CN103773488A - Hydrogenation method for reducing condensation point of diesel - Google Patents
Hydrogenation method for reducing condensation point of diesel Download PDFInfo
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- CN103773488A CN103773488A CN201210411609.9A CN201210411609A CN103773488A CN 103773488 A CN103773488 A CN 103773488A CN 201210411609 A CN201210411609 A CN 201210411609A CN 103773488 A CN103773488 A CN 103773488A
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Abstract
A hydrogenation method for reducing the condensation point of diesel comprises the following steps: raw oil is in contact with a hydrofining catalyst in a first reaction area for reaction, effluents in the first reaction area are subjected to separation and fractionation to obtain gases, naphtha fractions, low-condensation-point diesel fractions I and high-condensation-point heavy diesel fractions; the obtained high-condensation-point heavy diesel fractions enter a second reaction area, and are in contact with a hydro-upgrading condensation point reducing catalyst to carry out an isocracking condensation point reducing reaction; effluents in the second reaction area are subjected to separation and fractionation to obtain low-condensation-point diesel fractions II; the low-condensation-point diesel fractions and the low-condensation-point diesel fractions II are mixed to obtain low-condensation-point diesel. According to the invention, the process selectivity is improved, so that the low-condensation-point diesel yield is improved remarkably. Through the adoption of the hydrogenation method, No.-10 to No.-50 low-condensation-point diesel can be produced flexibly, the cetane number is increased as compared with that of the raw material, the content of impurities such as sulfur and nitrogen is reduced greatly, and the Europe IV diesel standard and the Europe V diesel standard can be met.
Description
Technical field
The present invention relates to a kind of hydro carbons in the situation that hydrogen exists, refine the process with upgrading.More particularly, be a kind of method of producing low-coagulation diesel oil after diesel oil fraction hydrogenating.
Background technology
The sustainable and healthy development of China's economy and the raising of living standards of the people make automobile come into ordinary family, and derv fuel oil is especially increased the demand of low-coagulation diesel oil thereupon.On the other hand, Environmental awareness and environmental requirement improve constantly the continuous quickening that has promoted diesel quality upgrading paces.Meanwhile, the lasting high enterprise of world's crude oil price and oil refining enterprise's benefit are constantly compressed.Therefore, how producing clean low-coagulation diesel oil cut, improving diesel yield is one of problem facing of oil Refining Technologies.
In diesel oil distillate, the component of high condensation point is mainly straight-chain paraffin, naphthenic hydrocarbon and aromatic hydrocarbons with long side chain.Therefore, can adopt the method that separates or transform high condensation point component to reduce diesel oil distillate condensation point.In addition, in actual production, also can produce a small amount of low-coagulation diesel oil by adding pour point depressant, but exist pour point depression amplitude limited, high in cost of production shortcoming.
The technique that adopts separation method to reduce diesel oil distillate condensation point has dewaxing by molecular sieve, urea dewaxing, solvent dewaxing etc., and these techniques exist the deficiencies such as flow process complexity, the high and low coagulation diesel oil yield of energy consumption are lower.For this reason, researchist has developed hydrodewaxing technology and hydroisomerizing pour point depression technology.
CN1061679C has introduced hydrodewaxing technology, and this technology is the technological process of carrying out shape slective cracking under hydrogen, middle pressure condition facing.It utilizes the pore passage structure of particular molecule sieve catalyst uniqueness and suitable acid sites, and the contour condensation point component of the normal paraffin in diesel raw material is carried out to selective cracking, thereby reduces the zero pour of diesel product, by-product part petroleum naphtha and liquefied gas simultaneously.Its acid material is mainly ZSM series and SAPO Series Molecules sieve.Adopt this technology, can reduce the condensation point of diesel oil distillate, because the straight-chain paraffin of high hexadecane value is converted, cetane value reduces, and diesel yield reduces, and hydrogen consumption increases.In addition, due to the hydrogenation ability of Hydrodewaxing catalyst a little less than, diesel product density is high, sulphur nitrogen content is higher, olefin(e) centent is high, oxidation stability is poor.
US 6652735, US 7261805, US 4419220 etc. have introduced isomerization-visbreaking technology.This technology adopts the noble metal catalyst of loading type, and two-stage process flow process, by special pore passage structure and the acidity of molecular sieve, tautomerizes to branched paraffin by long chain alkane and reaches the object that reduces condensation point.This technical matters flow process complexity, the catalyzer costliness of application, invest high, and the easy poisoning and deactivation of noble metal catalyst.
CN101724459A discloses a kind of method of hydrotreating that reduces condensation point of diesel oil, the first hydrofining of the method diesel raw material, then in high pressure hot separator, carry out flash distillation, the liquid phase stream that high pressure hot separator obtains enters the second hydroconversion reaction zone and carries out pour point depression and rear refining, the gaseous stream of high pressure hot separator mixes with the reaction effluent of the second hydroconversion reaction zone, enters later separation and fractionating system obtains diesel product.
Summary of the invention
The object of the invention is to provide a kind of method of hydrotreating that reduces condensation point of diesel oil.
Method provided by the invention comprises:
(1), after stock oil mixes with hydrogen, contact the hydrogenation saturated reaction that carries out hydrogenating desulfurization, hydrodenitrification and alkene and aromatic hydrocarbons with Hydrobon catalyst in the first reaction zone;
(2) first reaction zone effluents enter the first separation system and the first fractionating system, obtain gas, naphtha fraction, low-coagulation diesel oil cut I, and separation column bottom obtains high condensation point heavy gas oil cut;
(3) the high condensation point heavy gas oil cut of step (2) gained enters second reaction zone, contacts with hydro-upgrading pour point depression catalyzer, carries out the reaction of isocracking pour point depression;
(4) second reaction zone effluent enters the second separation system and after-fractionating system, obtains gas, naphtha fraction, low-coagulation diesel oil cut II;
(5) low-coagulation diesel oil cut I and low-coagulation diesel oil cut II are mixed to get the low solidifying product diesel oil of high yield.
Described hydro-upgrading pour point depression catalyzer contains porous support and loads on group vib metal and the 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.
Raw material of the present invention can be diesel oil distillate, can be also the mixing oil of diesel oil distillate and gasoline fraction.Wherein diesel oil distillate is selected from one or more of straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil and other diesel oil distillates.Gasoline fraction is selected from one or more of coker gasoline, catalytic gasoline and other gasoline fractions.The condensation point of described diesel oil distillate is between 30 ~-35 ℃, and cold filter clogging temperature is between 20 ~-20 ℃.
In step (1), diesel raw material or diesel oil mixing raw material mix with hydrogen, carry out the hydrogenation saturated reaction of hydrogenating desulfurization, hydrodenitrification, alkene and aromatic hydrocarbons in the first reaction zone through Hydrobon catalyst.Hydrogenating desulfurization and hydrodenitrification reaction can reduce the foreign matter contents such as the sulphur nitrogen in product.The hydrogenation saturated reaction of alkene and aromatic hydrocarbons can improve product storage stability, improves product diesel-fuel cetane number.
The reaction conditions of the first described reaction zone is: hydrogen dividing potential drop 3.0～15.0MPa, preferably 6.4～12.0MPa; 250～450 ℃ of temperature of reaction, preferably 300～420 ℃; Hydrogen to oil volume ratio 200～2000Nm
3/ m
3, preferably 500～1500Nm
3/ m
3; Volume space velocity 0.5～10h when liquid
-1, preferably 0.8～3.0h
-1.
In step (2), the first reaction zone effluent enters the first separation and the first fractionating system, isolates dry gas, liquefied gas, naphtha fraction, low-coagulation diesel oil cut I and high condensation point heavy gas oil cut.
The cut point of low-coagulation diesel oil cut I and high condensation point heavy gas oil cut is between 250 ℃ ~ 340 ℃.In diesel oil distillate, the component of high condensation point is mainly straight-chain paraffin, naphthenic hydrocarbon and aromatic hydrocarbons with long side chain, and molecular weight is larger, and boiling range is heavier, and condensation point is also higher, and therefore in diesel oil distillate, high condensation point component mainly concentrates in high boiling fraction.In addition, condensation point and cold filter clogging temperature can characterize research of cold flow properties of diesel fuel, but cold filter clogging temperature more approaches the use properties of diesel oil, and therefore, low-coagulation diesel oil not only wants condensation point index to meet the requirements, and cold filter clogging temperature index also needs to meet the requirements.The present inventor finds by research, and for part diesel oil, condensation point has reached requirement, but cold filter clogging temperature is undesirable.As, a kind of condensation point of low-coagulation diesel oil is-36 ℃, but its cold filter clogging temperature is only-23 ℃.Therefore, producing low-coagulation diesel oil not only needs to reduce condensation point, also needs to reduce cold filter clogging temperature.
The present inventor carries out the cutting of various different fractions sections by the diesel oil distillate to different, the cut point of having found low-coagulation diesel oil and high condensation point heavy gas oil component is also very crucial, on the one hand can be according to the specification of quality control of low-coagulation diesel oil product, preferably cut point is 250 ~ 340 ℃ on the other hand, more preferably 260 ~ 320 ℃.
In step (3), high condensation point heavy gas oil cut is all delivered to second reaction zone entrance and is contacted with hydro-upgrading isomerization-visbreaking catalyzer, carries out isomery and cracking reaction, reduces condensation point and cold filter clogging temperature.Second reaction zone effluent enters the second separation and after-fractionating system.
The reaction conditions of described second reaction zone is: hydrogen dividing potential drop 3.0～15.0MPa, preferably 6.4～12.0MPa; 280～450 ℃ of temperature of reaction, preferably 300～420 ℃; Hydrogen to oil volume ratio 200～2000Nm
3/ m
3, preferably 500～1500Nm
3/ m
3; Volume space velocity 0.5～10h when liquid
-1, preferably 0.8～5.0h
-1.
The admission space ratio of described Hydrobon catalyst and hydro-upgrading pour point depression catalyzer is: the preferred 60:40～90:10 of 40:60～95:5.
In a preferred embodiment; for preventing that Hydrobon catalyst is because of the coking such as alkene, colloid precursor coking and metal poisoning in diesel raw material; the hydrogenation protecting agent that can account for Hydrobon catalyst volume total amount 5～30% at the first reaction zone bed top loading; with protection Hydrobon catalyst, avoid the quick coking of Primary Catalysts bed.Protective material is made up 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), be also filled with post-refining catalyzer in the downstream of hydro-upgrading pour point depression catalyzer; Take the volume sum of hydro-upgrading pour point depression catalyzer as benchmark, the loadings of post-refining catalyzer is 10% ~ 50%.Second reaction zone effluent carries out post-refining reaction through post-refining catalyzer, reduces alkene and mercaptan sulfur content in the effluent of second reaction zone.Described post-refining catalyzer is identical with Hydrobon catalyst, or different.
Hydrobon catalyst and post-refining catalyzer can be the Hydrobon catalysts of loading type, can be also the Hydrobon catalysts of non-loading type.
Described load hydrogenation catalyst for refining is take composite alumina and composite oxygen SiClx as carrier, and in metal component, at least one is selected from VIII family, and at least one is selected from the metal component of group vib.Its preferred Hydrobon catalyst consists of: in oxide compound and take 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 one 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 meets: mR:[VIII
x(VIB-1)
y(VIB-2)
z] O
2; Wherein, represent that with VIB-1 a kind of group vib metal component VIB-2 represents another kind of group vib metal component; R represents at least one 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 represents respectively VIII family metal component, VIB-1 metal component, the molar fraction of VIB-2 metal component, x, y, the span of z meets (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 meets (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, organophosphate and sulfonate.
Described organic ammonium compound is selected from one or more in tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, TPAOH, hexamethylenetetramine, Dodecyl trimethyl ammonium chloride; Sulfonate is selected from sodium laurylsulfonate and/or Sodium dodecylbenzene sulfonate.In non-supported hydrogenation catalyst for refining, also contain binding agent, take catalyzer as benchmark, the content of described binding agent is no more than 75 % by weight.Preferably 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 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 containing molecular sieve.Hydro-upgrading pour point depression catalyzer contains porous support and loads on group vib metal and the 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 aperture concentration degree is 25～48.Further preferably the most probable aperture of this porous support is 5～10nm, and aperture concentration degree is 27～40.Described most probable aperture is to adopt BET method to measure, and described aperture concentration degree refers to and adopts in dV/dr that BET method the measures distribution curve with varying aperture, the ratio of the height at peak and the halfwidth at this peak, and dV/dr represents that specific pore volume amasss the differential to aperture.
In the present invention, term " most probable aperture " refers to: in the time adopting the pore structure of BET method measure sample, and in the distribution curve of the long-pending differential (, dV/dr) to aperture of the specific pore volume of acquisition with aperture, the corresponding aperture of maximum value of dV/dr.Adopt BET method to measure the pore structure of porous mass, known in those skilled in the art to the differential in aperture with the method for the distribution curve in aperture to obtain specific pore volume long-pending, for example can be according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety first version, the volumes such as Yang Cuiding) in the RIPP 151-90 that records the method that stipulates measure.
In the present invention, term " aperture concentration degree " refers to: in the time adopting the pore structure of BET method measure sample, the specific pore volume of acquisition amasss the differential in aperture in the distribution curve with aperture, 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, while there is multiple peak in the distribution curve at described dV/dr with varying aperture, the ratio of the peak height at each peak and the halfwidth at this peak all should meet 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 there is higher aperture concentration degree, the normal paraffin of long-chain can tautomerize to branched paraffin the unobstructed duct that diffuses out in duct, thereby reduce secondary cracking reaction, improved 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 last running conversion.Therefore, not only diesel yield is high for described hydro-upgrading pour point depression catalyzer, and 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.
In 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 mesoporous Si-Al.Be preferably one or more in aluminum oxide, silicon oxide and mesoporous Si-Al; More preferably aluminum oxide and/or silicon oxide.
The preparation method of described porous support, comprising: precursor, Beta molecular sieve, peptizing agent and the water that under roasting condition, can form heat-resistant inorganic oxide are mixed, to supply raw materials; Described raw material is sent in forcing machine, and after kneading, extruded in described forcing machine, to obtain formed body; Described formed body is carried out to roasting, and to obtain described porous support, wherein, described formed body is 40～150 ℃ in the temperature in the exit of described forcing machine.With forcing machine, raw material is being extruded, to obtain in the process of formed body, prior art is that to make the temperature of the formed body of extruding be near room temperature (lower than 40 ℃) conventionally by the cooling conditions control of described forcing machine, can make the most probable aperture of the porous support of being prepared by this formed body and aperture concentration degree meet previously described requirement but the present invention makes formed body be 40～150 ℃ in the temperature in the exit of described forcing machine.
Preferably, described formed body is 60～120 ℃ in the temperature in the exit of described forcing machine.Further preferably, described formed body is 60～100 ℃ in the temperature in the exit of described forcing machine, can obtain so higher aperture concentration degree.More preferably, described formed body is 60～98 ℃ in the temperature in the exit of described forcing machine.
The invention has the advantages that:
(1) the present invention has improved process choosing, thereby has improved significantly low-coagulation diesel oil yield.In raw material, the diesel component of low condensation point only contacts with catalyst for refining, avoids overcracking reaction to occur, and has reduced hydrogen consumption, has improved diesel yield.
(2) the present invention contacts the heavy gas oil cut of high condensation point with hydro-upgrading isomerization-visbreaking catalyzer, carries out isomery and part open loop cracking reaction, can obviously reduce condensation point and the cold filter clogging temperature of diesel oil distillate.Meanwhile, the naphthenic hydrocarbon being rich in diesel oil heavy constituent and aromatic hydrocarbons, through hydrocracking, have significantly reduced density, have improved hydrogen richness and cetane value.
(3) the present invention can produce the low-coagulation diesel oil of-10 ~-No. 50 flexibly, and cetane value is improved largely compared with raw material, and the foreign matter content such as sulphur, nitrogen significantly lowers, and can meet Europe IV and Europe V clean diesel standard.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet of a kind of method of hydrotreating that reduces condensation point of 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 mixes with hydrogen-rich gas 17 through feedstock pump and boosts, enters the first reaction zone 2 after heat exchange and process furnace preheating, contacts and carries out hydrofining reaction under certain condition with Hydrobon catalyst.The first reaction zone effluent enters separation system 3 and isolates hydrogen-rich gas 19 and liquid ingredient; Liquid ingredient enters the first fractionating system 4 and isolates gas 5, naphtha fraction 6, low-coagulation diesel oil cut 7 and high condensation point heavy gas oil cut 8.After high condensation point heavy gas oil cut 8 mixes with hydrogen, boost, enter second reaction zone 9 after the heating of heat exchange and process furnace through feedstock pump, contact with hydro-upgrading pour point depression catalyzer in second reaction zone, carry out the reaction of isocracking pour point depression.Second reaction zone effluent enters separation system 10 and isolates hydrogen-rich gas 20 and liquid ingredient, and liquid ingredient enters after-fractionating system 11 and cuts out gas 12, naphtha fraction 13, low-coagulation diesel oil cut 14.Low-coagulation diesel oil cut 7 and low-coagulation diesel oil cut 14 are mixed to get the low-coagulation diesel oil product of high yield.Hydrogen-rich gas 19 and hydrogen-rich gas 20 enter recycle hydrogen compression system 16 and obtain hydrogen-rich gas 17 and recycle after desulfurization, and hydrogen-rich gas 17 and pure hydrogen 18 are mixed into second reaction zone 9.
The following examples will be further described the present invention, but not thereby limiting the invention.
Hydro-upgrading pour point depression catalyzer E described in embodiment is prepared by following process:
Get C1 powder and (be purchased the company from sasol, contents on dry basis is 74.5 % by weight, for a kind of pseudo-boehmite, relative crystallinity is 93.1%, average particulate diameter is 53nm) 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 aluminum oxide and the hydrate of silicon oxide, in oxide compound, the content of silicon oxide is 10 % by weight, the content of aluminum oxide is 90 % by weight, average particulate diameter is 53nm) 46.9g, BETA60 molecular sieve (is purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 60, contents on dry basis is 83 % by weight) 24.1 grams, adding sesbania powder 3g is dry mixed evenly, to obtain dry powder.The concentrated nitric acid of 3.5mL is added in the beaker that is contained with 88mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture for extruding, the temperature of described deionized water is 70 ℃.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described forcing machine is 96 ℃.Extrudate is dried to 3 hours at 130 ℃.Then, under air atmosphere, at the temperature of 620 ℃, roasting 2 hours, in roasting process, the flow of air is 155L hour
-1, obtain porous support q 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 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, with this steeping fluid according to hole saturation method dipping porous support q, and the carrier after dipping is dried to 2 hours at 120 ℃ in air atmosphere, then roasting 5 hours in air atmosphere at 350 ℃, thus make hydro-upgrading pour point depression catalyzer E; 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 embodiment are RS-2000; protectant trade names are RG-20A, RG-20B; the trade names of the Hydrodewaxing catalyst described in comparative example are RDW-1, are all that Sinopec catalyzer branch office produces.
Non-supported hydrogenation catalyst for refining F described in embodiment is prepared by following process:
Take 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 100mL water, adds 1.4g tetraethylammonium bromide ((C under stirring
2h
5)
4nBr, Beijing, analytical pure), ammoniacal liquor to the pH value of mixing solutions that dropping concentration is 25% is 9, mixed solution is placed in to synthesis reaction vessel, Hydrothermal Synthesis 12h under 50 ℃ of air tight conditions, afterwards cooling, filter, washing, filter cake is dry 2 hours in 120 ℃, obtain non-supported hydrogenation catalyst for refining F, 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 example, diesel product yield is defined as in full cut product the ratio of diesel oil distillate per-cent in diesel oil distillate per-cent and raw material.
Embodiment 1
Take a kind of straight-run diesel oil A as raw material, first raw material A is contacted and carries out hydrofining with Hydrobon catalyst RS-2000 in the first reaction zone, the first reaction zone effluent enters the first separation system and the first fractionating system cuts out gas, naphtha fraction, low-coagulation diesel oil cut I and high condensation point heavy gas oil cut (boiling range is 325 ~ 376 ℃), the heavy gas oil cut of whole high condensation points enters the second hydroconversion reaction zone, contacts and carries out isomerization-visbreaking reaction with hydro-upgrading pour point depression catalyzer E in the second hydroconversion reaction zone; Second reaction zone effluent enters the second separation system and after-fractionating system cuts out gas, naphtha fraction, low-coagulation diesel oil cut II.Low-coagulation diesel oil cut I and low-coagulation diesel oil cut II are mixed to get the low-coagulation diesel oil product of high yield.
The admission space of Hydrobon catalyst, hydro-upgrading pour point depression catalyzer E is than being 85:15.In order to prevent the coking such as alkene, gum asphalt precursor coking and the metal poisoning in raw material, at the first reaction zone top loading a small amount of protective material RG-20A, RG-20B.Load a small amount of post-refining catalyzer RS-2000 in hydro-upgrading pour point depression catalyzer E bottom.List in table 1 in stock oil character, reaction conditions and product property are listed in table 2.
Data from table 2 can find out, under the reaction conditions relaxing, diesel product yield is 93.4%, and freezing point reduction is to-36 ℃, and cold filter clogging temperature is reduced to-29 ℃, and sulphur content is less than 10 μ g/g, is a kind of low-coagulation diesel oil that meets Europe V standard.
Comparative example 1
Comparative example 1 is by raw material A, first first raw material A is carried out to hydrofining, then enters hydrodewaxing reaction bed.Hydrobon catalyst adopts RS-2000, and Hydrodewaxing catalyst adopts RDW-1, post-refining catalyst loading RS-2000, and 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.
Result from comparative example 1 can find out, although diesel product condensation point is reduced to-37 ℃, its cold filter clogging temperature only has-24 ℃, does not reach the requirement of-No. 35 diesel low-temperature liquidities.And diesel product yield only has 85.1%, sulphur content is up to 140 μ g/g, and its density is high, and cetane value is lower.
Can find out from the result of embodiment 1 and comparative example 1, in the time 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 a kind of catalytic diesel oil B as raw material, carry out pour point depression according to method provided by the invention.High condensation point heavy gas oil cut boiling range is 265 ~ 379 ℃.Hydrobon catalyst is non-supported hydrogenation catalyst for refining F, and the admission space of Hydrobon catalyst, hydro-upgrading pour point depression catalyzer E is than being 60:40.Stock oil character is listed in table 1, and reaction conditions and product property are listed in table 3.
From table 3, data can be found out, the freezing point reduction of diesel product is to-26 ℃, and cold filter clogging temperature is reduced to-16 ℃, and yield has reached 91.4%, and cetane value is increased to 51.2, and sulphur content significantly reduces.
Embodiment 3
Urge straight bavin mixing oil C as raw material take one, carry out pour point depression according to method provided by the invention.High condensation point heavy gas oil cut boiling range is 315 ~ 371 ℃.Hydrobon catalyst is non-supported hydrogenation catalyst for refining F, and the admission space of Hydrobon catalyst, hydro-upgrading pour point depression catalyzer E is than being 70:30.Stock oil character is listed in table 1, and reaction conditions and product property are listed in table 3.
From table 3, data can be found out, the freezing point reduction of diesel product is to-27 ℃, and cold filter clogging temperature is reduced to-18 ℃, and yield has reached 95.1%, and cetane value is increased to 53.5, and sulphur content significantly reduces.
Embodiment 4
Take a kind of coking gasoline and diesel D as raw material, carry out pour point depression according to method provided by the invention.High condensation point heavy gas oil cut boiling range is 340 ~ 360 ℃.Hydrobon catalyst is RS-2000, and the admission space of Hydrobon catalyst, hydro-upgrading pour point depression catalyzer E is than being 90:10.Stock oil character is listed in table 1, and reaction conditions and product property are listed in table 3.
From table 3, data can be found out, the freezing point reduction of diesel product is to-30 ℃, and cold filter clogging temperature is reduced to-18 ℃, and yield has reached 96.3%, and cetane value is increased to 54.5, and sulphur content significantly reduces.
Table 1 stock oil character
| Analysis project | Raw material A | Raw material B | Raw material C | Raw material D |
| Full cut character | ||||
| Density (20 ℃)/(g/cm 3） | 0.8308 | 0.8893 | 0.8458 | 0.8361 |
| Sulphur content/(μ g/g) | 2203 | 3000 | 3500 | 3100 |
| Nitrogen content/(μ g/g) | 78 | 560 | 177 | 2300 |
| Condensation point/℃ | -8 | 4 | -10 | -14 |
| Cold filter clogging temperature/℃ | 4 | 8 | 1 | -3 |
| Actual measurement cetane value | 54.2 | 37.1 | 47.2 | |
| Boiling range (ASTM D-86)/℃ | ||||
| IBP | 214 | 189 | 200 | 112 |
| 10％ | 257 | 225 | 242 | 157 |
| 50％ | 290 | 285 | 285 | 253 |
| 90％ | 346 | 357 | 342 | 337 |
| FBP | 376 | 379 | 371 | 360 |
| < 165 ℃ of cut yield/% | 17.6 | |||
| > 165 ℃ of cut yield/% | 82.4 |
[0078]table 2 processing condition and product property
| Comparative example 1 | Embodiment 1 | |
| Stock oil | A | A |
| Processing condition | ||
| Hydrogen dividing potential drop/MPa | 6.4 | 6.4 |
| The first reaction zone temperature/℃ | 355 | 350 |
| Second reaction zone temperature/℃ | 360 | 360 |
| Cumulative volume air speed/h -1 | 1.1 | 1.30 |
| Standard state hydrogen to oil volume ratio | 700 | 800 |
| Product diesel oil distillate | ||
| Yield/% | 85.1 | 93.4 |
| Density (20 ℃)/(g/cm 3） | 0.8385 | 0.8235 |
| Sulphur content/(μ g/g) | 140 | <10.0 |
| Condensation point/℃ | -37 | -36 |
| Cold filter clogging temperature/℃ | -24 | -29 |
| Actual measurement cetane value | 48.5 | 55.7 |
[0080]table 3 processing condition and product property
| Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Stock oil | B | C | D |
| Processing condition | |||
| Hydrogen dividing potential drop/MPa | 9.5 | 8.0 | 6.4 |
| The first reaction zone temperature/℃ | 360 | 355 | 350 |
| Second reaction zone temperature/℃ | 365 | 355 | 355 |
| Cumulative volume air speed/h -1 | 1.05 | 1.20 | 1.50 |
| Standard state hydrogen to oil volume ratio | 800 | 700 | 700 |
| Product diesel oil distillate | |||
| Yield/% | 92.4 | 95.1* | 96.3* |
| Density (20 ℃)/(g/cm 3） | 0.8328 | 0.8241 | 0.8282 |
| Sulphur content/(μ g/g) | <10.0 | <10.0 | <10.0 |
| Condensation point/℃ | -27 | -41 | -30 |
| Cold filter clogging temperature/℃ | -18 | -30 | -18 |
| Actual measurement cetane value | 51.2 | 53.5 | 54.5 |
* product diesel oil distillate accounts for the per-cent of diesel oil distillate in petrol and diesel oil mixing raw material.
Claims (14)
1. a method of hydrotreating that reduces condensation point of diesel oil, comprising:
(1), after stock oil mixes with hydrogen, contact the hydrogenation saturated reaction that carries out hydrogenating desulfurization, hydrodenitrification and alkene and aromatic hydrocarbons with Hydrobon catalyst in the first reaction zone;
(2) first reaction zone effluents enter the first separation system and the first fractionating system, obtain gas, naphtha fraction, low-coagulation diesel oil cut I, and separation column bottom obtains high condensation point heavy gas oil cut;
(3) the high condensation point heavy gas oil cut of step (2) gained enters second reaction zone, contacts with hydro-upgrading pour point depression catalyzer, carries out the reaction of isocracking pour point depression;
(4) second reaction zone effluent enters the second separation system and after-fractionating system, obtains gas, naphtha fraction, low-coagulation diesel oil cut II;
(5) low-coagulation diesel oil cut I and low-coagulation diesel oil cut II are mixed to get the low solidifying product diesel oil of high yield;
Described hydro-upgrading pour point depression catalyzer contains porous support and loads on group vib metal and the 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, described stock oil is diesel oil distillate, or the mixing oil of diesel oil distillate and gasoline fraction, and wherein diesel oil distillate is selected from one or more of straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil and other diesel oil distillates; The condensation point of described diesel oil distillate is between 30 ~-35 ℃, and cold filter clogging temperature is between 20 ~-20 ℃.
3. in accordance with the method for claim 1, it is characterized in that, in described step (2), the cut point of low-coagulation diesel oil cut I and high condensation point heavy gas oil cut is between 250 ℃ ~ 340 ℃.
4. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the first described reaction zone is: hydrogen dividing potential drop 3.0～15.0MPa, 250～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～2000Nm
3/ m
3, volume space velocity 0.5～10h when liquid
-1;
The reaction conditions of described second reaction zone is: hydrogen dividing potential drop 3.0～15.0MPa, 280～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～2000Nm
3/ m
3, volume space velocity 0.5～10h when liquid
-1.
5. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the first described reaction zone is: hydrogen dividing potential drop 6.4～12.0MPa, 300～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 500～1500Nm
3/ m
3, volume space velocity 0.8～3.0h-1 when liquid;
The reaction conditions of described second reaction zone is: hydrogen dividing potential drop 6.4～12.0MPa, 300～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 500～1500Nm
3/ m
3, volume space velocity 0.8～5.0h when liquid
-1.
6. in accordance with the method for claim 1, it is characterized in that, in the second reaction zone of described step (3), be also filled with post-refining catalyzer in the downstream of hydro-upgrading pour point depression catalyzer; Take the volume of hydro-upgrading pour point depression catalyzer as benchmark, the loadings of supplementing Hydrobon catalyst is 10% ~ 50%.
7. according to the method described in claim 1 or 6, it is characterized in that, described Hydrobon catalyst and post-refining catalyzer are load hydrogenation catalyst for refining, or non-supported hydrogenation catalyst for refining.
8. in accordance with the method for claim 7, 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 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.
9. in accordance with the method for claim 7, it is characterized in that, described non-supported hydrogenation catalyst for refining contains at least one 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 meets: mR:[VIII
x(VIB-1)
y(VIB-2)
z] O
2; Wherein, represent that with VIB-1 a kind of group vib metal component VIB-2 represents another kind of group vib metal component; R represents at least one 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 represents respectively VIII family metal component, VIB-1 metal component, the molar fraction of VIB-2 metal component, x, y, the span of z meets (y+z): x=10:1～1:10.
10. in accordance with the method for claim 9, 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 meets (y+z): x=3:1～1:3, and y:z=3:1～1:3.
11. in accordance with the method for claim 9, it is characterized in that, described organic additive is selected from organic ammonium compound, one or more in sulfonate and phosphoric acid salt.
12. in accordance with the method for claim 1, it is characterized in that, the porous support of described hydro-upgrading pour point depression catalyzer 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, described most probable aperture is to adopt BET method to measure, described aperture concentration degree refers to and adopts in dV/dr that BET method the measures distribution curve with varying aperture, the ratio of the height at peak and the halfwidth at this peak, dV/dr represents the long-pending differential to 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.
13. in accordance with the method for claim 12, it is characterized in that, the most probable aperture of described porous support is 2～20nm, and aperture concentration degree is 25～48.
14. in accordance with the method for claim 12, 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 mesoporous Si-Al.
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| CN105013405A (en) * | 2015-03-31 | 2015-11-04 | 山东胜星化工有限公司 | Combined reaction device reinforcing pour point depressing of diesel by two-time hydrogenation |
| CN109294746A (en) * | 2017-07-25 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of method that grease type raw material adds hydrogen to prepare diesel oil distillate |
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