CN103773430A - Wax oil hydrotreating method - Google Patents
Wax oil hydrotreating method Download PDFInfo
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- CN103773430A CN103773430A CN201210408518.XA CN201210408518A CN103773430A CN 103773430 A CN103773430 A CN 103773430A CN 201210408518 A CN201210408518 A CN 201210408518A CN 103773430 A CN103773430 A CN 103773430A
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Abstract
The invention relates to a wax oil hydrotreating method. According to the wax oil hydrotreating method, wax oil is mixed with light distillate oil, then enters into a hydrotreating reactor for reaction under the effects of hydrogen and a hydrotreating catalyst; hydrotreated produced oil enters into a cold high-pressure separator for gas-liquid separation, a separated gas phase effluent is cycled for use, a liquid phase effluent enters into a low pressure separator; a liquid phase effluent obtained by the low pressure separator enters into a fractionating tower for separation to obtain gases, gasoline, diesel and tail oil, and the tail oil is used as a raw material for catalytic cracking. According to the method, in the premise of no transformation of an original diesel oil hydrofining unit separation system, the problem of oil and water separation in produced oil can be solved, device investment due to transformation of the cold high-pressure separator into a hot high-pressure separator can be saved, the hydrogen loss can be reduced, operating load of a heating furnace can be reduced, and the device energy consumption can be reduced.
Description
Technical field
The present invention relates to a kind of wax oil hydrogenation treatment process, specifically relate to a kind of wax oil hydrogenation treatment process by Revamping of A Diesel Hydrofining Unit To Gas Oil Hydrotreating Unit.
Background technology
Within the scope of our times, oil property becomes gradually heavy, becomes bad; in addition the sustainable development of world economy and the increasingly stringent of legislations of environmental protection; need to produce a large amount of light clean fuels; these all require existing oil Refining Technologies to improve, and produce satisfactory product with minimum cost.
Produce in the working method of light-end products at heavy feed stock, catalytic cracking (FCC) still accounts for critical role.The light-end products of catalytic cracking technology direct production are second-rate, and especially the sulphur content of catalytic gasoline is higher, and catalytic diesel oil sulphur content and aromaticity content are high, cetane value is low.Therefore, catalytic cracking product does not meet the requirement of clean fuel.In order to improve the quality of catalytic cracking product, need certain processing means, topmost approach has two kinds, i.e. and catalytic cracking generates oil subsidy and fills hydrofining and catalytically cracked material pre-treatment.FCC raw material can be avoided loss of octane number in catalytic gasoline hydrogenation treating process after pretreatment, and also has following advantage: the replacement frequency that can reduce FCC catalyzer; Reduce FCC coke yield; Improving FCC product distributes, improves object product yield, reduces non-object product yield; Directly improve FCC quality product, reduce product sulphur content; Reduce FCC revivifier SO
x, NO
xquantity discharged etc., therefore FCC raw material pretreatment process 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.
Along with the continuous increase of catalytically cracked material demand, Diesel Oil Hydrofining Unit changes VGO and is on the increase, Diesel Oil Hydrofining Unit generally adopts cold high score flow process, and comprise waterflood system at air cooler entrance, the ammonium salt producing for solubilizing reaction process, prevents blocking pipe and air cooler.And VGO adopts hot high score flow process conventionally.When adopt diesel hydrotreating unit be transformed into Wax Oil Hydrogenation Unit carry out wax oil hydrogenation process time, because hydrotreatment process is a process that hydrogenation of unsaturated hydrocarbons is saturated, do not have scission reaction to occur, after hydrotreatment, generate oil viscosity high, density is large, can form water-oil emulsion with the de-mineralized water injecting before air cooler, not easily separated thorough in cold high score, cause generating and in oil, carry a part of water and bring fractionating system into, improve fractionating system operation easier, make fractionating system fluctuation larger.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of wax oil hydrogenation treatment process, the method can effectively reduce hydrotreatment and generate oil viscosity and density, make hydrotreatment after product just sulfur-bearing can not be entered to fractionating system by water entrainment containing ammonia sewage drain separator after cold high score separates, and reduce process furnace load, reduce the energy consumption of device.
Wax oil hydrogenation treatment process of the present invention comprises the steps:
(1) wax oil enters hydrotreating reactor after mixing with benzoline, under the effect of hydrogen and hydrotreating catalyst, reacts;
(2) step (1) gained hydrotreatment is flowed out thing and after water filling and air cooling, is entered cold high pressure separator and carry out oil, gas, water three phase separation, the gas phase that separation obtains recycles, the liquid phase obtaining enters light pressure separator, and the sulfur-bearing obtaining is containing ammonia sewage drain separator;
(3) liquid phase that step (2) mesolow separator obtains enters separation column, separates and obtains gas, gasoline, diesel oil and tail oil.
In the inventive method, virgin naphtha, coking naphtha, virgin kerosene, coking kerosene, catalytic diesel oil that the described benzoline of step (1) is various sources, one or more in straight-run diesel oil and coker gas oil, preferably coker gasoline and/or coker gas oil; Described wax oil raw material initial boiling point is generally 280 ℃～440 ℃, and final boiling point is generally 450 ℃～700 ℃.In described raw material, benzoline and wax oil raw material ratio are 1:10～10:1, preferably 1:10～1:1.
In the present invention, in method, hydrotreatment operational condition comprises: reaction pressure 5.0～35.0MPa, preferably 6.0～19.0MPa; Average reaction temperature is 200 ℃～480 ℃, preferably 270 ℃～450 ℃; Volume space velocity is 0.1～15.0h
-1, preferably 0.2～3.0h
-1; Hydrogen to oil volume ratio is 100:1～2500:1, preferably 400:1～2000:1.
In the inventive method, the catalyzer that hydrotreatment adopts can be various commercial catalysts, also can be prepared by state of the art.Described hydrotreating catalyst comprises the hydrogenation metal of carrier and institute's load.Take the weight of catalyzer as benchmark, generally include metal component of group VIB in the periodic table of elements, count 10%～35% as tungsten and/or molybdenum with oxide compound, be preferably 15%～30%; Group VIII metal counts 1%～7% as nickel and/or cobalt with oxide compound, is preferably 1.5%～6%.Carrier is inorganic refractory oxide, is generally selected from aluminum oxide, amorphous silicon aluminium, aluminium dioxide, titanium oxide etc.Commodity hydrogenation pretreatment catalyst mainly contains, as the FF-14 of Fushun Petrochemical Research Institute (FRIPP) development, FF-18, FF-24, FF-26, FF-36, the hydrogenation catalysts such as FH-46, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, ICR 179 hydrogenation catalysts such as grade, Uop Inc. is newly developed HC-P, HC-K UF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907, above-mentioned catalyzer is carry out can be for processing method of the present invention after conventional sulfidizing.
The inventive method by adding a certain proportion of benzoline jointly to carry out hydrotreatment in raw material, hydrotreatment be can reduce and oil viscosity and density generated, be conducive to promote hydrotreatment products fully to separate at cold high pressure separator with the water injecting before air cooler, make sulfur-bearing contain ammonia sewage in cold high pressure separator with regard to drain separator, avoid further bringing sulfur-bearing into fractionating system containing ammonia sewage, by so can reduce the fluctuation of separation column, under not to the prerequisite of original Diesel Oil Hydrofining Unit separation system transformation, solve the problem that in oil, profit is difficult to separation that generates, save the plant investment that cold high score is transformed into hot high score.And in the time that benzoline is coker gasoline and/or coker gas oil, because the alkene in coker gasoline and coker gas oil just can react at a lower temperature, and exothermic heat of reaction is obvious, can make like this stock oil enter reactor with lesser temps, utilize olefin saturated heat release to improve temperature of reaction, reduce the operational load of process furnace, reduce plant energy consumption.
Accompanying drawing explanation
Fig. 1 is the principle flow chart of processing method of the present invention.
Embodiment
As shown in Figure 1, the concrete technology flow process of the inventive method is as follows: wax oil 1 and benzoline 2 enter hydrotreating reactor 4 after mixing with hydrogen 3, with the hydrotreating catalyst contact reacts in reactor, the hydrotreatment outflow thing 5 that reaction obtains enters cold high pressure separator 6 and carries out oil, gas, water three phase separation after water filling and air cooling, the gas phase 7 that separation obtains recycles, the liquid phase 8 obtaining enters light pressure separator 9 and further separates, and the sour water treatment unit that the sulfur-bearing that separation obtains is delivered to outside device containing ammonia sewage is further processed; The liquid phase 10 that light pressure separator 9 obtains enters separation column 11, obtains respectively gas 12, gasoline 13, diesel oil 14 and tail oil 15 through separating, and tail oil 15 is as catalytically cracked material.
Further illustrate particular case of the present invention below by specific embodiment, but be not limited to following embodiment.The present invention's wax oil feedstock property used is in table 1, and benzoline is coker gasoline and coker gas oil mixture, and blending ratio is 1:3, and specific nature is in table 2, and wherein, coker gasoline and coker gas oil mixture are mixed refining than being 1:4 with wax oil.
Various catalyzer involved in the present invention are the commercial catalyst of Fushun Petrochemical Research Institute (FRIPP) development and production.Wherein, protective material in hydrotreating reactor is FZC100, FZC102B, the FZC103 catalyzer that FRIPP develops; catalyst for demetalation is FZC-204 catalyzer; hydrotreating catalyst in hydrotreating reactor is the FF-24 hydrogenation catalyst that Fushun Petrochemical Research Institute develops, and specific nature is in table 3.The processing condition of hydrotreating reactor are in table 4, and hydrotreatment reaction gained gasoline, diesel oil and tail oil character are respectively in table 5, table 6 and table 7.
Table 1 wax oil main character
| Stock oil title | Decompressed wax oil |
| Density (20 ℃), gcm -3 | 0.9232 |
| Boiling range/℃ | |
| IBP/10% | 311.7/364.8 |
| 30%/50% | 407.6/435.9 |
| 70%/90% | 470.2/524.1 |
| 95%/EBP | 546.8/559.1 |
| Yield, % | 96.9 |
| Viscosity (50 ℃), mm 2·s -1 | 39.11 |
| Viscosity (100 ℃), mm 2·s -1 | 7.756 |
| Refractive power, n D 70 | 1.4899 |
| Condensation point, ℃ | 40 |
| Carbon residue, m% | 0.61 |
| Acid number, mgKOH/g | 0.14 |
| S，m% | 1.93 |
| N，μg·g -1 | 1594 |
| C，m% | 84.69 |
| H，m% | 12.30 |
The main character of table 2 coker gasoline and coker gas oil
| Stock oil title | Coker gasoline | Coker gas oil |
| Density, g/cm 3 | 0.75 | 0.82 |
| Boiling range, ℃ | <200 | 200-350 |
| Boiling range (ASTMD86), ℃ | ||
| Initial boiling point/10% | 38/55 | 177/186 |
| 30%/50% | 128/138 | 224/248 |
| 70%/90% | 151/165 | 279/321 |
| / final boiling point | 180 | 340 |
| Sulphur, m% | 0.71 | 1.12 |
| Nitrogen, μ gg -1 | 220 | 855 |
Table 3 FF-24 catalyzer physico-chemical property
| Analysis project | FF-24 |
| Chemical constitution | |
| MoO 3 | 2.0 |
| NiO | 3.0 |
| CoO | 2.0 |
| Particle diameter/mm | 1.3 |
| Pore volume/mLg -1 | ≮0.38 |
| Specific surface area/m 2·g -1 | ≮190 |
| Shape | Trifolium bar |
| Natural density/gcm -3 | ～0.75 |
| Tap density/gcm -3 | ～0.83 |
| Crushing strength/Nmm -1 | ≥16.0 |
Table 4 technological condition
| Stock oil | Lightweight material |
| Catalyzer | FZC-100/FZC-102B/FZC-103/FZC-204/FF-24 |
| Reaction stagnation pressure, MPa | 10.0 |
| Hydrogen to oil volume ratio | 1000:1 |
| Volume space velocity, h -1 | 1.2 |
| Temperature of reaction, ℃ | 350 |
| Chemical hydrogen consumption | 1. 0 |
Table 5 hydrogenated gasoline main character
| Product | Gasoline |
| Density (20 ℃), gcm -3 | 0.7235 |
| Boiling range, ℃ | |
| IBP/10% | 42/73 |
| 50%/90% | 130/180 |
| EBP | 202 |
| Sulphur, μ gg -1 | 5 |
| Alkene, % | 0.15 |
Table 6 hydrogenated diesel oil main character
| Product | Diesel oil |
| Density (20 ℃), g/cm 3 | 0.8174 |
| Boiling range (ASTM D86), ℃ | |
| IBP/10% | 180/216 |
| 30%/50% | 234/263 |
| 70%/90% | 298/320 |
| FBP | 346 |
| Sulphur, μ gg -1 | 8 |
| Cetane index (ASTM D4737-96a) | 58.1 |
Table 7 tail oil main character
| Density (20 ℃, g/cm 3） | 0.8783 |
| Boiling range, ℃ | |
| IBP/10% | 235.1/341.1 |
| 30%/50% | 397.3/430.8 |
| 70%/90% | 464.5/521.7 |
| 95%/EBP | 559.0/559.0 |
| Viscosity (50 ℃), mm 2·s -1 | 18.85 |
| Viscosity (100 ℃), mm 2·s -1 | 4.98 |
| Refractive power, n D 70 | 1.4687 |
| Condensation point, ℃ | 36 |
| Carbon residue, m% | 0.01 |
| S，μg·g -1 | 559 |
| N，μg·g -1 | 123 |
| C，m% | 86.60 |
| H，m% | 12.96 |
Claims (9)
1. a wax oil hydrogenation treatment process, comprises the steps:
(1) wax oil enters hydrotreating reactor after mixing with benzoline, under the effect of hydrogen and hydrotreating catalyst, reacts;
(2) step (1) gained hydrotreatment is flowed out thing and after water filling and air cooling, is entered cold high pressure separator and carry out oil, gas, water three phase separation, the gas phase that separation obtains recycles, the liquid phase obtaining enters light pressure separator, and the sulfur-bearing obtaining is containing ammonia sewage drain separator;
(3) liquid phase that step (2) mesolow separator obtains enters separation column, separates and obtains gas, gasoline, diesel oil and tail oil.
2. in accordance with the method for claim 1, it is characterized in that: virgin naphtha, coking naphtha, virgin kerosene, coking kerosene, catalytic diesel oil that described benzoline is various sources, one or more in straight-run diesel oil and coker gas oil.
3. it is characterized in that in accordance with the method for claim 2: described benzoline is coker gasoline and/or coker gas oil.
4. in accordance with the method for claim 1, it is characterized in that: described wax oil initial boiling point is 280 ℃～440 ℃, final boiling point is 450 ℃～700 ℃.
5. it is characterized in that in accordance with the method for claim 1: in described raw material, benzoline and wax oil ratio are 1:10～10:1.
6. it is characterized in that in accordance with the method for claim 1: in described raw material, benzoline and wax oil ratio are 1:10～1:1.
7. in accordance with the method for claim 1, it is characterized in that: described hydrotreatment operational condition is: reaction pressure is 5.0～35.0MPa, average reaction temperature is 200 ℃～480 ℃, and volume space velocity is 0.1～15.0h
-1, hydrogen to oil volume ratio is 100:1～2500:1.
8. it is characterized in that in accordance with the method for claim 1: described hydrotreatment operational condition is: reaction pressure is 6.0～19.0MPa; Average reaction temperature is 270 ℃～450 ℃; Volume space velocity is 0.2～3.0h
-1; Hydrogen to oil volume ratio is 400:1～2000:1.
9. in accordance with the method for claim 1, it is characterized in that: described hydrotreating catalyst comprises carrier and active metal component, take the weight of catalyzer as benchmark, active metal component comprises group VIB metal and/or group VIII metal, and carrier is inorganic refractory oxide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988646A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Wax oil hydrogenation processing and hydrofinishing group technology |
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| US20090159493A1 (en) * | 2007-12-21 | 2009-06-25 | Chevron U.S.A. Inc. | Targeted hydrogenation hydrocracking |
| CN102071057A (en) * | 2010-12-29 | 2011-05-25 | 何巨堂 | Two-stage high-nitrogen high-aromatic oil hydro-conversion method |
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| CN101412923A (en) * | 2007-10-18 | 2009-04-22 | 中国石油化工股份有限公司 | Hydro-upgrading combined method |
| US20090159493A1 (en) * | 2007-12-21 | 2009-06-25 | Chevron U.S.A. Inc. | Targeted hydrogenation hydrocracking |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988646A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Wax oil hydrogenation processing and hydrofinishing group technology |
| CN109988646B (en) * | 2017-12-29 | 2022-07-12 | 中国石油化工股份有限公司 | Wax oil hydrotreating and hydrofining combined process |
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