratio of described Hydrobon catalyst I and hydro-upgrading pour point depression catalyzer is: 20: 80～80: 20.
In a preferred embodiment; for preventing that Hydrobon catalyst I is because of the coking of coking precursor and metal poisonings such as the alkene in the coking gasoline and diesel raw material, colloids; can account at the first reaction zone bed top loading the hydrogenation protecting agent of Hydrobon catalyst I volume total amount 5～30%; with protection Hydrobon catalyst I, avoid the quick coking of Primary Catalysts bed.Protective material is comprised of the alumina supporter with diplopore distribution of 1.0～5.0 heavy % nickel oxide, 5.5～10.0 heavy % molybdenum oxides and surplus.
In another preferred embodiment, in the second reaction zone of described step (3), also be filled with Hydrobon catalyst II in the downstream of hydro-upgrading pour point depression catalyzer; Take the volume sum of Hydrobon catalyst I and hydro-upgrading pour point depression catalyzer as benchmark, the loadings of Hydrobon catalyst II is 10%～50%.The second reaction zone effluent carries out the post-refining reaction through Hydrobon catalyst II, reduces alkene and mercaptan sulfur content in the second reaction zone effluent.
Described Hydrobon catalyst II is identical with Hydrobon catalyst I, and is perhaps different.
Hydrobon catalyst I can be the Hydrobon catalyst of loading type, also can be the Hydrobon catalyst of non-loading type.
Described load hydrogenation catalyst for refining is take composite alumina and composite oxygen SiClx as carrier, at least aly in the metal component is selected from VIII family, and at least a metal component that is selected from group vib.Its preferred Hydrobon catalyst consists of: in oxide compound and take the catalyzer total amount as benchmark, the content of nickel and/or cobalt is 1～10 heavy %, and molybdenum and tungsten sum are greater than 10～50 heavy %, and surplus is carrier.
Described non-supported hydrogenation catalyst for refining contains at least a VIII family metal component, at least two kinds of group vib metal components and organic additive, and the content of a kind of VIII family metal component, at least two kinds of group vib metal components and organic additive satisfies: mR:[VIII
x(VIB-1)
y(VIB-2)
z] O
2Wherein, represent a kind of group vib metal component VIB-2 with VIB-1 and represent another kind of group vib metal component; R represents at least a organic additive; M represents every mole of [VIII
x(VIB-1)
y(VIB-2)
z] O
2In the mole number of contained organic additive, the span of m is 0.1～2, take the total amount of VIII family metal component, VIB-1 metal component and VIB-2 metal component as benchmark; X, y, z represent respectively VIII family metal component, the VIB-1 metal component, and the molar fraction of VIB-2 metal component, x, y, the span of z satisfies (y+z): x=10: 1～1: 10.
Described group VIII metal component is cobalt, nickel and composition thereof, and described group vib metal component is molybdenum and tungsten; Preferred described x, y, the span of z satisfies (y+z): x=3: 1～1: 3, and y: z=3: 1～1: 3.
Described organic additive is selected from one or more in organic ammonium compound, sulfonate and the organophosphate.Described organic ammonium compound is selected from one or more in tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, TPAOH, hexamethylenetetramine, the Dodecyl trimethyl ammonium chloride; Sulfonate is selected from sodium laurylsulfonate and/or Sodium dodecylbenzene sulfonate.Also contain binding agent in the non-supported hydrogenation catalyst, take catalyzer as benchmark, the content of described binding agent is no more than 75 % by weight.Preferred described binding agent is aluminum oxide, silicon oxide, silica-alumina, and take catalyzer as benchmark, the content of described binding agent is no more than 30 % by weight.
Non-supported hydrogenation catalyst is compared with load hydrogenation catalyst, and its active centre density is much higher, has load hydrogenation catalyst incomparable superelevation hydrogenating desulfurization, denitrogenation and arene saturating activity.Therefore, under same reaction conditions, the aromaticity content of product property, sulphur content, nitrogen content are lower, and product property is more excellent; In the like products character situation, reaction conditions more relaxes.
The hydro-upgrading pour point depression catalyzer that described second reaction zone adopts is a kind of non-noble metal supported catalyzer that contains molecular sieve.Hydro-upgrading pour point depression catalyzer contains porous support and loads on group vib metal and group VIII metal on this porous support, in oxide compound, take the total amount of this catalyzer as benchmark, the content of described group vib metal is 10～40 % by weight, is preferably 15～30 % by weight; The content of described group VIII metal is 2～10 % by weight, is preferably 2.5～6.5 % by weight; The content of described porous support is 50～88 % by weight, is preferably 63.5～82.5 % by weight.
Described porous support contains heat-resistant inorganic oxide and Beta molecular sieve, the most probable aperture of this porous support is 1～30nm, the aperture concentration degree of this porous support is 22～48, and the most probable aperture of preferred described porous support is 2～20nm, and the aperture concentration degree is 25～48.The most probable aperture of further preferred this porous support is 5～10nm, and the aperture concentration degree is 27～40.Described most probable aperture is to adopt the BET method to measure, and described aperture concentration degree refers to adopt in the distribution curve of dV/dr with varying aperture of BET method mensuration, and the ratio of the height at peak and the halfwidth at this peak, dV/dr represent the long-pending differential to the aperture of specific pore volume.
Among the present invention, term " most probable aperture " refers to: when adopting the pore structure of BET method measure sample, the long-pending differential to the aperture of the specific pore volume of acquisition (that is, and dV/dr) in the distribution curve with the aperture, the corresponding aperture of the maximum value of dV/dr.Adopt the BET method to measure the pore structure of porous mass, known in those skilled in the art to obtain the long-pending differential to the aperture of specific pore volume with the method for the distribution curve in aperture, for example can be according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety first version, the volumes such as Yang Cuiding) among the RIPP 151-90 of record the method stipulated measure.
Among the present invention, term " aperture concentration degree " refers to: when adopting the pore structure of BET method measure sample, and in the long-pending distribution curve of differential with the aperture to the aperture of the specific pore volume of acquisition, the ratio of the halfwidth at peak height and this peak.The ratio of the halfwidth at peak height and this peak is larger, shows that the aperture intensity of porous support is higher.
According to the present invention, when having a plurality of peak in the distribution curve of described dV/dr with varying aperture, the ratio of the peak height at each peak and the halfwidth at this peak all should satisfy above-mentioned requirements.
Described hydro-upgrading pour point depression catalyzer, on the one hand because its porous support has larger aperture and pore volume, and has a higher aperture concentration degree, the normal paraffin of long-chain can tautomerize to branched paraffin and the unobstructed duct that diffuses out in the duct, thereby reduced the secondary cracking reaction, improved the low-coagulation diesel oil yield.Acid and the good coupling of hydrogenation activity has promoted open loop cracking and the isocracking of macromole long chain alkane of polycyclic aromatic hydrocarbons on the other hand, has reduced doing of diesel oil distillate, has promoted the boiling range reach of last running.Therefore, not only diesel yield is high for described hydro-upgrading pour point depression catalyzer, and the pour point depression amplitude is large, and pour point depression is effective.
Take the total amount of described heat-resistant inorganic oxide and Beta molecular sieve as benchmark, the content of described Beta molecular sieve is 0.1～66 % by weight, is preferably 0.2～50 % by weight, more preferably 0.5～30 % by weight, more preferably 0.75～20 % by weight; The content of described heat-resistant inorganic oxide can be 34～99.9 % by weight, is preferably 50～99.8 % by weight, more preferably 70～99.5 % by weight, more preferably 80～99.25 % by weight.
Among the present invention, term " heat-resistant inorganic oxide " refers under oxygen or oxygen-containing atmosphere, and decomposition temperature is not less than the inorganic oxygen-containing compound of 300 ℃ (for example: decomposition temperature is 300～1000 ℃).Described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium white, Thorotrast and the mesoporous Si-Al.Be preferably in aluminum oxide, silicon oxide and the mesoporous Si-Al one or more; More preferably aluminum oxide and/or silicon oxide.
The preparation method of described porous support comprises: precursor, Beta molecular sieve, peptizing agent and the water that will can form heat-resistant inorganic oxide under roasting condition mix, to supply raw materials; Described raw material is sent in the forcing machine, and in described forcing machine, after kneading, extruded, to obtain formed body; Described formed body is carried out roasting, and to obtain described porous support, wherein, the temperature of described formed body in the exit of described forcing machine is 40～150 ℃.With forcing machine raw material is being extruded, in the process that obtains formed body, it is near room temperature (being lower than 40 ℃) that prior art is controlled to be the temperature that makes the formed body of extruding with the cooling conditions of described forcing machine usually, but the present invention make the temperature of formed body in the exit of described forcing machine be 40～150 ℃ can be so that satisfy previously described requirement by most probable aperture and the aperture concentration degree of the porous support of this formed body preparation.
Preferably, the temperature of described formed body in the exit of described forcing machine is 60～120 ℃.Further preferably, the temperature of described formed body in the exit of described forcing machine is 60～100 ℃, can obtain so higher aperture concentration degree.More preferably, the temperature of described formed body in the exit of described forcing machine is 60～98 ℃.
The invention has the advantages that:
(1) adopt preferred hydro-upgrading isomerization-visbreaking catalyzer, obviously reduce the condensation point of diesel oil distillate, the heavy gas oil component of high condensation point is circulated to second reaction zone and again carries out the upgrading and pour point reducing reaction and can improve the purpose product yield.
(2) low-coagulation diesel oil that can direct production-10～-No. 35, product sulphur content, nitrogen content and aromaticity content reduce, and cetane value improves.
Description of drawings
Accompanying drawing is the method flow schematic diagram of production low-coagulation diesel oil provided by the invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.Raw material 1 boosts through feedstock pump, after hydrogen mixes, enters the first reaction zone 2 through heat exchange and process furnace preheating, contacts with Hydrobon catalyst I under certain condition and carries out hydrofining reaction.Reaction effluent directly enters the second hydroconversion reaction zone 3 without separating, react through hydro-upgrading pour point depression catalyzer and Hydrobon catalyst II at the second hydroconversion reaction zone, the second reaction zone resultant enters separation system 4 and fractionating system 5 cuts out gas, naphtha fraction, low solidifying product diesel oil and heavy gas oil cut 6.Heavy gas oil cut 6 is some or all of to be circulated to the second reaction zone entrance and again to carry out isomery and cracking reaction and further reduce condensation point.
The following examples will be further described the present invention, but not thereby limiting the invention.
Hydro-upgrading pour point depression catalyst B described in the embodiment prepares by following process:
Get the C1 powder and (be purchased the company from sasol, contents on dry basis is 74.5 % by weight, be a kind of pseudo-boehmite, relative crystallinity is 93.1%, average particulate diameter is that 53nm takes from the Chang Ling catalyst plant, sasol company produces, relative crystallinity 93.1%, grain size are 53.0nm, and contents on dry basis is 74.5%) 60.4g, SIRAL 10 powder (are purchased the company from sasol, contents on dry basis is 74.5 % by weight, for the mixture of the hydrate of the hydrate of aluminum oxide and silicon oxide, in oxide compound, the content of silicon oxide is 10 % by weight, the content of aluminum oxide is 90 % by weight, and average particulate diameter is that 53nm is purchased the company from sasol, and silica content is 10%, contents on dry basis is 74.5%) 46.9g, BETAeta60 molecular sieve (be purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 60, and contents on dry basis is 83 % by weight) 24.1 grams, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.The concentrated nitric acid adding of 3.5mL is contained with in the beaker of 88mL hot deionized water, mixes, to obtain acid solution.With acid solution and dry powder blend, and stir, obtain be used to the raw mix of extruding, the temperature of described deionized water so that obtain (temperature of raw mix is 70 ℃.The mixture (temperature is 70 ℃) that obtains is sent in the banded extruder, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the extrudate temperature in the exit of described forcing machine is 968 ℃.Extrudate is lower dry 3 hours at 130 ℃.Then, under air atmosphere, under 620 ℃ temperature, roasting 2 hours, in the roasting process, the flow of air is 155L. hour-1, obtains porous support A after being cooled to room temperature.The most probable aperture of this porous support is that 8.8nm, aperture concentration degree are 29.2, and crushing strength is 27.5N/mm.
Ammonium metawolframate (being purchased from the Chang Ling catalyst plant) and nickelous nitrate (being purchased from the sharp chemical reagent factory of Beijing benefit) are dissolved in the water, be mixed with steeping fluid, flood porous support A with this steeping fluid according to the hole saturation method, and the carrier after will flooding under 120 ℃ in air atmosphere dry 2 hours, then roasting 5 hours in air atmosphere under 350 ℃, thus make hydro-upgrading pour point depression catalyst B; Take the total amount of this catalyzer as benchmark, in oxide compound, WO
3Be respectively 27.0 % by weight and 2.6 % by weight with NiO content.
The trade names of the load hydrogenation catalyst for refining described in the embodiment are RS-1000, and the trade names of Hydrodewaxing catalyst are RDW-1, all are that Sinopec catalyzer branch office produces.
Non-supported hydrogenation catalyst for refining C described in the embodiment prepares by following process:
Take by weighing ammonium metawolframate ((NH
4)
2W
4O
1318H
2O, Sichuan, chemical pure) 5.4g, ammonium molybdate ((NH
4)
6Mo
7O
244H
2O, Tianjin, chemical pure) 3g, nickelous nitrate (Ni (NO
3)
26H
2O, Yixing, chemical pure) 10g joins in the 100mL water, stirs the lower 1.4g of adding tetraethylammonium bromide ((C
2H
5)
4NBr, Beijing, analytical pure), to drip concentration be 25% ammoniacal liquor to the pH value of mixing solutions be 9, mixed solution is placed synthesis reaction vessel, Hydrothermal Synthesis 12h under 50 ℃ of air tight conditions cools off afterwards, filters, washes, and filter cake was in 120 ℃ of dryings 2 hours, obtain non-supported hydrogenation catalyst for refining C, it consists of, take catalyzer as benchmark, and WO
3Be 49 % by weight, MoO
3Be 24 % by weight, NiO is 27 % by weight.
In embodiments of the invention and Comparative Examples, diesel product yield is defined as in the full cut product ratio of diesel oil distillate per-cent in the diesel oil distillate per-cent and raw material.
Embodiment 1
Take a kind of coking mixture of gasoline and gas oil 1. as raw material, first 1. raw material is carried out whole fraction oil hydrotreating at the first reaction zone, its reaction effluent directly enters the second hydroconversion reaction zone without separating, carry out upgrading and pour point reducing and post-refining reaction at the second hydroconversion reaction zone through hydro-upgrading pour point depression catalyzer and Hydrobon catalyst II, the second reaction zone resultant enters and separates and fractionating system cuts out the low product diesel oil that coagulates, and its heavy gas oil cut of 320～360 ℃ all is circulated to the second reaction zone entrance again to carry out isomery and cracking reaction and further reduce condensation point.The Hydrobon catalyst I of the first reaction zone filling is RS-1000, second reaction zone filling hydro-upgrading pour point depression catalyst B, and the Hydrobon catalyst II of second reaction zone filling is RS-1000, the admission space ratio of three partially catalyzed agent is: 50: 40: 10.
Stock oil character is listed in table 1, and reaction conditions and product property are listed in table 2.Data from table 2 can find out, under the reaction conditions that relaxes, diesel product yield is 88.6%, and condensation point is reduced to-41 ℃ by-2 ℃ of raw material diesel oil, and cold filter clogging temperature is reduced to-30 ℃, and cetane value is increased to 49.8 by 47.4 of raw material diesel oil.Sulphur content is less than 10 μ g/g simultaneously.It is a kind of low-coagulation diesel oil blend component that meets Europe V standard.
Comparative Examples 1
With raw material 1. Comparative Examples 1 is, first 1. raw material is at first carried out hydrofining, then enters the hydrodewaxing reaction bed.Hydrobon catalyst adopts RS-1000, and Hydrodewaxing catalyst adopts RDW-1, rear catalyst for refining filling RS-1000, and the admission space ratio of three partially catalyzed agent is: 50: 40: 10.These two kinds of catalyzer are China Petrochemical Industry's Chang Ling catalyst plant production.Result from Comparative Examples 1 can find out, diesel product yield only has 85.5%, and sulphur content is up to 146 μ g/g, and its density is high, and cetane value reduces.
Can find out from the result of embodiment 1 and Comparative Examples 1, when producing-No. 35 low-coagulation diesel oils, method provided by the present invention not only can improve diesel yield, and diesel quality increases substantially.
Embodiment 2
Take the coking mixture of gasoline and gas oil 1. as raw material, adopt method provided by the invention to carry out pour point depression, 340～360 ℃ heavy gas oil cut 30 % by weight are circulated to the second reaction zone entrance, employed catalyzer is respectively RS-1000, hydro-upgrading pour point depression catalyst B and RS-1000 catalyzer, and three partially catalyzed agent filling ratios are 45: 45: 10.Stock oil character is listed in table 1, and reaction conditions and product property are listed in table 2.
Data can be found out from table 2, and the freezing point reduction of diesel product is to-26 ℃, and cold filter clogging temperature is reduced to-14 ℃, and yield has reached 93.2%, and cetane value is increased to 48.5, the sulphur content decrease.
Embodiment 3
Take diesel oil 2. as raw material, adopt method provided by the invention to carry out pour point depression, 300～380 ℃ heavy gas oil cut 80 % by weight are circulated to the second reaction zone entrance, employed catalyzer is respectively RS-1000, hydro-upgrading pour point depression catalyst B and RS-1000 catalyzer, and three partially catalyzed agent filling ratios are 40: 50: 10.Stock oil character is listed in table 1, and reaction conditions and product property are listed in table 3.
Data can be found out from table 2, and the freezing point reduction of diesel product is to-45 ℃, and cold filter clogging temperature is reduced to-32 ℃, and yield has reached 88.2%, and cetane value is increased to 43.0, the sulphur content decrease.
Embodiment 4
Take diesel oil 2. as raw material, the method that adopts the present invention to disclose is carried out pour point depression, 330～380 ℃ heavy gas oil cut 60 % by weight are circulated to the second reaction zone entrance, employed catalyzer is respectively non-supported hydrogenation catalyst for refining C, hydro-upgrading pour point depression catalyst B and non-supported hydrogenation catalyst for refining C, and three partially catalyzed agent filling ratios are 50: 40: 10.Stock oil character is listed in table 1, and reaction conditions and product property are listed in table 3.
Data can be found out from table 3, and the freezing point reduction of diesel product is to-29 ℃, and cold filter clogging temperature is reduced to-14 ℃, and yield has reached 93.1%, and cetane value is increased to 49.1, the sulphur content decrease.
Table 1 stock oil character
| Stock oil | ① | ② |
| Full cut character | ||
| Density (20 ℃)/(g/cm 3) | 0.8361 | - |
| Sulphur content/(μ g/g) | 3100 | - |
| Nitrogen content/(μ g/g) | 2300 | - |
| Boiling range (ASTM D-86)/℃ | ||
| IBP | 102 | - |
| 10％ | 148 | - |
| 50％ | 249 | - |
| 90％ | 336 | - |
| FBP | 359 | - |
| ＜165 ℃ of cuts, weight/% | 19.75 | - |
| ＞165 ℃ of cuts, weight/% | 80.25 | - |
| ＞165 ℃ of diesel oil distillate character | ||
| Density (20 ℃)/(g/cm 3) | 0.8519 | 0.8893 |
| Sulphur content/(μ g/g) | 3300 | 3000 |
| Nitrogen content/(μ g/g) | 2700 | 560 |
| Condensation point/℃ | -10 | 4 |
| Cold filter clogging temperature/℃ | -2 | 8 |
| The actual measurement cetane value | 47.4 | 37.1 |
| Boiling range (ASTM D-86)/℃ | ||
| IBP | 186 | 189 |
| 50％ | 279 | 285 |
| 90％ | 340 | 357 |
| FBP | 357 | 379 |
Table 2 processing condition and product property
| Comparative Examples 1 | Embodiment 1 | Embodiment 2 | |
| Stock oil | ① | ① | ① |
| Processing condition | |||
| Hydrogen dividing potential drop/MPa | 7.5 | 7.5 | 6.4 |
| The first reaction zone (making with extra care) temperature/℃ | 355 | 355 | 357 |
| Second reaction zone (pour point depression) temperature/℃ | 365 | 365 | 353 |
| Cumulative volume air speed/h -1 | 0.63 | 0.63 | 0.80 |
| The standard state hydrogen to oil volume ratio | 800 | 800 | 1000 |
| The product diesel oil distillate | |||
| Yield/% | 85.5 | 88.6 | 93.2 |
| Density (20 ℃)/(g/cm 3) | 0.8503 | 0.8144 | 0.8175 |
| Sulphur content/(μ g/g) | 146 | ＜10 | ＜50 |
| Condensation point/℃ | -44 | -41 | -26 |
| Cold filter clogging temperature/℃ | -31 | -30 | -14 |
| The actual measurement cetane value | 45.2 | 49.8 | 48.5 |
Table 3 processing condition and product property
| Embodiment 3 | Embodiment 4 | |
| Stock oil | ② | ② |
| Processing condition | ||
| Hydrogen dividing potential drop/MPa | 6.4 | 11.0 |
| The first reaction zone (making with extra care) temperature/℃ | 355 | 345 |
| Second reaction zone (pour point depression) temperature/℃ | 375 | 355 |
| Cumulative volume air speed/h -1 | 0.85 | 1.45 |
| The standard state hydrogen to oil volume ratio | 800 | 1000 |
| The product diesel oil distillate | ||
| Yield/% | 88.2 | 93.1 |
| Density (20 ℃)/(g/cm 3) | 0.8526 | 0.8534 |
| Sulphur content/(μ g/g) | ＜10.0 | ＜10.0 |
| Condensation point/℃ | -45 | -29 |
| Cold filter clogging temperature/℃ | -32 | -14 |
| The actual measurement cetane value | 43.0 | 49.1 |
Claims (17)
1. method of producing high-grade low-freezing diesel oil comprises:
(1) diesel raw material contacts the hydrogenation saturated reaction that carries out hydrogenating desulfurization, hydrodenitrification reaction and alkene and aromatic hydrocarbons with after hydrogen mixes with Hydrobon catalyst at the first hydroconversion reaction zone,
The reaction effluent of (2) first hydroconversion reaction zones directly enters second reaction zone without separation and contacts with hydro-upgrading pour point depression catalyzer, carries out the pour point depression reaction,
(3) the second reaction zone effluent enters separation system and fractionating system, and the heavy gas oil cut circulation of separation column bottom enters the second reaction zone entrance;
Described hydro-upgrading pour point depression catalyzer contains porous support and loads on group vib metal and group VIII metal on this porous support, in oxide compound, take the total amount of this catalyzer as benchmark, the content of described group vib metal is 10～40 % by weight, the content of described group VIII metal is 2～10 % by weight, and the content of described porous support is 50～88 % by weight.
2. in accordance with the method for claim 1, it is characterized in that, the boiling range of the described heavy gas oil cut of step (3) is 280～390 ℃.
3. in accordance with the method for claim 1, it is characterized in that, the admission space ratio of described Hydrobon catalyst I and hydro-upgrading pour point depression catalyzer is: 20: 80～80: 20.
4. in accordance with the method for claim 1, it is characterized in that, in the second reaction zone of described step (3), also be filled with Hydrobon catalyst II in the downstream of hydro-upgrading pour point depression catalyzer; Take the volume sum of Hydrobon catalyst I and hydro-upgrading pour point depression catalyzer as benchmark, the loadings of Hydrobon catalyst II is 10%～50%.
5. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the first reaction zone is: hydrogen dividing potential drop 3.0～15.0MPa, 250～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～2000, volume space velocity 0.5～10h during liquid
-1
The reaction conditions of second reaction zone is: hydrogen dividing potential drop 3.0～15.0MPa, 280～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～2000, volume space velocity 0.5～10h during liquid
-1
6. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the first reaction zone is: hydrogen dividing potential drop 6.4～12.0MPa, 300～420 ℃ of temperature of reaction; Hydrogen to oil volume ratio 500～1500; Volume space velocity 0.8～3.0h during liquid
-1
The reaction conditions of second reaction zone is: hydrogen dividing potential drop 6.4～12.0MPa, 300～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 500～1500, volume space velocity 0.8～5.0h during liquid
-1
7. in accordance with the method for claim 1, it is characterized in that, described diesel raw material can be the mixing oil of diesel oil distillate and gasoline fraction, and wherein the condensation point of diesel oil distillate is between 30～-35 ℃, and cold filter clogging temperature is between 20～-20 ℃.
8. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst I is the load hydrogenation catalyst for refining, or the non-supported hydrogenation catalyst for refining.
9. in accordance with the method for claim 8, it is characterized in that, described load hydrogenation catalyst for refining, take composite alumina and composite oxygen SiClx as carrier, it consists of: in oxide compound and take the catalyzer total amount as benchmark, the content of nickel and/or cobalt is 1～10 heavy %, and molybdenum and tungsten sum are greater than 10 to 50 heavy %, and surplus is carrier.
10. in accordance with the method for claim 8, it is characterized in that, described non-supported hydrogenation catalyst for refining contains at least a VIII family metal component, at least two kinds of group vib metal components and organic additive, and the content of a kind of VIII family metal component, at least two kinds of group vib metal components and organic additive satisfies: mR:[VIII
x(VIB-1)
y(VIB-2)
z] O
2Wherein, represent a kind of group vib metal component VIB-2 with VIB-1 and represent another kind of group vib metal component; R represents at least a organic additive; M represents every mole of [VIII
x(VIB-1)
y(VIB-2)
z] O
2In the mole number of contained organic additive, the span of m is 0.1～2, take the total amount of VIII family metal component, VIB-1 metal component and VIB-2 metal component as benchmark; X, y, z represent respectively VIII family metal component, the VIB-1 metal component, and the molar fraction of VIB-2 metal component, x, y, the span of z satisfies (y+z): x=10: 1～1: 10.
11. in accordance with the method for claim 10, it is characterized in that, described group VIII metal component is cobalt, nickel and composition thereof, and described group vib metal component is molybdenum and tungsten; Described x, y, the span of z satisfies (y+z): x=3: 1～1: 3, and y: z=3: 1～1: 3.
12. in accordance with the method for claim 10, it is characterized in that, described organic additive is selected from the organic ammonium compound, one or more in sulfonate and the organophosphate.
13. in accordance with the method for claim 4, it is characterized in that, described Hydrobon catalyst II is identical with Hydrobon catalyst I, and is perhaps different.
14. in accordance with the method for claim 1, it is characterized in that, described porous support contains heat-resistant inorganic oxide and Beta molecular sieve, the most probable aperture of this porous support is 1～30nm, the aperture concentration degree of this porous support is 22～48, and described most probable aperture is to adopt the BET method to measure, and described aperture concentration degree refers to adopt in the distribution curve of dV/dr with varying aperture of BET method mensuration, the ratio of the height at peak and the halfwidth at this peak, dV/dr represent the long-pending differential to the aperture of specific pore volume; Take the total amount of described heat-resistant inorganic oxide and Beta molecular sieve as benchmark, the content of described Beta molecular sieve is 0.1～66 % by weight, and the content of described heat-resistant inorganic oxide is 34～99.9 % by weight.
15. in accordance with the method for claim 14, it is characterized in that, the most probable aperture of described porous support is 2～20nm, and the aperture concentration degree is 25～48.
16. method according to claim 14 is characterized in that, the most probable aperture of described porous support is 5～10nm, and the aperture concentration degree is 27～40.
17. in accordance with the method for claim 14, it is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium white, Thorotrast and the mesoporous Si-Al.
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| CN109988604A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of hydrogenation coupling process producing low freezing point diesel fuel |
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