CN101942328B - Hydrogenation method for gasoline and diesel - Google Patents
Hydrogenation method for gasoline and diesel Download PDFInfo
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- CN101942328B CN101942328B CN 200910012492 CN200910012492A CN101942328B CN 101942328 B CN101942328 B CN 101942328B CN 200910012492 CN200910012492 CN 200910012492 CN 200910012492 A CN200910012492 A CN 200910012492A CN 101942328 B CN101942328 B CN 101942328B
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Abstract
The invention discloses a hydrogenation method for gasoline and diesel, comprising: mixing gasoline raw materials and hydrogen; passing through a first reaction region under a gasoline hydrogenation refined condition, wherein a hydrogenation refined catalyst is used in the first reaction region, and the gasoline materials are coke gasoline and/ or catalytic gasoline; mixing reaction effluent with diesel materials, passing through a second reaction region under a diesel hydrogenation refined condition, gas-liquid separating the effluent of the second reaction region, further treating a gas phase and then recycling, a liquid phase entering into a product fractionation system. The method effectively uses the heat energy discharged when performing secondary processing gasoline hydrogenation, and the method is featured with simple technological process and low energy consumption.
Description
Technical field
The present invention relates to a kind of hydrocarbon hdyrotreating method, specifically a kind of gasoline, diesel hydrogenation for removal sulphur, deolefination, take off the virtue method of hydrotreating.
Background technology
The heaviness of crude oil is becoming a kind of trend, therefore, in order to improve the output of gasoline, diesel oil, the former oil require of most of heaviness carries out the secondary processing methods such as delayed coking and catalytic cracking, and secondary processing oil product shared proportion in gasoline, diesel oil blending component is increasing.And owing to containing the impurity such as a large amount of sulphur, nitrogen, alkene, aromatic hydrocarbons in secondary processing of gasoline, diesel oil, can not directly as blend component, need just to can be used as the blend component use after general hydrofining.For example delayed coking is the residual oil weight-lightening means that generally adopt, coking is at high temperature to carry out degree of depth thermally splitting take residual oil as raw material, a kind of secondary processing process of obtain fraction oil and refinery coke, wherein major part adopts delayed coking process, its advantage is to process various poor residuums, process is simple, investment and process cost are low, its shortcoming is that in coker gasoline and coker gas oil, unsaturated hydrocarbons content is high, and the content of the non-hydrocarbons such as sulfur-bearing, nitrogen is also high, has brought larger difficulty for further processing treatment.The gasoline of the processing technology, particularly secondary processing of the distillates such as relevant gasoline, diesel oil, the processing technology of diesel oil distillate more and more come into one's own under such background.
The processing mode that hydrogenation is carried out in hydrogenation or mixing is carried out respectively in the gasoline of secondary processing and the general employing of diesel oil distillate raw material, and every kind of mode all has characteristics and the deficiency of himself.
US5114562 discloses a kind of two-stage hydrogenation technique of utilizing from the technology of middle distillate production low sulfur and low aromatics product.Its technological process is for to remove H from first paragraph reactor liquid product out through the hydrogen air lift
2S and NH
3After, then heat up through heat exchange, enter into the second segment reactor.This technique first reactor stream needs hydrogen air lift and heat exchange heating process comparatively complicated, and energy consumption is high.
CN02109671.6 discloses a kind of coking full fraction oil hydrogenation refining method, under the middle pressure condition, charking full distillate oil contacts with Hydrobon catalyst, and reaction product is isolated gas-liquid two-phase through high score, and gas-phase product is circulated to the coking full fraction oil hydrogenation refining reactor as recycle hydrogen; Liquid product enters separation column and isolates gasoline, diesel oil and wax oil.This Technology exists the large shortcoming of reaction bed temperature rise, the cold hydrogen cooling of needs between reaction bed.
CN200410050729.6 discloses a kind of diesel oil fraction hydrogenating treatment process.Be first lighting end and last running with the stock oil fractionation, the first reaction zone is sent in lighting end, contact with Hydrobon catalyst, second reaction zone is sent in last running, contact with Hydrobon catalyst, two reaction zone liquid products are mixed into refining distillate, this raw materials technology need fractionation be light, weigh two components, technique is comparatively complicated.
CN200610045708.4 discloses a kind of method by producing high grade of diesel oil by charking full distillate oil, charking full distillate oil is separated into coking light distillate and coking heavy distillate, wherein contain part solar oil cut in light ends oil, heavy distillate is to do higher heavy gas oil cut.The coking heavy distillate carries out hydro-upgrading, and the hydro-upgrading product mixes with coking light distillate and carries out hydrofining and process.The method can obtain to maximum high-quality clean diesel, simultaneously can obtain high-quality petroleum naphtha, but the characteristics of low, the temperature rise of starting temperature when the method does not take full advantage of coking light distillate hydrogenation, coking heavy distillate carry out carrying out after hydro-upgrading necessity that hydrofining processes and not obvious again.
Summary of the invention
Large for reactor temperature rise in prior art, the deficiency that reaction heat can't take full advantage of the invention provides a kind of vapour, diesel oil distillate oil working method, and the method can be utilized the reaction heat of coker gasoline and/or catalytic gasoline, and technique is simple, and energy consumption is less.
Gasoline of the present invention and diesel hydrogenation method comprise following content:
(1) gasoline stocks mixes with hydrogen, under the gasoline hydrofinishing condition through the first reaction zone, the first reaction zone uses Hydrobon catalyst, gasoline stocks is coker gasoline and/or catalytic gasoline, and gasoline stocks mainly carries out olefin saturation and a small amount of hydrodesulfurization reaction at the first reaction zone;
(2) first reaction zone reaction effluents mix with diesel raw material, process second reaction zone under the diesel oil hydrofining condition, second reaction zone uses Hydrobon catalyst, diesel raw material is one or more in straight-run diesel oil, coker gas oil, catalytic cracking diesel oil etc., mainly carries out the reaction such as hydrogenating desulfurization, aromatic saturation of deep hydrodesulfurizationof, the diesel raw material of gasoline stocks at second reaction zone.
(3) reaction effluent of second reaction zone carries out gas-liquid separation, and gas phase recycles after further processing, and liquid phase enters the product fractionating system.
The first reaction zone is 1: 3～3: 1 with the admission space ratio of second reaction zone used catalyst, and this need to require specifically to determine according to ratio and character, selected Hydrobon catalyst character and the quality product of gasoline stocks, diesel raw material.
In gasoline of the present invention and diesel oil distillate oil working method, the gasoline hydrofinishing condition that the first reaction zone adopts is as follows: 150 ℃～350 ℃ of temperature of reaction, preferred 200 ℃～300 ℃, reaction pressure 3.0MPa～10.0MPa, preferred 4.0MPa～8.0MPa, volume space velocity 1.0h during liquid
-1～10.0h
-1, preferred 2.0h
-1～6.0h
-1, hydrogen to oil volume ratio 100～600, preferred 200～400.The diesel oil hydrofining condition of second reaction zone is as follows: 300 ℃～500 ℃ of temperature of reaction, preferred 340 ℃～380 ℃, reaction pressure 3.0MPa～10.0MPa, preferred 4.0MPa～8.0MPa, volume space velocity 1.0h during liquid
-1～6.0h
-1, preferred 1.5h
-1～4.0h
-1, hydrogen to oil volume ratio 200～1000, preferred 400～800.Wherein during second reaction zone liquid volume space velocity than the low 0～3h of the first reaction zone
-1, the temperature of reaction of second reaction zone is higher 0～200 ℃ than the first reaction zone.Two reaction zones can be arranged in a reactor, also can be arranged in two or more reactors.The average reaction temperature of above-mentioned each reaction zone of temperature of reaction.
in the inventive method, at the first reaction zone owing to being gasoline stocks hydrogenation olefin saturated, therefore reaction conditions relaxes, simultaneously, secondary processing of gasoline (coker gasoline, catalytically cracked gasoline) in raw material, alkene and diene content are higher, can produce higher reaction heat in reaction process, therefore, utilize the heat that produces in the first reaction zone, the diesel raw material that adds in second reaction zone need not heat before entering reactor or only need a small amount of heating can satisfy the temperature of reaction requirement that two anti-diesel hydrogenation for removal sulphur take off aromatic hydrocarbons, simultaneously, the reaction heat that has absorbed gasoline fraction due to the diesel oil distillate of second reaction zone is compared with traditional coking/catalytic gasoline hydrogenation and has been solved the reaction coking problem, extended the work-ing life of catalyzer.
In the inventive method, the main olefin saturation that occurs in the first reaction zone, therefore, H in the first reaction zone effluent hydrogen
2S and NH
3Content is lower, and therefore, effluent need not to remove H
2S and NH
3Can directly enter second reaction zone and carry out desulfurization, take off the aromatic hydrocarbons reaction, this sampling technology is more simple, has reduced running cost.
In the inventive method, when producing low-sulfur, low fragrant diesel product, again secondary processing of gasoline has been carried out the refining of the degree of depth, can obtain sulphur, nitrogen content less than the gasoline products of 0.5 μ g/g, the gasoline products of gained can be directly or through mediation as the catalytic reforming charging.Technique of the present invention is flexible, can regulate secondary processing of gasoline and diesel oil processing ratio according to the refinery need of production.
Description of drawings
Fig. 1 is invention vapour, diesel oil distillate oil working method schematic flow sheet.
Wherein: 1-gasoline stocks, 2-diesel raw material, 3-the first reaction zone, 4-second reaction zone, 5-reaction effluent.
Embodiment
In gasoline of the present invention, diesel oil distillate oil working method, step (1) and the described Hydrobon catalyst of step (2) refer to have hydrogenating desulfurization, the non-noble metal hydrogenation catalyst for refining of hydrogenation of olefins, the saturated function of aromatic hydrogenation.This non-precious metal catalyst generally exists with the oxidation state form before use, need to carry out prevulcanized, makes non-noble metal oxide be converted into sulfide and just has reactive behavior, and therefore, non-precious metal catalyst in use will keep sulphided state.The present invention's Hydrobon catalyst used can adopt conventional gasoline hydrogenation treatment catalyst and diesel oil hydrofining catalyst, and in practice, some Hydrobon catalyst can be used for gasoline hydrofinishing simultaneously also can be used for diesel oil hydrofining.Hydrobon catalyst is generally take group vib and/or group VIII metal as active ingredient, take aluminum oxide or silicon-containing alumina as carrier, the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni, and catalyzer can use suitable auxiliary agent as required.Take the weight of catalyzer as benchmark, the group vib metal content is counted 4wt%～28wt% with oxide compound, and the group VIII metal content is counted 2wt%～15wt% with oxide compound, and its character is as follows: specific surface is 100～650m
2/ g, pore volume are 0.15～0.8ml/g.Step (1) and step (2) can adopt identical Hydrobon catalyst, the different Hydrobon catalyst of preferred employing, step (1) adopts Ni-Mo, Ni-W or the Ni-W-Mo class Hydrobon catalyst of Hydrobon catalyst such as low-metal content, Hydrobon catalyst such as Co-Mo, Ni-Mo, Ni-W or Ni-W-Mo class Hydrobon catalyst that step (2) adopts, the relative step 1 of this catalyst metal content is higher.
Technical process of the present invention as shown in Figure 1, enter reactor from the first reaction zone 3 tops after gasoline stocks 1 and hydrogen mixing preheating, under existing, the sulphided state Hydrobon catalyst carries out hydrogenation reaction, reaction effluent with enter second reaction zone 4 after diesel raw material 2 is mixed, under existing, the sulphided state Hydrobon catalyst carries out hydrogenation reaction, reaction effluent 5 discharges enter separation system and carry out gas-liquid separation, the liquid phase of gained is all or part of as product, and gas-phase product uses as recycle hydrogen after purifying.
Below by embodiment, the present invention program and effect are described.
Composition and the main character of table 1 embodiment used catalyst
| Project | Catalyst A | Catalyst B |
| Chemical constitution, % (massfraction) | ||
| MoO 3 | 13.8 | 4.2 |
| NiO | 2.3 | 9.3 |
| CoO | - | - |
| WO 3 | - | 20.2 |
| Carrier | Aluminum oxide | Silicon-containing alumina |
| Physico-chemical property | ||
| Pore volume, ml/g | 0.44 | 0.45 |
| Specific surface area, m 2/g | 179 | 201 |
Table 2 stock oil character
| Stock oil | Stock oil A | Stock oil B |
| Density, g/cm 3 | 0.7331 | 0.8469 |
| Boiling range, ℃ | 56～198 | 199～379 |
| Sulphur content, μ g/g | 360 | 8800 |
| Nitrogen content, μ g/g | 58 | 316 |
| Aromaticity content, wt% | 6.3 | 21.5 |
| Alkene/V% | 41.6 | - |
Table 3 embodiment 1～4 operational condition that adopts
Table 4 embodiment 1～4 evaluation result
Claims (10)
1. a gasoline and diesel hydrogenation method comprise following content:
(1) gasoline stocks mixes with hydrogen, and through the first reaction zone, the first reaction zone uses Hydrobon catalyst under the gasoline hydrofinishing condition, and gasoline stocks is coker gasoline and/or catalytic gasoline;
(2) first reaction zone reaction effluents mix with diesel raw material, and through second reaction zone, second reaction zone uses Hydrobon catalyst under the diesel oil hydrofining condition;
(3) reaction effluent of second reaction zone carries out gas-liquid separation, and gas phase recycles after further processing, and liquid phase enters the product fractionating system.
2. it is characterized in that in accordance with the method for claim 1: diesel raw material is one or more in straight-run diesel oil, coker gas oil, catalytic cracking diesel oil.
3. it is characterized in that in accordance with the method for claim 1: the first reaction zone is 1: 3～3: 1 with the admission space ratio of second reaction zone used catalyst.
4. in accordance with the method for claim 1, it is characterized in that: the gasoline hydrofinishing condition that the first reaction zone adopts is as follows: 150 ℃～350 ℃ of temperature of reaction, reaction pressure 3.0MPa～10.0MPa, volume space velocity 1.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio 100～600.
5. in accordance with the method for claim 1, it is characterized in that: the gasoline hydrofinishing condition that the first reaction zone adopts is as follows: 200 ℃～300 ℃ of temperature of reaction, reaction pressure 4.0MPa～8.0MPa, volume space velocity 2.0h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio 200～400.
6. in accordance with the method for claim 1, it is characterized in that: the diesel oil hydrofining condition of second reaction zone is as follows: 300 ℃～500 ℃ of temperature of reaction, reaction pressure 3.0MPa～10.0MPa, volume space velocity 1.0h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio 200～1000.
7. in accordance with the method for claim 1, it is characterized in that: the diesel oil hydrofining condition of second reaction zone is as follows: 340 ℃～380 ℃ of temperature of reaction, reaction pressure 4.0MPa～8.0MPa, volume space velocity 1.5h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio 400～800.
8. in accordance with the method for claim 1, it is characterized in that: step (1) and the described Hydrobon catalyst of step (2) are the non-noble metal hydrogenation catalyst for refining, the non-noble metal hydrogenation catalyst for refining is take group vib and/or group VIII metal as active ingredient, the group vib metal is Mo and/or W, and the group VIII metal is Co and/or Ni.
9. according to the described method of claim 1 or 8, it is characterized in that: step (1) adopts identical Hydrobon catalyst with step (2), perhaps adopts different Hydrobon catalysts.
10. in accordance with the method for claim 1, it is characterized in that: the Hydrobon catalyst that step (1) adopts is Ni-Mo, Ni-W or Ni-W-Mo Hydrobon catalyst, and the Hydrobon catalyst that step (2) adopts is Co-Mo, Ni-Mo, Ni-W or Ni-W-Mo Hydrobon catalyst.
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|---|---|---|---|
| CN 200910012492 CN101942328B (en) | 2009-07-09 | 2009-07-09 | Hydrogenation method for gasoline and diesel |
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|---|---|---|---|
| CN 200910012492 CN101942328B (en) | 2009-07-09 | 2009-07-09 | Hydrogenation method for gasoline and diesel |
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|---|---|
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| CN101942328B true CN101942328B (en) | 2013-06-05 |
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| CN102876366B (en) * | 2011-07-11 | 2015-08-12 | 中国石油化工股份有限公司 | A kind of Unionfining treatment process |
| CN103059967B (en) * | 2011-10-21 | 2014-12-31 | 中国石油化工股份有限公司 | Mixed hydrogenation method for catalytic cracking gasoline and coking diesel oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003086567A1 (en) * | 2002-04-05 | 2003-10-23 | Fluor Corporation | Combined hydrotreating process and configurations for same |
| CN101003750A (en) * | 2006-01-19 | 2007-07-25 | 中国石油化工股份有限公司 | Method for producing high grade of diesel oil from charking full distillate oil |
| EP2025396A1 (en) * | 2002-04-03 | 2009-02-18 | Fluor Corporation | Combined hydrotreating and process |
| CN100489068C (en) * | 2004-10-29 | 2009-05-20 | 中国石油化工股份有限公司 | Diesel fuel fraction hydrotreating method |
-
2009
- 2009-07-09 CN CN 200910012492 patent/CN101942328B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2025396A1 (en) * | 2002-04-03 | 2009-02-18 | Fluor Corporation | Combined hydrotreating and process |
| WO2003086567A1 (en) * | 2002-04-05 | 2003-10-23 | Fluor Corporation | Combined hydrotreating process and configurations for same |
| CN100489068C (en) * | 2004-10-29 | 2009-05-20 | 中国石油化工股份有限公司 | Diesel fuel fraction hydrotreating method |
| CN101003750A (en) * | 2006-01-19 | 2007-07-25 | 中国石油化工股份有限公司 | Method for producing high grade of diesel oil from charking full distillate oil |
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