CN1417298A - Combined hydrogenation method of producing diesel oil with high cetane number and low solidifying point - Google Patents
Combined hydrogenation method of producing diesel oil with high cetane number and low solidifying point Download PDFInfo
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Abstract
The combined hydrogenation method of producing diesel oil with high cetane number and low solidifying point includes contacting the raw material oil and hydrogen with hydrogenating upgrading catalyst or hydrogenating cracking catalyst first, contacting the unseparated reaction effluent with pour point reducing hydrocatalyst feeding the cooled reaction product into high pressure separator to separate liquid product further flowing to the fractionating system and returning the hydrogen-rich gas to reactor. The said method can raise the cetane number of diesel oil and lower the solidifying point simultaneously in the same equipment.
Description
Technical field
The invention belongs to a kind ofly in the method that has under the situation of hydrogen refining hydrocarbon ils, more particularly, is a kind of method of hydrotreating that improves diesel cetane-number, reduces condensation point of diesel oil.
Background technology
Along with the environmental consciousness enhancing of global range, many countries have especially formulated strict standard to motor spirit to petroleum products.China can not make an exception, and except that the new gasoline of having put into effect, diesel product specification, can predict in the near future and will have product up-gradation action faster.For diesel product, the variation of sulphur content and cetane value stands in the breach in the quality index.
In addition, along with China's rapid economic development, society's economic behaviour in winter is active day by day, and market will increase sharply to the demand of low-coagulation diesel oil; The Northeast that China is vast, along with adjustment, recovery and the development of large-area economic structure, winter is to low-coagulation diesel oil, and especially the demand to the low-coagulation diesel oil of condensation point＜-35 ℃ also will increase considerably.Along with the significantly investment of country to highway, will promote the intercommunication significantly of north and south in winter, thing goods and materials, this also can promote the demand of low-coagulation diesel oil, and along with the great development of western (nine provinces, a municipality directly under the Central Government), winter, the demand to low-coagulation diesel oil also can increase.
From China's diesel oil demand trend, in recent years, China's low-sulfur, high hexadecane value, the low engine diesel oil that coagulates will face short possibility, and with existing refinery flowage structure, can't address this problem.Therefore, must change existing work flow, employ new technology or carry out the combination of original technology.
As everyone knows, China's catalytic cracking diesel oil proportion is very high.The characteristics of catalytic cracking diesel oil generally are foreign matter content height such as density height, aromaticity content height, sulphur nitrogen, cetane index is low, stability is poor, can not directly dispatch from the factory as processed oil.After normally passing through hydrofining, and after being in harmonious proportion with straight-run diesel oil, could satisfy existing diesel oil national standard.And general catalytic cracking diesel oil condensation point height, even also can't reach the low-coagulation diesel oil standard through hydrofining.
At the high-sulfur nitrogen of catalytic cracking diesel oil, high aromatic hydrocarbons, low cetane value, can adopt existing MHUG technology to solve.This technology adopts Hydrobon catalyst and two doses of series connection of hydrocracking catalyst once by flow process, in depress operation, make and urge bavin or urge the bavin and the impurity major parts such as sulphur nitrogen of straight bavin mixing raw material to remove, density reduces, cetane value improves.
And, can adopt existing hydrodewaxing (being also referred to as Hydrodewaxing) technology (being called hydrodewaxing abroad) to solve for the high problem of condensation point of diesel oil.This technology was carried out commerical test first by Mobil company in 1974, realized industrialization in 1978, and its technical name is abbreviated as MDDW (Mobil Distillate Dewaxing).Used pour point depression catalyzer is a carrier with the ZSM-5 molecular sieve, and is loaded with little metal, and the anti-sulphur of this catalyzer, anti-nitrogen and shape slective cracking are very capable.Brief description of the process is as follows: stock oil and hydrogen are mixed into process furnace, be heated to specified temperature and enter that product behind reactor, the pour point depression separates in high-pressure separator with hydrogen, hydrogen recycle is used, generate oil and enter separation column, fractionate out gasoline and diesel oil distillate respectively.The catalyst runs cycle of MDDW is short, must carry out coke burning regeneration behind the inactivation, and shut-down regeneration can bring unnecessary financial loss.Therefore in order to guarantee that Hydrodewaxing catalyst can be activity stabilized for a long time, improve quality product simultaneously, add a hydrofining section usually in its front.Hydrofining and hydrodewaxing combination process have some reports.
CN1257107A discloses a kind of method of producing high-grade low-freezing diesel oil by distillate, is that hydrofining is directly connected with hydrodewaxing.Distillate carries out hydrofining earlier, enters the hydrodewaxing reaction bed then.Hydrobon catalyst and Hydrodewaxing catalyst can be in same reactor two different beds, also can be in placed in-line two different reactors.The NiO content of its Hydrobon catalyst is higher, and the anti-coking performance is good; Hydrodewaxing catalyst is acid suitable, anti-NH
3And H
2S.Although hydrofining and hydrodewaxing combination process can prolong the pour point depression life of catalyst, and remove impurity such as sulphur, nitrogen in the distillate, improve its oxidation stability to a certain extent, can not effectively improve diesel-fuel cetane number.
USP4,409,130 disclose a kind of method that improves catalyst stability.Mix or layering filling (Hydrobon catalyst places on the pour point depression catalyzer) by Hydrobon catalyst and dewaxing catalyst (or hydrogenation conversion catalyst), can effectively prolong catalyzer work-ing life.
USP4,917,789 disclose a kind of catalysis pour point depression technology, and operational path is: distillate faces the hydrogen dewaxing more earlier by after the hydrotreatment desulfurization, after perhaps facing hydrogen earlier and dewaxing, carries out the hydrotreatment desulfurization again.
Above-mentioned problems of the prior art are, can not improve diesel-fuel cetane number simultaneously and reduce the condensation point of diesel oil.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of combined hydrogenation method of producing high hexadecane value, low-coagulation diesel oil.
Method provided by the invention adopts the single hop one-pass flow process of connecting, and stock oil is earlier through hydro-upgrading or hydrocracking, and effluent carries out hydrodewaxing without separation.Catalyst for hydro-upgrading or hydrocracking catalyst can be seated in the interior different beds of same reactor with Hydrodewaxing catalyst, also can be seated in two reactors respectively.Catalyst for hydro-upgrading or hydrocracking catalyst can be adjusted in 25: 75～75: 25 scope with the admission space ratio of Hydrodewaxing catalyst.
Method provided by the invention can improve diesel-fuel cetane number simultaneously and reduce the condensation point of diesel oil in same set of device.
Embodiment
Method provided by the invention comprises:
With the stock oil of sulfur-bearing, nitrogen and polycyclic aromatic hydrocarbons with hydrogen at the best 4.5～10.0MPa of hydrogen dividing potential drop 3.0～12.0MPa, average reaction temperature is 300～420 ℃ best 330～390 ℃, stock liquid hourly space velocity LHSV 0.1～5.0hr
-1Best 0.3～3.0hr
-1, contacting with catalyst for hydro-upgrading or hydrocracking catalyst under the condition of the best 400～1000v/v of hydrogen-oil ratio 200～1200v/v, reaction effluent does not separate hydrogen sulfide and ammonia, directly contacts with Hydrodewaxing catalyst according to above-mentioned same reaction conditions.Reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous gas circulation is returned reactor.
Used stock oil is the mixture of catalytic cracking diesel oil or catalytic cracking diesel oil and straight-run diesel oil among the present invention.Generally between 150～450 ℃, density is 0.8～0.95g/cm to the boiling range of stock oil
3, so the present invention is applicable to the mixture of almost various types of catalytic cracking diesel oils or catalytic cracking diesel oil and straight-run diesel oil.Because catalyst for hydro-upgrading or hydrocracking catalyst that the present invention uses have good anti-sulphur, anti-nitrogen ability, therefore sulphur content can be up to 1.2m% in the stock oil, nitrogen content can be up to 2000ppm, but in order to prolong the running period of catalyzer, the nitrogen content of stock oil preferably is controlled at ≯ 1000ppm, sulphur content preferably is controlled at 5000ppm, can guarantee that like this catalyzer is not less than 6 years entire life before regeneration; Again because the Hydrodewaxing catalyst that the present invention uses also has good anti-nitrogen ability, so the nitrogen content in the pour point depression section feeding can allow up to 200ppm, preferably less than 100ppm.
Catalyst for hydro-upgrading that uses among the present invention or hydrocracking catalyst are a kind of VIB and/or VIII family non-precious metal catalyst that loads on the molecular sieve.Because this catalyzer has the saturated and open loop cracking performance of good aromatic hydrocarbons, so be used to the hydrotreatment of the mixture of the higher catalytic cracking diesel oil of aromaticity content or catalytic cracking diesel oil and straight-run diesel oil, can significantly reduce product density, improve cetane value, simultaneously impurity such as the sulphur in the effective elimination raw material, nitrogen.This catalyzer has good anti-sulphur, anti-nitrogen ability simultaneously.
The Hydrodewaxing catalyst that uses among the present invention is a small amount of VIII family hydrogenation/dehydrogenation non-precious metal catalyst on a kind of ZSM-5 of loading on molecular sieve.This catalyst activity height can reduce the product condensation point significantly; Cracking has good selectivity to straight-chain paraffin, and the product gas yield is low; Have, this catalyzer can anti-sulphur, easy poisoning material such as nitrogen, so refining after product without separation, can feed this beds, and loss of activity is very slow, can guarantee at least two years first running periods again.Catalyst for hydro-upgrading or hydrocracking catalyst can be adjusted in 25: 75～75: 25 scope with the admission space ratio of Hydrodewaxing catalyst.
If stock oil character is relatively poor as the carbon residue content height; for falling, the pressure that prevents beds reaches limit value too quickly; can before catalyst for hydro-upgrading or hydrocracking catalyst, add a certain amount of protective material with the running of assurance device long period ground; protectant add-on is generally 1～30% of catalyst for hydro-upgrading or hydrocracking catalyst volume, decides according to raw material properties.Protective material can use one or both.
In the hydrodewaxing bed, can generate a spot of mercaptan and easy polymeric material in the reaction process, therefore at a spot of back of filling, Hydrodewaxing catalyst back finishing agent, guarantee that the product stability is good, back finishing agent loadings is not higher than the 30vol.% of Hydrodewaxing catalyst.Back finishing agent loadings can be regulated by the requirement of product property.
By method provided by the invention, the distillation of gained full distillate oil is obtained raw gasline and diesel product.Cutting temperature can be arbitrary temperature between 150～200 ℃ between raw gasline and the diesel oil.Diesel yield is higher than 85m%, and sulphur content is lower than 50ppm, and cetane value improves at least 6 units with respect to stock oil, and the condensation point of diesel oil reduces significantly.
Method advantage provided by the invention is:
1, the present invention adopts a kind of hydrocracking catalyst and the series connection of a kind of Hydrodewaxing catalyst once to pass through flow process, realized in same set of device, just reaching desulfurization, denitrogenation, aromatic hydrocarbons is saturated and the multiple purpose of selective paraffin cracking, thereby direct production goes out the low-coagulation diesel oil of low-sulfur, high hexadecane value.
2, good quality of product of the present invention, product distribute desirable: diesel product sulphur, nitrogen content are low, and oxidation stability is good, the cetane value height, and condensation point and cold filter clogging temperature are low, are high-grade low-freezing diesel oil, and the diesel quality yield is not less than 85%; Naphtha product sulphur, nitrogen content are low, and virtue is dived high, is good reformer feed.
3, the hydrocracking catalyst that uses among the present invention has well anti-, sulphur nitrogen ability, so can directly process the stock oil of foreign matter contents such as high-sulfur, nitrogen; After the hydrocracking section, impurity such as organosulfur, nitrogen major part is removed in the raw material, has prolonged the running period of Hydrodewaxing catalyst greatly.
4, the present invention can carry out the flexible of production decision according to the variation of temperature in season.Can produce high-grade low-freezing diesel oil-10 ,-20 and-No. 35 by hydro-upgrading and hydrodewaxing process combination.
The following examples will give further instruction to present method, but therefore not limit present method.
Used stock oil A, B, C is respectively the mixture of catalytic cracking diesel oil, catalytic cracking diesel oil, catalytic cracking diesel oil and straight-run diesel oil among the embodiment, and its character is as shown in table 1.
Embodiment 1
Is 360 ℃, liquid hourly space velocity LHSV 1.2hr with hydrogen in hydrogen dividing potential drop 6.4MPa, temperature of reaction with stock oil A
-1, hydrogen-oil ratio 700v/v condition under contact with catalyst for hydro-upgrading RIC-1 (producing) by Changling Refinery Chemical Industry Co., Ltd. of China Petrochemical Industry catalyst plant, reaction effluent does not separate hydrogen sulfide and ammonia, is 360 ℃, liquid hourly space velocity LHSV 2.0hr in hydrogen dividing potential drop 6.4MPa, temperature of reaction
-1, hydrogen-oil ratio 700v/v condition under contact with Hydrodewaxing catalyst RDW-1 (produced by Changling Refinery Chemical Industry Co., Ltd. of China Petrochemical Industry catalyst plant, following Comparative Examples is identical with the used Hydrodewaxing catalyst of embodiment).The reaction effluent that comes out from the hydrodewaxing section enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous hydrogen recycle is returned reactor.
Processing condition, product distribute and product property is listed in table 2.By table 2 as seen, the cetane value of diesel product is 41.5, improves 6.3 units than stock oil A; The condensation point of diesel product is-38 ℃, reduces by 49 ℃ than stock oil A, and the condensation point of diesel product meets the requirement of-No. 35 low-coagulation diesel oils.
Comparative Examples 1
Compare with embodiment 1, first section is hydrofining rather than hydro-upgrading in the Comparative Examples 1, and second section also is hydrodewaxing.
Is 357 ℃, liquid hourly space velocity LHSV 1.2hr with hydrogen in hydrogen dividing potential drop 6.4MPa, temperature of reaction with stock oil A
-1, hydrogen-oil ratio 700v/v condition under contact with catalyst for hydro-upgrading RIC-1, reaction effluent does not separate hydrogen sulfide and ammonia, is 357 ℃, liquid hourly space velocity LHSV 2.0hr in hydrogen dividing potential drop 6.4MPa, temperature of reaction
-1, hydrogen-oil ratio 700v/v condition under contact with Hydrodewaxing catalyst RDW-1.The reaction effluent that comes out from the hydrodewaxing section enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous hydrogen recycle is returned reactor.
Processing condition, product distribute and product property is listed in table 2.By table 2 as seen, though the condensation point of diesel product is-31 ℃, the cetane value of diesel product only is 37.7, than embodiment 1 low 3.8 units.
Comparative Examples 2
Compare with embodiment 1, first section is hydrofining rather than hydro-upgrading in the Comparative Examples 2, and second section also is hydrodewaxing.
Is 357 ℃, liquid hourly space velocity LHSV 1.2hr with hydrogen in hydrogen dividing potential drop 6.4MPa, temperature of reaction with stock oil A
-1, hydrogen-oil ratio 700v/v condition under contact with catalyst for hydro-upgrading RIC-1, reaction effluent does not separate hydrogen sulfide and ammonia, is 362 ℃, liquid hourly space velocity LHSV 2.0hr in hydrogen dividing potential drop 6.4MPa, temperature of reaction
-1, hydrogen-oil ratio 700v/v condition under contact with Hydrodewaxing catalyst RDW-1.The reaction effluent that comes out from the hydrodewaxing section enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous hydrogen recycle is returned reactor.
Processing condition, product distribute and product property is listed in table 2.By table 2 as seen, though the condensation point of diesel product is low to moderate-46 ℃, the cetane value of diesel product only is 36.8, than embodiment 1 low 4.7 units.
Embodiment 2
Is 350 ℃, liquid hourly space velocity LHSV 1.2hr with hydrogen in hydrogen dividing potential drop 6.4MPa, temperature of reaction with stock oil B
-1, hydrogen-oil ratio 700v/v condition under contact with hydrocracking catalyst RT-1 (producing) by Changling Refinery Chemical Industry Co., Ltd. of China Petrochemical Industry catalyst plant, reaction effluent does not separate hydrogen sulfide and ammonia, is 335 ℃, liquid hourly space velocity LHSV 2.0hr in hydrogen dividing potential drop 6.4MPa, temperature of reaction
-1, hydrogen-oil ratio 700v/v condition under contact with Hydrodewaxing catalyst RDW-1.The reaction effluent that comes out from the hydrodewaxing section enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous hydrogen recycle is returned reactor.
Processing condition, product distribute and product property is listed in table 3.By table 3 as seen, the cetane value of diesel product is 43.3, improves 10.0 units than stock oil B; The condensation point of diesel product is-40 ℃, reduces by 30 ℃ than stock oil B, and the condensation point of diesel product meets the requirement of-No. 35 low-coagulation diesel oils.
Embodiment 3
Is 350 ℃, liquid hourly space velocity LHSV 1.2hr with hydrogen in hydrogen dividing potential drop 6.4MPa, temperature of reaction with stock oil B
-1, hydrogen-oil ratio 700v/v condition under contact with hydrocracking catalyst RT-1, reaction effluent does not separate hydrogen sulfide and ammonia, is 340 ℃, liquid hourly space velocity LHSV 2.0hr in hydrogen dividing potential drop 6.4MPa, temperature of reaction
-1, hydrogen-oil ratio 700v/v condition under contact with Hydrodewaxing catalyst RDW-1.The reaction effluent that comes out from the hydrodewaxing section enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous hydrogen recycle is returned reactor.
Processing condition, product distribute and product property is listed in table 3.By table 3 as seen, the cetane value of diesel product is 41.6, improves 8.3 units than stock oil B; The condensation point of diesel product is lower than-50 ℃, and the condensation point of diesel product meets the requirement of-No. 50 low-coagulation diesel oils.
Embodiment 4
Is 350 ℃, liquid hourly space velocity LHSV 1.2hr with hydrogen in hydrogen dividing potential drop 8.0MPa, temperature of reaction with stock oil B
-1, hydrogen-oil ratio 700v/v condition under contact with hydrocracking catalyst RT-1, reaction effluent does not separate hydrogen sulfide and ammonia, is 335 ℃, liquid hourly space velocity LHSV 2.0hr in hydrogen dividing potential drop 8.0MPa, temperature of reaction
-1, hydrogen-oil ratio 700v/v condition under contact with Hydrodewaxing catalyst RDW-1.The reaction effluent that comes out from the hydrodewaxing section enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous hydrogen recycle is returned reactor.
Processing condition, product distribute and product property is listed in table 3.By table 3 as seen, the cetane value of diesel product is 46.6, improves 13.3 units than stock oil B; The condensation point of diesel product is-31 ℃, reduces by 21 ℃ than stock oil B, and the condensation point of diesel product meets the requirement of-No. 20 low-coagulation diesel oils.
Embodiment 5
Is 350 ℃, liquid hourly space velocity LHSV 1.2hr with hydrogen in hydrogen dividing potential drop 6.4MPa, temperature of reaction with stock oil C
-1, hydrogen-oil ratio 700v/v condition under contact with hydrocracking catalyst RT-1, reaction effluent does not separate hydrogen sulfide and ammonia, is 350 ℃, liquid hourly space velocity LHSV 2.0hr in hydrogen dividing potential drop 6.4MPa, temperature of reaction
-1, hydrogen-oil ratio 700v/v condition under contact with Hydrodewaxing catalyst RDW-1.The reaction effluent that comes out from the hydrodewaxing section enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous hydrogen recycle is returned reactor.
Processing condition, product distribute and product property is listed in table 3.By table 3 as seen, the cetane value of diesel product is 41.2, improves 6.4 units than stock oil C; The condensation point of diesel product is-42 ℃, reduces by 39 ℃ than stock oil C, and the condensation point of diesel product meets the requirement of-No. 35 low-coagulation diesel oils.
Table 1
| The stock oil numbering | ????A | ????B | ????C |
| Density (20 ℃), g/cm 3 | ????0.8827 | ????0.8666 | ????0.8608 |
| Refractive power, n d 20 | ????1.5062 | ????1.4872 | ????1.4915 |
| Sulphur, ppm | ????1212 | ????967 | ????1034 |
| Nitrogen, ppm | ????796 | ????495 | ????724 |
| Condensation point, ℃ | ????11 | ????-10 | ????-3 |
| Cold filter clogging temperature, ℃ | ????12 | ????-5 | ????- |
| Aniline point, ℃ | ????49.1 | ????47.7 | ????- |
| Boiling range D-86, ℃ | |||
| Initial boiling point/5% | ????193/211 | ????183/196 | ????179/193 |
| 10％/20％ | ????222/235 | ????207/220 | ????202/- |
| 30％/50％ | ????250/280 | ????233/256 | ????226/252 |
| 70％/80％ | ????329/353 | ????286/304 | ????296/- |
| 90%/do | ????375/394 | ????327/361 | ????340/365 |
| Cetane index D4737 | ????39.4 | ????38.7 | ????40.3 |
| Cetane value (actual measurement) | ????35.2 | ????33.3 | ????34.8 |
Table 2
| Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | |
| Stock oil | ????A | ????A | ????A |
| Processing condition: hydrogen dividing potential drop, the MPa temperature of reaction, ℃ volume space velocity, h -1Hydrogen-oil ratio, Nm 3/m 3 | ????6.4 ????360/360 ????1.2/2.0 ????700 | ????6.4 ????357/357 ????1.5/2.0 ????700 | ????6.4 ????357/362 ????1.5/2.0 ????700 |
| Product distributes: raw gasline diesel oil | ????8.18 ????91.82 | ????9.69 ????87.42 | ????10.57 ????85.90 |
| Product property: density (20 ℃), g/cm 3Refractive power, n d 20Sulphur, ppm nitrogen, ppm viscosity (20 ℃), mm 2/ s condensation point, ℃ cold filter clogging temperature, ℃ aniline point, ℃ aromatic hydrocarbons, the m% close flash point, ℃ color (D1500), look bromine valency, gBr/100g acidity, mgKOH/100ml 10% carbon residue, m% boiling range ASTM D-86, ℃ initial boiling point/5% 10%/20% 30%/50% 70%/80% 90%/do cetane index cetane value | ????0.8488 ????1.4685 ????2.0 ????0.9 ????3.944 ????-38 ????-41 ????55.8 ????-- ????74 ????＜2.0 ????0.34 ????0.95 ????0.04 ????187/201 ????209/219 ????229/250 ????292/320 ????361/396 ????44.4 ????41.5 | ????0.8662 ????1.4844 ????3.3 ????5.6 ????4.304 ????-31 ????-26 ????50.2 ????43.4 ????61 ????＜2.0 ????0.62 ????0.99 ????0.08 ????190/204 ????212/222 ????232/253 ????295/321 ????357/394 ????40.6 ????37.7 | ????0.8685 ????1.4860 ????4.1 ????6.3 ????4.175 ????-46 ????-42 ????47.4 ????46.3 ????68 ????＜2.0 ????0.59 ????1.11 ????0.08 ????187/201 ????210/221 ????231/251 ????292/319 ????355/395 ????39.6 ????36.8 |
Table 3
| The embodiment numbering | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Stock oil | ????B | ????B | ????B | ????C |
| Processing condition: hydrogen dividing potential drop, the MPa temperature of reaction, ℃ volume space velocity, h -1Hydrogen-oil ratio, Nm 3/m 3 | ????6.4 ????350/335 ????1.2/2.0 ????700 | ????6.4 ????350/340 ????1.2/2.0 ????700 | ????8.0 ????350/335 ????1.2/2.0 ????700 | ????6.4 ????350/350 ????1.2/2.0 ????700 |
| Product distributes: raw gasline diesel oil | ????7.100 ????92.603 | ????7.644 ????91.759 | ????6.969 ????92.332 | ????6.875 ????93.125 |
| Product property: density (20 ℃), g/cm 3Refractive power, n d 20Sulphur, ppm nitrogen, the ppm condensation point, ℃ cold filter clogging temperature, ℃ aniline point, ℃ close flash point, ℃ viscosity (20 ℃), mm 2/ s acidity; MgKOH/100ml boiling range ASTM D-86, ℃ initial boiling point/5% 10%/20% 30%/50% 70%/80% 90%/do Cetane lndex Cetane number | ????0.8432 ????1.4655 ????1.0 ????0.5 ????-40 ????-21 ????61.3 ????71 ????3.478 ????1.14 ????180/192 ????200/211 ????221/240 ????266/281 ????305/345 ????42.3 ????43.3 | ????0.8444 ????1.4660 ????0.8 ????0.4 ????＜-50 ????-40 ????60.3 ????70 ????3.040 ????1.27 ????180/192 ????200/210 ????220/239 ????264/279 ????302/341 ????41.6 ????41.6 | ????0.8390 ????1.4617 ????0.8 ????0.4 ????-31 ????-13 ????66.2 ????68 ????3.588 ????1.02 ????180/193 ????202/212 ????223/243 ????269/285 ????308/349 ????44.4 ????46.6 | ????0.8358 ????1.4657 ????1.4 ????0.8 ????-42 ????-21 ????57.5 ????67 ????3.040 ????0.88 ????176/189 ????196/205 ????214/232 ????268/289 ????317/356 ????43.6 ????41.2 |
Claims (7)
1, a kind of combined hydrogenation method of producing high hexadecane value, low-coagulation diesel oil, it is characterized in that stock oil, hydrogen contact with catalyst for hydro-upgrading or hydrocracking catalyst earlier, reaction effluent then contacts with Hydrodewaxing catalyst without separating, reaction effluent enters high-pressure separator through cooling, isolated product liquid enters fractionating system, and rich hydrogenous gas circulation is returned reactor.
2, according to the method for claim 1, it is characterized in that described stock oil is the mixture of catalytic cracking diesel oil or catalytic cracking diesel oil and straight-run diesel oil, the boiling range of stock oil is between 150～450 ℃, and density is 0.8～0.95g/cm
3
3, according to the method for claim 1, it is characterized in that the condition of hydro-upgrading or hydrocracking, hydrodewaxing is: hydrogen dividing potential drop 3.0～12.0MPa, temperature of reaction is 300～420 ℃, liquid hourly space velocity 0.1～5.0hr
-1, hydrogen-oil ratio 200～1200v/v.
4, according to the method for claim 3, it is characterized in that the condition of hydro-upgrading or hydrocracking, hydrodewaxing is: hydrogen dividing potential drop 4.5～10.0MPa, temperature of reaction is 330～390 ℃, liquid hourly space velocity 0.3～3.0hr
-1, hydrogen-oil ratio 400～1000v/v.
5,, it is characterized in that described catalyst for hydro-upgrading or hydrocracking catalyst are a kind of VIB and/or VIII family non-precious metal catalyst that loads on the molecular sieve according to the method for claim 1.
6,, it is characterized in that described Hydrodewaxing catalyst is a small amount of VIII family hydrogenation/dehydrogenation non-precious metal catalyst on a kind of ZSM-5 of loading on molecular sieve according to the method for claim 1.
7, according to claim 1,5 or 6 method, it is characterized in that described catalyst for hydro-upgrading or hydrocracking catalyst and the admission space ratio of Hydrodewaxing catalyst are 25: 75～75: 25.
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| CNB011342714A CN1171976C (en) | 2001-10-30 | 2001-10-30 | Combined hydrogenation method of producing diesel oil with high cetane number and low solidifying point |
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| CNB011342714A CN1171976C (en) | 2001-10-30 | 2001-10-30 | Combined hydrogenation method of producing diesel oil with high cetane number and low solidifying point |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092575B (en) * | 2006-06-22 | 2011-08-10 | 中国石油化工股份有限公司 | Method for producing diesel oil with low sulphur and low arene |
| CN103805268A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing clean diesel oil with low condensation point by treating inferior diesel oil |
| CN103805237A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
| CN103805238A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low condensation point by gradation technology |
| CN103805270A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of low-condensation point diesel oil |
| CN103805262A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of diesel oil with low condensation point |
| CN104611033A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low freezing point |
| CN104611043A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Low freezing point diesel fuel production method |
| CN103805255B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyzer grating technology is utilized to produce the method for hydrogenation low-coagulation diesel oil |
| CN103805258B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of combined technical method producing low freezing point diesel oil |
| CN103805254B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of combined technical method of low freezing point diesel production |
| CN107177375A (en) * | 2016-03-10 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of straight-run diesel oil produces the method for hydrogen cracking of jet fuel |
| CN107177376A (en) * | 2016-03-10 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
| CN107177377A (en) * | 2016-03-10 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of method of straight-run diesel oil HYDROGENATED JET FUEL |
| CN107177374A (en) * | 2016-03-10 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil produces jet fuel |
| CN107345164A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
-
2001
- 2001-10-30 CN CNB011342714A patent/CN1171976C/en not_active Expired - Lifetime
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092575B (en) * | 2006-06-22 | 2011-08-10 | 中国石油化工股份有限公司 | Method for producing diesel oil with low sulphur and low arene |
| CN103805268B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of poor ignition quality fuel that processes produces the method cleaning low-coagulation diesel oil |
| CN103805237A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
| CN103805238A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low condensation point by gradation technology |
| CN103805270A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of low-condensation point diesel oil |
| CN103805262A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of diesel oil with low condensation point |
| CN103805254B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of combined technical method of low freezing point diesel production |
| CN103805268A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing clean diesel oil with low condensation point by treating inferior diesel oil |
| CN103805238B (en) * | 2012-11-07 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of grating technology produces the method for hydrogenation low-coagulation diesel oil |
| CN103805237B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of method utilizing catalyzer grating technology to produce low-coagulation diesel oil |
| CN103805262B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | The production method of low-coagulation diesel oil |
| CN103805255B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyzer grating technology is utilized to produce the method for hydrogenation low-coagulation diesel oil |
| CN103805258B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of combined technical method producing low freezing point diesel oil |
| CN103805270B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of production method of low-coagulation diesel oil |
| CN104611043A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Low freezing point diesel fuel production method |
| CN104611033A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low freezing point |
| CN104611033B (en) * | 2013-11-05 | 2016-08-17 | 中国石油化工股份有限公司 | The method producing hydrogenation low-coagulation diesel oil |
| CN104611043B (en) * | 2013-11-05 | 2016-11-16 | 中国石油化工股份有限公司 | The production method of low-coagulation diesel oil |
| CN107177374A (en) * | 2016-03-10 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil produces jet fuel |
| CN107177376A (en) * | 2016-03-10 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
| CN107177377A (en) * | 2016-03-10 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of method of straight-run diesel oil HYDROGENATED JET FUEL |
| CN107177375A (en) * | 2016-03-10 | 2017-09-19 | 中国石油化工股份有限公司 | A kind of straight-run diesel oil produces the method for hydrogen cracking of jet fuel |
| CN107177377B (en) * | 2016-03-10 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of method of straight-run diesel oil HYDROGENATED JET FUEL |
| CN107177376B (en) * | 2016-03-10 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
| CN107177374B (en) * | 2016-03-10 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of method of straight-run diesel oil production jet fuel |
| CN107177375B (en) * | 2016-03-10 | 2020-10-16 | 中国石油化工股份有限公司 | Hydrocracking method for producing jet fuel from straight-run diesel oil |
| CN107345164A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
| CN107345164B (en) * | 2016-05-05 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
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