CN101412926B - Hydro-upgrading combined method - Google Patents
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- CN101412926B CN101412926B CN 200810134139 CN200810134139A CN101412926B CN 101412926 B CN101412926 B CN 101412926B CN 200810134139 CN200810134139 CN 200810134139 CN 200810134139 A CN200810134139 A CN 200810134139A CN 101412926 B CN101412926 B CN 101412926B
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Abstract
The invention discloses a hydroprocessing and upgrading integration method, in particular a wax oil hydroprocessing and diesel hydroupgrading integration process. The method comprises the following steps: raw wax oil passes through a first reaction zone in the presence of hydrogen first, liquid obtained after separation of products is taken as catalytic cracking raw materia; the gas phase obtained through separation is mixed with diesel raw material to enter a second reaction zone; and gas after separation of products in the second reaction zone is recycled after desulfurization, and liquid obtained after separation is subjected to fractionation to obtain hydrogenant naphtha and hydrogenant diesel. The method aims at technical characteristics of wax oil hydroprocessing and hydroupgrading, integrates the two technologies for application, simplifies process flow, and reduces equipment, investment and operating cost at the same time of reaching high product quality. The method is applied to newly built equipment to reduce equipment investment and applied to expanding reformation of the prior devices.
Description
Technical field
The present invention relates to a kind of hydro-upgrading combined method, particularly wax oil hydrogenation is processed and the diesel oil hydrogenation modification combined method.
Background technology
The sustainable development of world economy and the increasingly stringent of environmental regulation need to produce a large amount of light clean fuels at present, and these all require existing oil Refining Technologies is improved, and produce satisfactory product with minimum cost.Along with the worsening shortages of crude resources and heaviness, in poor quality development, catalytic cracking (FCC) and coking become the important means of production light Fuel product, but the quality product that these two kinds of techniques obtain generally is difficult to the finger figureofmerit requirement that reaches strict.In the light Fuel quality product system, sulphur content is most important index, how to reduce sulphur content in the petroleum products and be one of most significant problems that current refining of petroleum industry faces, the cetane value of diesel product receives publicity always in addition, and its specification requirement is also more and more stricter.At present, be applied widely in Clean Fuel Production take desulfurization and upgrading as the main purpose hydrogenation technique.Such as the hydrogenation preconditioning technique of catalytically cracked material, light hydrocarbons (such as diesel oil distillate) hydro-upgrading technology etc.
Wherein diesel oil fraction hydrogenating modification technology main purpose is to improve the quality product of diesel oil, existing diesel oil hydrogenation modification such as CN1156752A and CN1289832A etc., although can increase substantially diesel-fuel cetane number and reduce the foreign matter contents such as sulphur, nitrogen, this technology is only applicable to the diesel raw material that cetane value is low, aromaticity content is high.
FCC raw material hydrogenation preconditioning technique can be avoided loss of octane number in the catalytic gasoline hydrogenation treating process, and has following advantage: the replacing speed that can reduce the FCC catalyzer; Reduce the FCC coke yield; Improving the FCC product distributes, improves the purpose product yield, reduces non-purpose product yield; Directly improve the FCC quality product, reduce the product sulphur content; Reduce the quantity discharged of FCC revivifier SOx, NOx etc., so FCC raw material hydrogenation pretreatment technology is widely used in modern refineries.Existing catalytically cracked material preconditioning technique mainly contains: US3983029 and US6793804 disclose hydroprocessing technique and catalyzer, CN1313379 discloses a kind of hydroprocessing process of poor-quality raw material for catalytic cracking, and CN1646665 discloses the hydrotreatment of hydrocarbon raw material.
Wax oil hydrogenation processing and two kinds of technological processs of diesel oil hydrogenation modification are independent operation in the prior art, although can satisfy the purpose requirement, because two cover processing unit (plant)s are fully independent, each own independently equipment and pipeline, certainly will cause total investment expenses high, the high deficiency of process cost.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of for wax oil hydrogenation desulfurization and diesel oil hydrogenation modification combination process, can produce on the basis of reducing to greatest extent construction investment qualified diesel product and fine quality catalytic cracking raw material oil.
A kind of hydro-upgrading combined method, raw material comprise wax oil feedstock and diesel oil distillate oil raw material, comprise the steps:
A, under the hydrotreatment operational condition, wax oil stock oil is through the hydrotreating catalyst bed, the hydrotreatment reaction effluent separates in high pressure hot separator and obtains gas phase and liquid phase, gas phase comprises hydrogen and light hydrocarbons, liquid phase is the hydrogenation wax oil;
B, under the hydro-upgrading operational condition, diesel raw material oil mixes with the gas phase that step a obtains and passes through the catalyst for hydro-upgrading bed; Catalyst for hydro-upgrading is the catalyst for hydro-upgrading that contains modified Y molecular sieve;
C, step b reaction effluent enter gas-liquid separator, and gas phase recycles behind depriving hydrogen sulphide, and liquid phase enters the fractionating system fractionation and obtains various hydrocarbon productss.
It is 350～620 ℃ of heavy endss that the described wax oil stock oil of step a generally comprises boiling range, as being one or more in the various vacuum gas oils (VGO) that obtain in the petroleum refining process, deasphalted oil (DAO), coker gas oil (CGO), heavy cycle oil (HCO) etc., also can be from coal tar, gelatin liquefaction wet goods.
The described hydrotreating catalyst of step a is conventional hydrotreating catalyst, can be various commercial catalysts, as Fushun Petrochemical Research Institute (FRIPP) development and production 3926,3936, the hydrotreating catalyst such as CH-20,3996, FF-14, FF-16, FF-18, FF-26, the catalyzer such as HR-416, HR-448 of Compaynie Francaise des Petroles (IFP), the TK-525 of Denmark Tuo Pusuo company (Topsor), TK-557 catalyzer, KF-752, the KF-840 of He Lan AKZO N. V (AKZO), KF-901, KF-907 etc.The FH-FS of bulk phase catalyst such as Fushun Petrochemical Research Institute (FRIPP) development and production etc.Above-mentioned hydrotreating catalyst also can be prepared by this area knowledge, common hydrotreating catalyst (loaded catalyst, active metallic content is relatively low, generally count 20%～45% with oxide compound) general first Kaolinite Preparation of Catalyst carrier, then use pickling process supported active metal component, bulk phase catalyst (active metallic content is high, generally counts 50%～85% with oxide compound) generally adopts the coprecipitation method preparation.
The described hydrotreatment operational condition of step a is: reaction pressure 3.0～20.0MPa, hydrogen to oil volume ratio are 200: 1～2500: 1, and volume space velocity is 0.1～8.0h
-1, 260 ℃～455 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 4.0～18.0MPa, hydrogen to oil volume ratio 300: 1～2000: 1, volume space velocity 0.2～6.0h
-1, 280～444 ℃ of temperature of reaction.The working pressure of high pressure hot separator is system pressure, and temperature is generally 180～410 ℃, is preferably 220～390 ℃.Contain the light hydrocarbons that the wax oil hydrogenation treating processes produces in the isolated gas phase of high pressure hot separator, such as diesel oil distillate and gasoline fraction, this light hydrocarbons carries out the diesel oil hydrogenation modification reaction, can obtain quality products.
The described diesel oil of step b can comprise one or more mixing oil of straight-run diesel oil, coker gas oil, catalytic diesel oil, liquefied coal coil light ends etc., also can comprise the light ends such as straight-run spirit, coker gasoline, and its boiling range is generally 64 ℃～390 ℃.
The described catalyst for hydro-upgrading bed of step b can be for using separately catalyst for hydro-upgrading, also can use with the Hydrobon catalyst grating, grating generally is that reaction mass contacts with Hydrobon catalyst first when using, and then contacts with catalyst for hydro-upgrading.Wherein catalyst for hydro-upgrading is the catalyst for hydro-upgrading that contains Modified Zeolite Y, and catalyzer contains WO by weight
315%～30%, NiO or CoO2%～15%, Modified Zeolite Y 10%～45% can contain auxiliary agent such as F simultaneously, and F content is 1%～9% by weight, and carrier is aluminum oxide and/or amorphous aluminum silicide.Wherein Modified Zeolite Y has following character: lattice constant is 2.436～2.444nm, and infrared total acid (160 ℃) is 0.5～1.1mmol/g.Catalyst for hydro-upgrading can the commodity in use catalyzer, such as 3963 catalyzer of Fushun Petrochemical Research Institute's development and production, FC-18 catalyzer etc., also can prepare by this area knowledge.Hydrobon catalyst can adopt the common Hydrobon catalyst in this area, also can adopt high-activity hydrofining catalyst, also can adopt common Hydrobon catalyst and high-activity hydrofining catalyst to be used by suitable way.Catalyzer can be selected the commercial catalysts that suits, such as Hydrobon catalysts such as FH-5A, the FDS-4A of Fushun Petrochemical Research Institute's development and production, FH-98, FH-DS, FH-UDS, or by the existing method preparation in this area.
The described hydro-upgrading operational condition of step b is: stagnation pressure 4.0MPa～18.0MPa, temperature of reaction is 300 ℃～440 ℃, volume space velocity 0.3h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 100: 1～2000: 1.Because hydrotreatment and hydro-upgrading are serial flow, hydro-upgrading is low than hydrotreatment pressure usually, is generally 0.01～2.0MPa.
Compared with prior art, the present invention is by optimization technological process and optimize suitable catalyzer grating and operational condition, and different inferior raw materials are improved the quality of products under optimum, has finally obtained desirable comprehensive process effect.In technical process, the inventive method and two kinds of raw materials add respectively man-hour relatively: the advantage such as have saving equipment (gas-liquid separation equipment, stripping apparatus, compressor etc.), technical process is short, facility investment is low, process cost is low, and also the ability of circulating hydrogen compressor can reduce more than 30%.Wax oil hydrogenation is processed and is adopted hot high score flow process simultaneously, can save cold high score and cold low subset, and two cover systems share hydrogen gas system and desulphurization system, can save make-up hydrogen compressor, circulating hydrogen compressor and a cover desulphurization system.The light hydrocarbons oil product that hydrotreatment obtains directly enters the hydro-upgrading reaction zone, further improves the quality of products, and can save the separation system equipment of this component, has reduced simultaneously energy consumption.
Description of drawings
Fig. 1 is one embodiment of the present invention schematic flow sheets.
Embodiment
At first wax oil hydrogenation is processed stock oil 1 and is mixed into hydrotreating reactor 3 with circulating hydrogen 2, obtains the low hydrotreatment resultants 4 of impurity such as sulfur-bearing, nitrogen.Hydrotreatment resultant 4 separates in high pressure hot separator 5 and obtains liquid hydrogenation wax oil and directly enter catalytic cracking, separates the gas phase (gas phase comprises hydrogen and light hydrocarbons) 7 that obtains and is mixed into hydro-upgrading reactor 9 with hydro-upgrading diesel raw material oil 8.Through series reaction, obtain hydro-upgrading resultant 10.Hydro-upgrading resultant 10 separates the H 2 S-containing gas 12 that obtains and enters de-hydrogen sulfide column 13 in high-pressure separator 11, use with new hydrogen 16 mixed cycle after 15 superchargings of circulation gas 14 process circulating hydrogen compressors behind the depriving hydrogen sulphide that obtains.Separate the liquid 17 that obtains in the high-pressure separator 11 and enter stripping tower 18 (if gasoline fraction is more in 17, can change separation column into), then obtain gas products 19, gasoline (or petroleum naphtha) 20 and diesel product 21.
Use the main character of stock oil to see Table 1, hydrotreatment operational condition and the results are shown in Table 2, hydrofining operational condition and structure see Table 3.
Table 1 stock oil character
| The stock oil title | Stock oil-1 | Stock oil-2 | Stock oil-3 | Stock oil-4 |
| The source | Diesel oil 1 | |
Coking gasoline and diesel | Wax oil |
| Density (20 ℃)/gcm -3 | 0.8762 | 0.9541 | 0.8201 | 0.9126 |
| The boiling range scope, ℃ | 175～370 | 165～375 | 64～357 | 340～550 |
| Sulphur content, wt% | 2.05 | 0.78 | 0.95 | 2.74 |
| Nitrogen content, wt% | 0.06 | 0.09 | 0.07 | 0.09 |
| Cetane value | 37.1 | 19.5 | ||
| Aromaticity content, wt% | 42.3 | 75.1 | 15.9 | 52.5 |
Table 2 hydrotreatment operational condition and result
| Numbering | Embodiment 1 | |
Embodiment 3 | Embodiment 4 |
| Stock oil | Stock oil-4 | Stock oil-4 | Stock oil-4 | Stock oil-4 |
| Catalyzer | FF-14 | FF-14 | FF-18 | FF-18 |
| Reaction pressure/MPa | 8.0 | 6.0 | 15.0 | 12.0 |
| Average reaction temperature/℃ | 370 | 360 | 365 | 350 |
| LHSV/h -1 | 1.5 | 1.2 | 0.8 | 1.8 |
| Hydrogen to oil volume ratio (v/v) | 500∶1 | 700∶1 | 1300∶1 | 800∶1 |
| The high pressure hot separator temperature, ℃ | 260 | 200 | 400 | 300 |
| The wax oil yield, wt% | 93.5 | 94.2 | 88.9 | 91.4 |
| Sulphur content/μ gg -1 | 2000 | 3000 | 300 | 800 |
Table 3 hydro-upgrading operational condition and result
| Numbering | Embodiment 1 | |
Embodiment 3 | Embodiment 4 |
| Stock oil | Stock oil-1 | Stock oil-1 | Stock oil-2 | Stock oil-3 |
| Catalyzer | FH-98/ 3963 | FC-18 | FH-98/ 3963 | FH-98/ FC-18 |
| Catalyst ratio (v/v) | 40/60 | / | 50/50 | 20/80 |
| Reaction pressure/MPa | 7.7 | 5.5 | 14.5 | 11.5 |
| Average reaction temperature/℃ | 360 | 350 | 370 | 364 |
| LHSV/h -1 | 1.8 | 1.3 | 0.8 | 3.5 |
| Hydrogen to oil volume ratio (v/v) | 300∶1 | 600∶1 | 800∶1 | 400∶1 |
| ＜145 ℃ of naphtha fractions | ||||
| Sulphur content/μ gg -1 | ＜5 | ＜5 | ＜5 | ＜5 |
| 〉=145 ℃ of diesel oil distillates | ||||
| Density (20 ℃)/gcm -3 | 0.8285 | 0.8341 | 0.8465 | 0.8204 |
| Sulphur content/μ gg -1 | ＜10 | ＜10 | ＜10 | ＜10 |
| Cetane value | 53.6 | 51.8 | 49.5 | 54.6 |
From above embodiment, can find out, the maximum characteristics of this combination process are, rationally utilize the features of hydroprocessing technique and hydrogenation modifying process technology, when keeping the different device purpose to require, owing to adopted combination process, greatly reduced facility investment and the process cost of device.Simultaneously, the light hydrocarbons that the wax oil hydrogenation treating processes is produced directly enters Diesel Oil Hydrofining Unit behind hot high score, namely can improve the diesel product quality, has saved again separating device, and greatly improved the utilization ratio of heat owing to do not need the air-cooler cooling, reduced plant energy consumption.Owing to adopt the series winding flow process, can reduce the circulating hydrogen compressor load.
Claims (8)
1. hydro-upgrading combined method, raw material comprise wax oil feedstock and diesel oil distillate oil raw material, comprise the steps:
A, under the hydrotreatment operational condition, wax oil stock oil is through the hydrotreating catalyst bed, the hydrotreatment reaction effluent separates in high pressure hot separator and obtains gas phase and liquid phase;
B, under the hydro-upgrading operational condition, diesel raw material oil mixes with the gas phase that step a obtains and passes through the catalyst for hydro-upgrading bed, catalyst for hydro-upgrading is the catalyst for hydro-upgrading that contains modified Y molecular sieve; Wherein modified Y molecular sieve has following character: lattice constant is 2.436～2.444nm, and 160 ℃ of infrared total acids are 0.5～1.1mmol/g;
C, step b reaction effluent enter gas-liquid separator, and gas phase recycles behind depriving hydrogen sulphide, and liquid phase enters the fractionating system fractionation and obtains hydrocarbon products;
Wherein the described diesel raw material oil of step b comprises one or more in straight-run diesel oil, coker gas oil, catalytic diesel oil, the liquefied coal coil light ends, also contains straight-run spirit or coker gasoline in the diesel raw material oil.
2. in accordance with the method for claim 1, it is characterized in that the described wax oil stock oil of step a is one or more in vacuum gas oil, deasphalted oil, coker gas oil, the heavy cycle oil, perhaps from coal tar or liquefied coal coil.
3. in accordance with the method for claim 1, it is characterized in that the described hydrotreatment operational condition of step a is: reaction pressure 3.0～20.0MPa, hydrogen to oil volume ratio are 200: 1～2500: 1, and volume space velocity is 0.1～8.0h
-1, 260 ℃～455 ℃ of temperature of reaction; The high pressure hot separator temperature is 180～410 ℃.
4. in accordance with the method for claim 1, it is characterized in that the described hydrotreatment operational condition of step a is: reaction pressure 4.0～18.0MPa, hydrogen to oil volume ratio 300: 1～2000: 1, volume space velocity 0.2～6.0h
-1, 280～444 ℃ of temperature of reaction, high pressure hot separator temperature are 220～390 ℃.
5. in accordance with the method for claim 1, it is characterized in that containing in high pressure hot separator is told among the step a the gas phase light hydrocarbons that the wax oil hydrogenation treating processes produces.
6. in accordance with the method for claim 1, it is characterized in that the described hydro-upgrading operational condition of step b is: stagnation pressure 4.0MPa～18.0MPa, temperature of reaction is 260 ℃～440 ℃, volume space velocity 0.3h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio is 100: 1～2000: 1.
7. according to claim 1,3 or 6 described methods, it is characterized in that the pressure of step a than the high 0.01～2.0MPa of pressure of step b, being convenient to hydrogen can the tandem circulation.
8. in accordance with the method for claim 1, it is characterized in that step c is described through using with new hydrogen mixed cycle after the supercharging of gas phase process circulating hydrogen compressor behind the depriving hydrogen sulphide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102465030B (en) * | 2010-11-05 | 2014-07-23 | 中国石油化工股份有限公司 | Hydrogenation process combination method |
| CN103074103A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Combined hydrotreating method |
| CN109988650B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrogenation modification and hydrofining combined method for poor diesel oil |
| CN111996035A (en) * | 2020-09-14 | 2020-11-27 | 中国石化北海炼化有限责任公司 | Wax oil hydrogenation upgrading system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260376A (en) * | 1999-03-08 | 2000-07-19 | 中国石化集团洛阳石油化工工程公司 | Converting and combining method for hydrogenation of hydrocarbon |
| CN1458233A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for coking full fraction oil hydrogenation refining |
| US7108779B1 (en) * | 2003-09-25 | 2006-09-19 | Uop Llc | Hydrocarbon desulfurization process |
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- 2008-07-17 CN CN 200810134139 patent/CN101412926B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260376A (en) * | 1999-03-08 | 2000-07-19 | 中国石化集团洛阳石油化工工程公司 | Converting and combining method for hydrogenation of hydrocarbon |
| CN1458233A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for coking full fraction oil hydrogenation refining |
| US7108779B1 (en) * | 2003-09-25 | 2006-09-19 | Uop Llc | Hydrocarbon desulfurization process |
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