CN102465025B - Method for processing inferior gasoline - Google Patents
Method for processing inferior gasoline Download PDFInfo
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- CN102465025B CN102465025B CN201010539215.2A CN201010539215A CN102465025B CN 102465025 B CN102465025 B CN 102465025B CN 201010539215 A CN201010539215 A CN 201010539215A CN 102465025 B CN102465025 B CN 102465025B
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- coking
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Abstract
The invention discloses an improved method for processing inferior gasoline. The method comprises the steps of: mixing an inferior gasoline raw material and a refined effluent, and feeding a mixture into a settler for settling coking matters; mixing a decoked mixed feed and hydrogen, feeding a mixture into a hydrogenation reactor through a heating furnace for reaction; and mixing one part of the refined effluent and the inferior gasoline raw material for heat transfer, introducing the residual refined effluent into a separator for separation, wherein a liquid phase is used as a product to be discharged out of a device, and a gaseous phase is used as recycle hydrogen. In the method disclosed by the invention, a heat exchanger is omitted, a fresh feed is directly mixed with partial hydrogenation products for heat exchanging, so that not only is the heat exchanging efficiency is increased, but also the coking of the heat exchanger is avoided; the mixed feed subjected to heat exchanging is settled by the settler to obtain the coking matters generated in the heat exchanging process, so that the feeds of the heating furnace and a hydrorefining reactor are optimized, the raw materials are prevented from being coked in the reactor and the heating furnace, and the operation cycle of a gasoline hydrogenation device is prolonged.
Description
Technical field
The present invention relates to a kind of hydrocarbon hydroprocessing technique, specifically a kind of hydrogenation method of inferior patrol.
Background technology
Along with the reinforcement of environmental regulation, the clean gasoline new standard that formulate countries in the world has proposed more and more stricter restriction to sulphur content.Therefore the sulphur content, reducing in gasoline is the key subjects that oil refining enterprise faces.And in clear gusoline generates, hydrotreatment remains the most effective technology at present.In gasoline hydrogenation technology, it is the more gasoline hydrogenation technology of applying at present that Hydrogenation of Coker Gasoline generates feed ethylene technology, but due to as secondary processing of gasoline, in coker gasoline, exist the coking precursors such as higher alkene, diolefine, colloid, raw material is in very easily coking in interchanger and Furnace Production Process, produce pressure drop, thereby reduce device running period, affect the performance of enterprises.
Patent CN200610103670.1 discloses a kind of method for processing inferior gasoline, in this patent, the bad gasoline such as coker gasoline removes sulphur and alkene through hydrofining reactor, but due to alkene, diolefine etc. in stock oil, easily coking material is more, be easy to coking and produce pressure drop, therefore cannot guarantee running period.
Patent CN200810113398.4 discloses a kind of method for processing inferior gasoline, and raw material inferior patrol is first through pre-reactor low temperature hydrogenation removing impurities matter, then enters main reactor reaction, but this technical process is more complicated, and facility investment is large.
Summary of the invention
Produce the problem of pressure drop for easy coking in the inferior patrol courses of processing such as coker gasoline, the invention provides a kind of improved method for processing inferior gasoline.
Method for processing inferior gasoline of the present invention comprises following content:
(1) bad gasoline is mixed with hydrofining effluent, enters scale trap sedimentation coking material;
(2) react except defocused mixture mixes with hydrogen and enter hydrofining reactor after process furnace heating, obtain refining effluent;
(3) part for the refining effluent of step (2) gained loops back in step (1), mixes with bad gasoline;
(4) remainder of the refining effluent of step (2) gained enters gas-liquid separator and separates, and obtains gas phase and liquid phase, and liquid phase goes out device as product, and gas phase is circulated in step (1) and is used as recycle hydrogen.
In inferior patrol hydrogenation method of the present invention, described bad gasoline is secondary processing of gasoline, as comprised coker gasoline, FCC gasoline etc.Hydrobon catalyst can use commercially available prod, also can be according to the conventional knowledge preparation in this area.
The catalyzer using in hydrogenator can be for conventional Hydrobon catalyst, preferably has the Hydrobon catalyst of following character: catalyzer is take aluminum oxide as carrier, take Mo and Co as active metal component; Catalyzer is containing MoO by weight
33.0～18.0w%, preferably 4.0～16.0w%, CoO 1.0～6.0w%, preferably 2.0～5.0w%, Co/Mo atomic ratio 0.1～1.0; The pore volume of catalyzer is 0.3～1.3mL/g, and specific surface area is 150～300m
2/ g.
In method for processing inferior gasoline of the present invention, the operational condition in hydrofining reaction district described in step (2) can be determined by the operational condition of this area routine.In general, hydrofining operational condition is as follows: 220 ℃～400 ℃ of temperature of reaction, preferably 260 ℃～350 ℃, reaction pressure 1.0MPa～6.0MPa, preferably 1.5MPa～4.0MPa, volume space velocity 1.0h when liquid
-1～10.0h
-1, preferably 2.0h
-1～6.0h
-1, hydrogen to oil volume ratio 50～400, preferably 80～200.
According to method for processing inferior gasoline of the present invention, the conventional settling vessel that wherein scale trap described in step (1) is this area, described scale trap can comprise single settling vessel, also can comprise two settling vessels in parallel.In the time that one of them settling vessel pressure drop is excessive, switches and use another settling vessel.Conventionally scale trap is designed to low ratio of height to diameter, to increase its trafficability characteristic and to improve settling efficiency.The aspect ratio of settling vessel is generally 1: 1～and 1: 5, preferably 1: 2～1: 3.
In scale trap, can pack the protective material of different size and different pore size into.Edge enters the direction of the Flow of Goods and Materials of settling vessel, and protectant particle size reduces gradually.Conventionally protective material can be the spheroid of diameter 3mm to 20mm.Protective material can use commercially available prod as required, also can be by the conventional knowledge preparation in this area.Protective material is generally inert ceramic balls or oxidation aluminum strip.According to the number of contained mechanical impurity, coke powder in raw material.Also can loading section Mo and/or Ni isoreactivity metal on protective material.
Volume space velocity is generally 1.0h when the liquid of mixture by scale trap in step (1)
-1～8.0h
-1, preferably 2.0h
-1～4.0h
-1.
Compared with prior art, the inventive method has following features:
Owing to containing higher alkene, diolefine in the secondary processing of gasoline such as coker gasoline, and in storage process, contact the coking precursor that easily produces colloid with oxygen, in regular price gasoline hydrogenation technique, in the time of these materials process interchanger and process furnace, flow velocity is slower, and temperature is higher, therefore, be easy to coking.The coking material generating is deposited on the pressure drop that induces reaction on interchanger and process furnace and increases, and finally causes device to be forced to stop work.In inferior patrol hydrogenation technique of the present invention, cancelled interchanger, fresh feed directly mixes heat-obtaining with partial hydrogenation product, like this, has both improved heat exchange efficiency, has avoided again interchanger coking, has reduced investment simultaneously.Parallel feeding after heat-obtaining goes out through settling vessel sedimentation the coking material producing in heat-obtaining process, like this, has optimized process furnace and hydrofining reactor charging, has avoided raw material at reactor and furnace coking, thereby has extended gasoline hydrogenation device running period.Process using raw material of the present invention directly mixes heat-obtaining with portioned product, and heat-obtaining efficiency is higher, and Hydrogenation of Coker Gasoline temperature rise is very large, and therefore, after going into operation, process furnace can cut out reaction process or underload uses.
Accompanying drawing explanation
Fig. 1 is a kind of principle process schematic diagram of method for processing inferior gasoline of the present invention.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described further.
As shown in Figure 1, fresh gasoline stocks is mixed with the hydrogenation products flowing out through pipeline 4 by pipeline 1, parallel feeding enters slurry tank 7 separate solid coking materials, then after mixing with from the hydrogen of pipeline 6, entering process furnace 10 heats, parallel feeding after heating enters hydrofining reactor 2 through pipeline 8 and reacts, a part for the refining effluent of gained is mixed with the fresh feed that pipeline 1 enters through pipeline 4, another part enters gas-liquid separator 5 through pipeline 3, through gas, after liquid separates, gas phase is used as recycle hydrogen through pipeline 6, liquid phase flows out reaction zone as product through pipeline 9.
Below by specific embodiment and comparative example explanation the present invention program and effect.
The composition of catalyzer and character are in table 1, and feedstock property used is in table 2, and embodiment 1～4 processing condition used are listed in table 3, and the evaluation result of embodiment 1～4 is in table 4, and embodiment 1～4 adopts coker gasoline raw material in table 2.
The physico-chemical property of table 1 catalyzer
Table 2 stock oil character
Table 3 hydrogenator operational condition
Table 4 product property table
Known by embodiment 1～4, technique of the present invention can utilize inferior patrol to produce qualified ethylene cracking material, and the pressure drop of 1 year reactor (hydrofining reactor) of device operation is without considerable change, and device can long-term operation.
Comparative example 1
Select old process, coker gasoline enters hydrogenator after interchanger and process furnace, coker gasoline process table 2 under the reaction conditions of embodiment 1～4 in, product property is suitable with embodiment 1～4, but device operation after two months, reactor pressure decrease rises to 300kPa by initial 60kPa, is forced to stop work.
Claims (9)
1. a method for processing inferior gasoline, comprises the following steps:
(1) bad gasoline is mixed with hydrofining effluent, enters scale trap sedimentation coking material;
(2) react except defocused mixture mixes with hydrogen and enter hydrofining reactor after process furnace heating, obtain refining effluent;
(3) part for the refining effluent of step (2) gained loops back in step (1), mixes with bad gasoline;
(4) remainder of the refining effluent of step (2) gained enters gas-liquid separator and separates, and obtains gas phase and liquid phase, and liquid phase goes out device as product, and gas phase is circulated in step (1) and is used as recycle hydrogen.
2. according to working method claimed in claim 1, it is characterized in that, described inferior patrol is coker gasoline or FCC gasoline.
3. according to working method claimed in claim 1, it is characterized in that, the catalyzer using in described hydrofining reactor has following character: take aluminum oxide as carrier, take Mo and Co as active metal component; Catalyzer is containing MoO by weight
33.0～18.0w%, CoO 1.0～6.0w%, Co/Mo atomic ratio 0.1～1.0; The pore volume of catalyzer is 0.3～1.3mL/g, and specific surface area is 150～300m
2/ g.
4. according to working method claimed in claim 1, it is characterized in that, described in step (2), the operational condition of hydrofining reaction is: 220 ℃～400 ℃ of temperature of reaction, reaction pressure 1.0MPa～6.0MPa, volume space velocity 1.0h when liquid
-1～10.0h
-1, hydrogen to oil volume ratio 50～400.
5. according to working method claimed in claim 1, it is characterized in that, the scale trap described in step (1) is one or two.
6. according to working method claimed in claim 1, it is characterized in that, the aspect ratio of described scale trap is 1: 1～1: 5.
7. according to working method claimed in claim 1, it is characterized in that, when the liquid of the mixture of described inferior patrol and hydrofining effluent by scale trap, volume space velocity is 1.0h
-1～6.0h
-1.
8. according to working method claimed in claim 1, it is characterized in that, edge enters the direction of the Flow of Goods and Materials of settling vessel, and protectant size reduces gradually.
9. according to working method claimed in claim 8, it is characterized in that, described protective material is inert ceramic balls or oxidation aluminum strip.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010539215.2A CN102465025B (en) | 2010-11-05 | 2010-11-05 | Method for processing inferior gasoline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010539215.2A CN102465025B (en) | 2010-11-05 | 2010-11-05 | Method for processing inferior gasoline |
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| Publication Number | Publication Date |
|---|---|
| CN102465025A CN102465025A (en) | 2012-05-23 |
| CN102465025B true CN102465025B (en) | 2014-05-21 |
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|---|---|---|---|
| CN201010539215.2A Active CN102465025B (en) | 2010-11-05 | 2010-11-05 | Method for processing inferior gasoline |
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| Country | Link |
|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431920A (en) * | 1944-12-21 | 1947-12-02 | Shell Dev | Catalytic treatment of sulfurbearing hydrocarbon distillates |
| CN1900230A (en) * | 2005-07-18 | 2007-01-24 | 法国石油研究所 | New process for olefinic gasoline desulfurisation which limits mercaptan content |
| CN101591565A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of hydrofinishing process of inferior patrol |
-
2010
- 2010-11-05 CN CN201010539215.2A patent/CN102465025B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431920A (en) * | 1944-12-21 | 1947-12-02 | Shell Dev | Catalytic treatment of sulfurbearing hydrocarbon distillates |
| CN1900230A (en) * | 2005-07-18 | 2007-01-24 | 法国石油研究所 | New process for olefinic gasoline desulfurisation which limits mercaptan content |
| CN101591565A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of hydrofinishing process of inferior patrol |
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|---|---|
| CN102465025A (en) | 2012-05-23 |
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