CN102839011B - Adsorption desulfurization method - Google Patents
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Abstract
The invention relates to an adsorption desulfurization method. According to the method, a hydrocarbon raw material and a hydrogen donor enter a fluidized bed reactor having a plurality of reaction zones from the bottom of the reactor; a reduced desulfurization adsorbent enters the reactor from the top; the hydrocarbon raw material and the hydrogen donor are subjected to countercurrent contact with the reduced desulfurization adsorbent, wherein the desulfurized hydrocarbon is separated; the sulfur-loaded spent desulfurization adsorbent enters a fluidized bed regenerator, and contacts a regeneration air to carry out regeneration; the regenerated desulfurization adsorbent enters a redactor, and contacts a reduction air to carry out reduction; and the reduced desulfurization adsorbent returns to the reactor from the bottom of the fluidized bed reactor. With the method of the present invention, a sulfur loading amount of a spent sorbent is substantially increased, a regeneration frequency of an adsorbent required by removal of unit amount of sulfur is reduced, and activity and stability of the desulfurization sorbent are increased.
Description
Technical field
The invention belongs to a kind of desulfurization of hydrocarbon oil method, specifically, is a kind of method being reduced sulphur content in hydrocarbon ils under hydro condition by the absorption of fluidized-bed countercurrent reaction.
Background technology
Along with people are to the pay attention to day by day of environment protection, to also more and more stricter as the restriction of sulphur content in the light hydrocarbon of fuel.For gasoline, European Union in 2005 just regulation sulphur content be no more than 50 micrograms/gram, and plan regulation sulphur content in the Europe V gasoline standard implemented in 2010 be less than 10 micrograms/gram.China in the state III standard regulation content of sulfur in gasoline come into effect on December 31st, 2009 be not more than 150 micrograms/gram, if therefore Chinese oil fuel standard is in line with international standards, also need to carry out deep desulfuration.
The main method of traditional fuel oil desulfurization is hydrogenating desulfurization.But along with the increasingly stringent of standard of fuel, hydrogenation depth improves, and needs harsher reaction conditions as higher reaction pressure etc.Simultaneously for gasoline, due to containing a large amount of alkene, raising hydrogenation severity will cause higher loss of octane number, and therefore some new sulfur methods continue to bring out, and are wherein especially concerned by people most with adsorption desulfurize.
US7427581, US7182918, US6869522 and US6274533 etc. adopt sorbent material to carry out desulfurization to light hydrocarbon oil under hydro condition, the feature such as have that desulfurization depth is high, hydrogen consumption is low, loss of octane number is few, can production sulphur content be 30 micrograms/gram below oil fuel.Sorbent used with zinc oxide, silica and alumina mixture for carrier, wherein zinc oxide accounts for 10 ~ 90 heavy %, silica accounts for 5 ~ 85 heavy %, aluminum oxide accounts for 5 ~ 30 heavy %.Active ingredient is the as-reduced metal of load, is made up of the one in the cobalt be carried on carrier, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, vanadium etc. or one.Carrier and metal component obtain sorbent material through mixing, after shaping, dry, roasting, 0.1 ~ 10.3MPa, 37.7 ~ 537.7 DEG C, weight hourly space velocity is 0.5 ~ 50h
-1with under the condition of facing hydrogen, capture on sorbent material by the sulphur in oil product, the hydrocarbon generated after sulfide cracking turns back in reaction mass, is recycled by cyclic regeneration containing sulfur absorbent.Although the method can realize deep desulfuration, reaction product sulphur content is larger by feed sulphur content influence of fluctuations.
CN101067093A adopts moving-burden bed reactor to carry out desulphurization reaction to catalytically cracked gasoline under the effect of absorbing desulfurization catalyst, and in moving-bed regeneration system rapidly, carries out cyclic regeneration reduction to the absorbing desulfurization catalyst of inactivation.Raw material enters reactor after preheating, and following current or adverse current and catalyst exposure, temperature of reaction 120 ~ 600 DEG C, reaction pressure 0.4 ~ 7.2MPa, weight hourly space velocity is 0.1 ~ 100h
-1, absorbing desulfurization catalyst translational speed is 0.02 ~ 1.0m/h, and the mol ratio of hydrogen and catalytically cracked gasoline raw material is react under the reaction conditions of 0.2 ~ 6.0, realizes desulfurization object.Although this reactive mode can utilize the reactive behavior of catalyzer to large extent, how to keep good fluidity when the relatively large sulphur of absorbing desulfurization catalyst load or become the key of application.
Adsorption desulfurize rate is except affecting by desulfuration adsorbent character, feed sulphur content and reaction conditions etc., and the impact that in raw material, dissimilar sulfide decreasing ratio carries sulfur content by desulfuration adsorbent is larger.Find in the research that contriver reacts at adsorption desulfurize, the sulphur content impact that the thiophenic sulfur decreasing ratio sorbent suspension in catalytically cracked gasoline is accumulated is comparatively large, some inorganic sulfurs, thioether and mercaptan sulfur etc. then sorbent suspension to carry the impact of sulfur content less.
Summary of the invention
The object of this invention is to provide a kind of desulfurizing method by adsorption, to improve the effect of desulfurization further.
Adsorption method provided by the invention comprises the following steps:
(1) hydrocarbon feed, hydrogen donor enter in this reactor bottom the fluidized-bed reactor with multi-reaction-area, desulfuration adsorbent after reduction enters in this reactor from the top of this reactor, desulfuration adsorbent counter current contact after hydrocarbon feed, hydrogen donor and reduction, the hydrocarbon after desulfurization goes to be separated;
(2) desulfuration adsorbent to be generated after carrying sulphur enters in fluid bed regenerator, regenerates with rejuvenating gas contacts;
(3) desulfuration adsorbent after regeneration enters in reducer, contacts reduce with reducing gas;
(4) desulfuration adsorbent after reduction returns in this reactor from the bottom of fluidized-bed reactor.
Described hydrocarbon feed is selected from one or more in Sweet natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas oil, preferred gasoline and/or diesel oil.Above-mentioned gasoline, kerosene, diesel oil and gas oil fraction are its full cut and/or its part narrow fraction.The sulphur content of described hydrocarbon feed 50 micrograms/gram more than, preferably 100 micrograms/gram more than.
Described hydrogen donor is selected from one or more the mixture in hydrogen, hydrogen-containing gas and hydrogen supply agent.Hydrogen refers to the hydrogen of various purity, one or more in hydrogen-containing gas preferred catalytic cracking (FCC) dry gas, coking dry gas, thermally splitting dry gas, hydrogen volume content is preferably more than 30%, and hydrogen supply agent is selected from one or more in naphthane, perhydronaphthalene, indane.
Described desulfuration adsorbent comprises various load metal oxide sorbent material, is loaded with the load metal oxide of metallic promoter agent, one or several in various sulphur transforming agent and sulfur absorbent.Described desulfuration adsorbent, for ease of fluidisation, is preferably microspheroidal, and its median size is 20 ~ 200 microns, preferably 40 ~ 100 microns.Described metal is that zinc and group VIII metal are as nickel etc.
The reaction conditions of adsorption desulfurize is as follows: temperature 200 ~ 550 DEG C preferably 300 ~ 500 DEG C, pressure 0.5 ~ 5MPa preferably 1.0 ~ 3.5MPa, weight hourly space velocity 0.1 ~ 100h
-1preferably 1 ~ 10h
-1, hydrogen donor and hydrocarbon feed volume ratio are 0.01-1000 preferably 0.05 ~ 500.
Regeneration condition is as follows: regeneration temperature is 300 ~ 800 DEG C preferably 350 ~ 600 DEG C, regeneration pressure 0.1 ~ 3.0MPa preferably 0.1 ~ 1.0MPa.Regeneration gas is oxygen-containing gas, is selected from the one in the mixture of the mixture of oxygen, air, oxygen and non-active gas, air and non-active gas, and described non-active gas, as nitrogen etc.
Reductive condition is as follows: reduction temperature is 250 ~ 550 DEG C preferably 300 ~ 450 DEG C, reduction pressure 0.2 ~ 5.0MPa preferably 0.5 ~ 3.5MPa.Described reducing gas is hydrogen or the gas being rich in hydrogen.
The described fluidized-bed reactor with multi-reaction-area is divided into plural reaction zone downwards successively from top, desulfuration adsorbent is transported to the reaction zone I being positioned at fluidized-bed reactor top after promoting, along with the increase of quantity of sorbent in the I of reaction zone, partial desulfurization sorbent material is delivered to the reaction zone II of I bottom, reaction zone by bypass, equally, desulfuration adsorbent in the II of reaction zone is delivered to the reaction zone III being positioned at its underpart through bypass, by that analogy.Reacted desulfuration adsorbent draws off from the reaction zone of fluidized-bed reactor bottommost, recycles after regeneration, reduction.
Pipeline through being equipped with guiding valve between every two adjacent reaction zones is communicated with, and along with the increase of desulfuration adsorbent amount in a upper reaction zone, the desulfuration adsorbent carried after sulphur is delivered to next reaction zone through bypass.The top of reaction zone I is provided with desulfurization hydrocarbon ils and hydrogen outlet, and desulfurization hydrocarbon ils and hydrogen donor are drawn through pipeline; The top of reaction zone I is provided with the desulfuration adsorbent entrance after reduction, and the desulfuration adsorbent after reduction is introduced through pipeline; The bottom of last reaction zone is provided with hydrocarbon oil containing surphur and hydrogen donor entrance, and hydrocarbon oil containing surphur and hydrogen are introduced through pipeline; Last reaction zone is also provided with desulfuration adsorbent to be generated outlet, and desulfuration adsorbent to be generated is drawn through pipeline.
The subregion of described fluidized-bed reactor reaction zone or can use the means such as wide bore distribution plate, grid, reactor reducing or use two and the series connection of plural fluidized-bed reactor to obtain by sorbent material Natural Division in the reactor.
The present invention compared with prior art, has following unforeseeable technique effect:
1, in fluid-bed sweetening reactor, desulfuration adsorbent and the hydrocarbon oil containing surphur counter current contact with favourable absorption sweetening effectiveness carry out adsorption desulfurize reaction, desulfuration adsorbent to be generated is in fluid bed regenerator and oxygen-containing gas and stream completes regeneration, sorbent material maintains fluidized, is conducive to the smooth and easy of realization response-regeneration and carries out continuously.
2, fluid-bed sweetening reactor is divided into plural reaction zone from top to bottom, sorbent material enters reactor from reactor head reaction zone, regeneration is drawn off from reactor bottom reaction zone, hydrocarbon oil crude material enters reactor from reactor bottom, achieves desulfuration adsorbent and always flows to and the counter current contact of reacting hydrocarbon ils.Low activity desulfuration adsorbent elder generation after a certain amount of sulphur of load and contact raw, remove the sulfide that inorganic sulfur wherein, mercaptan and thioether etc. easily remove, the adsorbent contact of the more difficult alkylthrophene sulfides that removes and high reactivity low-sulfur carrying capacity, improve on the basis of desulfuration adsorbent reactive behavior utilization ratio, significantly improve year sulfur content on sorbent material to be generated, reduce the regeneration frequency removing sorbent material needed for unit sulfur content, improve activity and the stability of desulfuration adsorbent.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of desulfurization of hydrocarbon oil method provided by the invention.
Fig. 2 is the adsorption desulfurize reactor assembly schematic diagram containing two reaction zones provided by the invention.
Embodiment
Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Fig. 1 is the method schematic diagram that hydrocarbon ils provided by the invention faces hydrogen adsorption desulfurization in fluidized-bed reactor.This figure comprises fluidized-bed reactor 2, fluid bed regenerator 15, reactor receptor 5, reducer 21, regenerator feed tank 12, Regenerator receiver 18 and the locking hopper 8 for being isolated by reaction-regeneration system.
Hydrocarbon oil containing surphur after preheating and hydrogen enter bottom reactor 2 through pipeline 1, contact with the desulfuration adsorbent in reactor, after desulphurization reaction, enter the strainer of reactor head, carry out finish separation, the hydrocarbon ils after desulfurization and hydrogen are sent to follow-up product separation system through pipeline 3.Reacted desulfuration adsorbent to be generated draws off from reactor bottom and is sent to reactor receptor 5 through pipeline 4, after stripping, locking hopper 8 is sent to through pipeline 6 and 7 successively in reactor receptor 5, after nitrogen replacement, change low pressure inert atmosphere into from hydrogen gas environment, displacement gas is sent to roasting kiln through pipeline 19 and burns.Desulfuration adsorbent to be generated is then delivered to regenerator feed tank 12 through pipeline 10 and 11 successively, pipeline 13 by being equipped with guiding valve between regenerator feed tank 12 with revivifier 15 is connected, and desulfuration adsorbent to be generated rises and the speed controlling to enter into revivifier by guiding valve through promoting air lift.Oxygen-containing gas enters into revivifier by pipeline 14 from regenerator bottoms, desulfuration adsorbent to be generated also flows with oxygen-containing gas and contacts through burning sulphur in revivifier 15, the desulfuration adsorbent after regenerating is obtained after burning carbon, sulfur-containing smoke gas is delivered to sulphur system processed through pipeline 16 after regenerator overhead is separated with regenerative sulfur binding sorbent material or alkali cleaning removes SOx, regenerative sulfur binding sorbent material is transported to Regenerator receiver 18 from reactor top emulsion zone through pipeline 17, promote with nitrogen and be delivered to locking hopper 8 through pipeline 19 and 7 successively, replace by hydrogen stripped in locking hopper 8 and change hydrogen gas environment into after boosting, be delivered in reducer 21 through pipeline 10 and 20 successively and reduce, regenerative sulfur binding sorbent material after reduction is delivered to the top of reactor 2 by pipeline 22, realize carrying out continuously of desulfurization absorption reaction.
Fig. 2 is the adsorption desulfurize reactor assembly schematic diagram containing two reaction zones provided by the invention, but this reactor is not limited to two reaction zones.
This reactor 2 is divided into two reaction zones from top to bottom successively: reaction zone I, reaction zone II, separate with wide bore distribution plate between reaction zone I and reaction zone II, reaction zone I is communicated with the pipeline 24 of reaction zone II through being equipped with guiding valve, along with the increase of desulfuration adsorbent amount in the I of reaction zone, the desulfuration adsorbent carried after sulphur is delivered to reaction zone II through bypass.The top of reaction zone I is provided with desulfurization hydrocarbon ils and hydrogen outlet, and desulfurization hydrocarbon ils and hydrogen are drawn through pipeline 3; The top of reaction zone I is provided with the desulfuration adsorbent entrance after reduction, and the desulfuration adsorbent after reduction is introduced through pipeline 22; The bottom of reaction zone II is provided with hydrocarbon oil containing surphur and hydrogen inlet, and hydrocarbon oil containing surphur and hydrogen are introduced through pipeline 2; The bottom of reaction zone II is also provided with desulfuration adsorbent to be generated outlet, and desulfuration adsorbent to be generated is drawn through pipeline 4.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.Table 1 listed in by the stock oil used in embodiment, comparative example, and desulfuration adsorbent is produced by China PetroChemical Corporation's catalyzer Nanjing branch office, and the trade mark is FCAS-R09, and with zinc oxide, silica and aluminum oxide for carrier, load Ni is as promotor.Use the reactor shown in Fig. 2, test according to the flow process shown in Fig. 1.
Embodiment 1
Containing on the fluidized-bed reactor of two reaction zones, selecting compared with the catalytically cracked gasoline raw material B of low sulfur content is reaction raw materials, uses hydrogen as hydrogen medium, temperature of reaction 400 DEG C, reaction pressure 1.4MPa, weight hourly space velocity be 5h
-1, react under the reaction conditions of hydrogen to oil volume ratio 45, concrete reaction conditions lists in table 2.Result shows, reaction product sulphur content in initial reaction stage lower than 0.5ppm (chromatographic detectability), along with the carrying out in reaction times, in product, sulphur content raises gradually, but due to feed sulphur content lower, only have 204.5ppm, therefore at the end of reaction, product sulphur content also only has 3.6ppm, and due to raw material olefin content also lower, make uprising figure penalties only have 0.2 unit.
Embodiment 2
Stretch tight on device in the fluidisation containing two reaction zones, select the catalytically cracked gasoline raw material A of higher sulfur content to be reaction raw materials, use hydrogen as hydrogen medium, temperature of reaction 400 DEG C, reaction pressure 1.4MPa, weight hourly space velocity be 5h
-1, react under the reaction conditions of hydrogen to oil volume ratio 45, concrete reaction conditions and the results are shown in table 2.Due to the increase of raw material olefin content, uprising figure penalties is 0.3 unit, compared with the raw material B that sulphur content is lower, raw material A sulphur content significantly increases, sulphur content in product is caused to rise comparatively fast with the prolongation in reaction times, but still remain on a lower level, at the end of reaction, product sulfur levels only has 10.8ppm.
Embodiment 3
Containing on the fluidized-bed reactor of two reaction zones, select the catalytically cracked gasoline raw material A of higher sulfur content to be reaction raw materials, use hydrogen as hydrogen medium, temperature of reaction 430 DEG C, reaction pressure 3.0MPa, weight hourly space velocity be 7h
-1, react under the reaction conditions of hydrogen to oil volume ratio 100, concrete reaction conditions and the results are shown in table 2.Due to the raising of reaction pressure and temperature of reaction, reaction product sulphur content only has 3.8ppm at the end of reaction, and uprising figure penalties only has 0.5 unit.Although the significantly increase of reaction pressure and reactive hydrogen oil ratio likely causes uprising figure penalties to strengthen, but owing to improve temperature of reaction simultaneously, inhibit the carrying out of hydrogenation reaction, the cracking ability of sorbent material strengthens simultaneously, small molecules hydro carbons increases, therefore the uprising index of product only reduces 0.5 unit, and bulk product liquid is received and still remained on 99.2%.
Comparative example 1
On the fluidized-bed reactor in single reaction district, select the catalytically cracked gasoline raw material A of higher sulfur content to be reaction raw materials, use hydrogen as hydrogen medium, temperature of reaction 400 DEG C, reaction pressure 1.4MPa, weight hourly space velocity be 5h
-1, react under the reaction conditions of hydrogen to oil volume ratio 45, concrete reaction conditions and the results are shown in table 2.Although in product, sulphur content is also lower when reaction starts, only has 0.5ppm, but along with the carrying out of reaction, in product, sulphur content is elevated to 43.1ppm, far above the 9.3ppm of embodiment 2, illustrate on the fluidized-bed reactor in single reaction district, the desulphurizing activated meeting of sorbent material declines fast along with the raising of sulphur charge capacity.
Table 1
| Raw material is numbered | A | B |
| Density (20 DEG C), kg/m 3 | 726.2 | 715.2 |
| Sulphur, ppm | 573.0 | 204.5 |
| Alkene, heavy % | 39.2 | 26.0 |
| Aromatic hydrocarbons, heavy % | 18.6 | 17.9 |
| Alkane, heavy % | 42.2 | 56.1 |
Table 2
Claims (13)
1. a desulfurizing method by adsorption, is characterized in that the method comprises the following steps:
(1) hydrocarbon feed, hydrogen donor enter in this reactor bottom the fluidized-bed reactor with multi-reaction-area, desulfuration adsorbent after reduction enters in this reactor from the top of this reactor, desulfuration adsorbent counter current contact after hydrocarbon feed, hydrogen donor and reduction, the hydrocarbon after desulfurization goes to be separated;
(2) desulfuration adsorbent to be generated after carrying sulphur enters in fluid bed regenerator, regenerates with rejuvenating gas contacts;
(3) desulfuration adsorbent after regeneration enters in reducer, contacts reduce with reducing gas;
(4) desulfuration adsorbent after reduction returns in this reactor from the top of fluidized-bed reactor;
The described fluidized-bed reactor with multi-reaction-area is divided into plural reaction zone downwards successively from top, desulfuration adsorbent is transported to the reaction zone I being positioned at fluidized-bed reactor top after promoting, along with the increase of quantity of sorbent in the I of reaction zone, partial desulfurization sorbent material is delivered to the reaction zone II of I bottom, reaction zone by bypass, equally, desulfuration adsorbent in the II of reaction zone is delivered to the reaction zone III being positioned at its underpart through bypass, by that analogy, reacted desulfuration adsorbent draws off from the reaction zone of fluidized-bed reactor bottommost, through regeneration, recycle after reduction.
2., according to the method for claim 1, it is characterized in that one or more that described hydrocarbon feed is selected from Sweet natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas oil.
3. according to the method for claim 1 or 2, it is characterized in that the sulphur content of described hydrocarbon feed 50 micrograms/gram more than.
4. according to the method for claim 1, it is characterized in that described hydrogen donor is selected from one or more the mixture in hydrogen, hydrogen-containing gas and hydrogen supply agent, hydrogen refers to the hydrogen of various purity, hydrogen-containing gas is selected from one or more in catalytic cracked dry gas, coking dry gas, thermally splitting dry gas, hydrogen volume content is more than 30%, and hydrogen supply agent is selected from one or more in naphthane, perhydronaphthalene, indane.
5., according to the method for claim 1, it is characterized in that described desulfuration adsorbent comprises various load metal oxide sorbent material, is loaded with the load metal oxide of metallic promoter agent, one or several in various sulphur transforming agent and sulfur absorbent.
6. according to the method for claim 1, it is characterized in that the reaction conditions of adsorption desulfurize is as follows: temperature 200 ~ 550 DEG C, pressure 0.5 ~ 5MPa, weight hourly space velocity 0.1 ~ 100h
-1, hydrogen donor and hydrocarbon feed volume ratio are 0.01-1000.
7. according to the method for claim 6, it is characterized in that the reaction conditions of adsorption desulfurize is as follows: temperature 300 ~ 500 DEG C, pressure 1.0 ~ 3.5MPa, weight hourly space velocity 1 ~ 10h
-1, hydrogen donor and hydrocarbon feed volume ratio are 0.05 ~ 500.
8. according to the method for claim 1, it is characterized in that regeneration condition is as follows: regeneration temperature is 300 ~ 800 DEG C, regeneration pressure 0.1 ~ 3.0MPa, regeneration gas is oxygen-containing gas, is selected from the one in the mixture of the mixture of oxygen, air, oxygen and non-active gas, air and non-active gas.
9. according to the method for claim 8, it is characterized in that regeneration condition is as follows: regeneration temperature is 350 ~ 600 DEG C, regeneration pressure 0.1 ~ 1.0MPa.
10. according to the method for claim 1, it is characterized in that reductive condition is as follows: reduction temperature is 250 ~ 550 DEG C, reduction pressure 0.2 ~ 5.0MPa, described reducing gas is hydrogen or the gas being rich in hydrogen.
11., according to the method for claim 10, is characterized in that reductive condition is as follows: reduction temperature is 300 ~ 450 DEG C, reduction pressure 0.5 ~ 3.5MPa.
12. according to the method for claim 1, it is characterized in that the pipeline through being equipped with guiding valve between every two the adjacent reaction zones of described reactor is communicated with, along with the increase of desulfuration adsorbent amount in a upper reaction zone, the desulfuration adsorbent carried after sulphur is delivered to next reaction zone through bypass, the top of reaction zone I is provided with desulfurization hydrocarbon ils and hydrogen outlet, and desulfurization hydrocarbon ils and hydrogen donor are drawn through pipeline; The top of reaction zone I is provided with the desulfuration adsorbent entrance after reduction, and the desulfuration adsorbent after reduction is introduced through pipeline; The bottom of last reaction zone is provided with hydrocarbon oil containing surphur and hydrogen inlet, and hydrocarbon oil containing surphur and hydrogen donor are introduced through pipeline; Last reaction zone is also provided with desulfuration adsorbent to be generated outlet, and desulfuration adsorbent to be generated is drawn through pipeline.
13. according to the method for claim 1, it is characterized in that the subregion of described reactor reaction zone or can use wide bore distribution plate, grid, reactor reducing means or use two and the series connection of plural fluidized-bed reactor to obtain by desulfuration adsorbent Natural Division in the reactor.
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| CN104560123B (en) * | 2013-10-29 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of method adsorbing desulfurization |
| CN104593047B (en) * | 2013-10-31 | 2016-03-23 | 中国石油化工股份有限公司 | A kind of adsorption desulfurize reaction unit and a kind of desulfurizing method by adsorption |
| CN103706345B (en) * | 2013-12-17 | 2016-08-17 | 南京工业大学 | Process for regenerating MOFs adsorbent for deep desulfurization of automotive diesel oil |
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| CN112745937B (en) * | 2019-10-31 | 2022-10-21 | 中国石油化工股份有限公司 | Catalytic cracking light product desulfurization method and device |
| AU2020374918A1 (en) * | 2019-10-31 | 2022-05-19 | China Petroleum & Chemical Corporation | Method and apparatus for desulfurization and separation of catalytically cracked light product |
| CN114570437B (en) * | 2020-12-02 | 2023-07-14 | 中国石油化工股份有限公司 | Method for removing sulfur in catalyst for moving bed propane dehydrogenation |
| CN115678595B (en) * | 2021-07-30 | 2024-03-12 | 中国石油化工股份有限公司 | Deep desulfurization method and system for gasoline |
| CN115678608B (en) * | 2021-07-30 | 2024-03-12 | 中国石油化工股份有限公司 | Deep desulfurization method and system for gasoline |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997007054A1 (en) * | 1995-08-14 | 1997-02-27 | The Pritchard Corporation | Process for desulfurizing gasoline and hydrocarbon feedstocks |
| CN101049927A (en) * | 2007-04-18 | 2007-10-10 | 清华大学 | Method for producing Nano carbon tubes continuously and equipment |
| CN101247883A (en) * | 2005-06-07 | 2008-08-20 | 中国石油化工股份有限公司 | Desulfurization in turbulent fluid bed reactor |
| CN101433819A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Desulphurization sorbent composition |
| JP4599754B2 (en) * | 2001-05-17 | 2010-12-15 | 株式会社Ｉｈｉ | Dry desulfurization equipment |
-
2011
- 2011-06-23 CN CN201110170217.3A patent/CN102839011B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997007054A1 (en) * | 1995-08-14 | 1997-02-27 | The Pritchard Corporation | Process for desulfurizing gasoline and hydrocarbon feedstocks |
| JP4599754B2 (en) * | 2001-05-17 | 2010-12-15 | 株式会社Ｉｈｉ | Dry desulfurization equipment |
| CN101247883A (en) * | 2005-06-07 | 2008-08-20 | 中国石油化工股份有限公司 | Desulfurization in turbulent fluid bed reactor |
| CN101049927A (en) * | 2007-04-18 | 2007-10-10 | 清华大学 | Method for producing Nano carbon tubes continuously and equipment |
| CN101433819A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Desulphurization sorbent composition |
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