CN1179021C - A kind of diesel oil adsorption desulfurization method - Google Patents
A kind of diesel oil adsorption desulfurization method Download PDFInfo
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- CN1179021C CN1179021C CNB021260168A CN02126016A CN1179021C CN 1179021 C CN1179021 C CN 1179021C CN B021260168 A CNB021260168 A CN B021260168A CN 02126016 A CN02126016 A CN 02126016A CN 1179021 C CN1179021 C CN 1179021C
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- diesel oil
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Abstract
一种含有机硫化物杂质的柴油吸附脱硫的方法，是将柴油在流化床或淤浆床反应器中与一种以镍为主要活性组分的非晶态合金吸附剂在室温-150℃、常压-2.0兆帕的条件下进行接触。该方法不但工艺简单、投资少、吸附剂可再生使用，而且脱硫率可达60重量%以上。A method for adsorption and desulfurization of diesel oil containing organic sulfide impurities is to combine diesel oil with an amorphous alloy adsorbent with nickel as the main active component in a fluidized bed or slurry bed reactor at room temperature -150 ° C , Contact under the condition of normal pressure -2.0 MPa. The method not only has simple process, less investment, and the adsorbent can be regenerated, but also the desulfurization rate can reach more than 60% by weight.
Description
Technical field
The invention relates to a kind of method of diesel oil adsorption desulfurizing, is the method that the sorbent material of the main active component diesel oil after to hydrogenating desulfurization carries out adsorption desulfurize about adopting with nickel particularly.
Background technology
Along with the increasingly stringent that environmental protection requires diesel quality, people improve constantly being limited in of sulphur content in the diesel oil fuel.Many countries maybe will carry out the regulation that the derv fuel oil sulphur content is not more than 500 μ gg-1, and European Union advised once that diesel oil sulphur content in 2000 was not more than 350 μ gg-1, and the directivity index that gives diesel oil sulphur content limit value in 2005 in addition is 50 μ gg-1.But there are indications that the European Community may be reduced to 10ppm with the sulphur content specification.The low sulfuration of diesel oil has been the common trend in the world.
In order to ensure desulfurization depth and make production cost low as far as possible, sophistication has important effect.And modern technique be on the one hand the exploitation low pressure deep desulfuration/aromatic hydrocarbons saturation process open money with saving; To develop the Hydrobon catalyst of excellent performance on the other hand, to remove dimethyldibenzothiophene that is difficult to hydrogenating desulfurization etc.But, use this ultra-deep hydrodesulfuration to need the revolution of technology, because it is high temperature, a high-pressure process that needs dedicated catalyst, this has just determined the equipment of this process and process cost higher, will need huge investment undoubtedly.
Except deep hydrodesulfurizationof, american energy Biosys Corp. has developed the diesel bio desulfurization technology, and the sulfide that this technology can be difficult to hydrogenating desulfurization to remove is removed.
An emerging in addition technology is to adopt the optionally sulfocompound in the adsorbing and removing diesel oil of sorbent material, as mercaptan, thiophene etc.Compare with traditional hydrodesulfurization, the advantage of absorption method has: do not consume hydrogen, can avoid producing unnecessary light component by product, do not need high temperature, highly compressed reaction conditions, facility investment and process cost are low.The main type of the sorbent material of research at present and use has: oxide adsorbent (γ-Al
2O
3, TiO
2, ZrO
2, ZnO
2, SiO
2), loaded metal (Ni, Na, K, Ca, oxide adsorbent Ba), adsorbent of molecular sieve (A, X, Y, TS-1, SAPO-34, MCM-41) and the adsorbent of molecular sieve of metal ion exchanged etc.
At USP6, once mentioned that Raney nickel can be used as sorbent material and removes after the hydrogenating desulfurization remaining thiophenic sulfur in the hydrocarbon fuel in 221,280, whether can regenerate report is never arranged but be used for Raney nickel behind the adsorption desulfurize.
Up to now, known to the inventor, the present report that with nickel is the amorphous alloy of main active component as the sorbent material of adsorption desulfurize still of no use.
Summary of the invention
The purpose of this invention is to provide a kind of new diesel oil adsorption desulfurizing method.
Desulfurizing method by adsorption provided by the invention comprise the diesel oil that will contain organic sulfide impurity with a kind of be that the amorphous alloy adsorbent of main active component contacts and carries out adsorption desulfurize with nickel, contact is to carry out in fluidized-bed or slurry bed reactor under the condition of room temperature-150 ℃, normal pressure-2.0 MPa.
Method provided by the present invention has no particular limits the diesel oil that contains organic sulfide that is suitable for, and can be straight-run diesel oil, catalytic diesel oil or coker gas oil, and its sulphur content can be 500-10000ppm in elementary sulfur weight.But consider that the organic sulfide of major part in the diesel oil such as mercaptan, thioether, thiophene etc. are easy to remove by the method for hydrogenation, for the purpose of economical and practical, preferably use the diesel oil after the hydrogenating desulfurization in the method provided by the invention, this moment, the machine sulfide that mainly contains wherein was thionaphthene and/or dibenzothiophene and the derivative thereof that ordinary method is difficult to remove, and its sulphur content is counted 20-500ppm with elementary sulfur weight.
Used in the present invention is only to have located a diffuse maximum at 45 ° in the X-ray diffractogram of amorphous alloy adsorbent of main active component in 2 θ are 20-80 ° scope with nickel, and it consists of a kind of metal among copper, molybdenum, cobalt, chromium and the tungsten of being selected from of the iron of aluminium, 0-40 weight % of nickel, the 1-80 weight % of 20-95 weight % and 0-20 weight %.
The preparation method of employed these amorphous alloy materials can be referring to other patent of the applicant in the inventive method, as: USP6,368,996; CN1073726A; CN1152475A and CN1272399A incorporate these documents into the present invention as a reference at this.
The particle diameter of used sorbent material is advisable with the 10-1000 micron in the method provided by the invention, and preferred particle diameter is the 30-500 micron.
Method provided by the invention both can be carried out in fluidized-bed reactor, also can carry out in slurry bed reactor.
When carrying out adsorption desulfurize in fluidized-bed reactor, volume space velocity is 2-40 hour-1 during adoptable liquid.
When carrying out adsorption desulfurize in slurry bed reactor, the absorbent concentration that can adopt is 0.5-20 weight %, and the residence time is 0.5-60 minute; Preferred absorbent concentration is 0.5-10 weight %, and the residence time is 2-30 minute.
Sorbent material behind the adsorption desulfurize is after liquid (diesel oil) solid (sorbent material) separates, but both part sent for regeneration, the part Returning reactor that circulates continued to use, and re-used after the whole sent for regeneration of also visual its sweetening effectiveness.
Desulfurizing method by adsorption provided by the invention has adopted that organic sulfide is had the ni based amorphous alloy of strong adsorptive power is sorbent material, simple, the less investment of technology not only, the renewable use of sorbent material, and having sweetening effectiveness preferably, the sulfur removal rate in the diesel oil behind the hydrogenation can reach more than the 60 weight %.This method can make up with traditional hydrodesulfurization to produce ultra-low-sulphur diesel.
Embodiment
The following examples will be described further processing method provided by the invention, but not thereby limiting the invention.
Embodiment 1
In present embodiment explanation the inventive method used a kind of be the preparation of the amorphous alloy adsorbent of main active component with nickel.
50 gram nickel, 50 gram aluminium are joined in the plumbago crucible, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, to be sprayed onto a rotating speed from the crucible nozzle be on 670 rev/mins the copper roller to this alloy liquid then, logical water coolant in the copper roller, alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, the flakey band is the 30-100 micron through being ground to particle diameter, obtains mother alloy.Mother alloy places hydrogen environment to heat-treat in 3 hours at 700 ℃ of following constant temperature.Mother alloy after heat treatment slowly joins in the there-necked flask that fills 500 grams, 20% aqueous sodium hydroxide solution, controls its temperature and is 100 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid is 7 with 80 ℃ distilled water washs to pH value.Prepared sorbent material is numbered sorbent material-1, and its composition is listed in table 1.
Embodiment 2
In present embodiment explanation the inventive method used a kind of be the preparation of the amorphous alloy adsorbent of main active component with nickel.
48.2 gram nickel, 50 gram aluminium, 1.8 gram chromium are joined in the plumbago crucible, it is heated to fusion more than 1600 ℃ in high frequency furnace, make its alloying, to be sprayed onto a rotating speed from the crucible nozzle be on 670 rev/mins the copper roller to this alloy liquid then, logical water coolant in the copper roller, alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, and the flakey band is the 30-100 micron through being ground to particle diameter.Slowly join then in the there-necked flask that fills 500 grams, 20% aqueous sodium hydroxide solution, control its temperature and be 100 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid is 7 with 80 ℃ distilled water wash pH values.Prepared sorbent material is numbered sorbent material-2, and its composition is listed in table 1.
Embodiment 3
In present embodiment explanation the inventive method used a kind of be the preparation of the amorphous alloy adsorbent of main active component with nickel.
44 gram nickel, 4 gram copper, 52 gram aluminium are joined in the plumbago crucible, it is heated to fusion more than 1600 ℃ in high frequency furnace, make its alloying, to be sprayed onto a rotating speed from the crucible nozzle be on 670 rev/mins the copper roller to this alloy liquid then, logical water coolant in the copper roller, alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, and the flakey band is the 30-100 micron through being ground to particle diameter.Slowly join then in the there-necked flask that fills 500 grams, 20% aqueous sodium hydroxide solution, control its temperature and be 100 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid is 7 with 80 ℃ distilled water wash pH values.Prepared sorbent material is numbered sorbent material-3, and its composition is listed in table 1.
Embodiment 4-7
Step according to embodiment 3 prepares employed sorbent material among the present invention, and different is component and content difference.The sorbent material of preparing-4 to the composition of sorbent material-7 is listed in table 1.
Table 1
Embodiment sorbent material numbering sorbent material is formed
1 sorbent material-1 Ni
92Al
8
2 sorbent materials-2 Ni
84Cr
3.3Al
12.7
3 sorbent materials-3 Ni
74Cu
7.0Al
19
4 sorbent materials-4 Ni
86.7Co
8.3Al
5
5 sorbent materials-5 Ni
87Fe
2Cr
3Al
8
6 sorbent materials-6 Ni
90Mo
2.5Al
7.5
7 sorbent materials-7 Ni
58.4Fe
32.3Al
9.3
The following examples 8-17 explanation adopts fluidized-bed to implement the result of the inventive method.
Embodiment 8-14
These examples have illustrated the removal effect of desulfurizing method by adsorption provided by the invention to organic sulfide in the diesel oil.
Embodiment has chosen and has a kind ofly removed the raw material of the catalytic diesel oil of most of sulfide as adsorption desulfurize through hydrogenating desulfurization, and its essential property is as follows: density 0.8400g/cm
3, boiling range 204-371 ℃, sulphur content 70ppm.
At internal diameter 14mm, external diameter 18mm, adding the 20ml granularity in the fluidized-bed reactor of long 540mm is the sorbent material of 40-60 micron, with pump diesel raw material is squeezed into from reactor bottom.The sulphur content of absorption back diesel oil is measured with high resolution gas-chromatography-atomic emission spectrum detector (GC-AED), and gained the results are shown in table 2.Table 3 has been listed the forward and backward sulfur compound distribution of diesel oil adsorption desulfurizing in the example 12.
Table 2
Implement temperature, pressure air speed absorption back sulphur and contain desulfurization degree
Sorbent material
Example (℃) (MPa) (h
-1) amount (ppm) (heavy %)
8 sorbent materials-1 60 0.5 59 87.1
9 sorbent materials-2 80 0.5 5 14 80.0
10 sorbent materials-3 100 0.5 5 21 70.0
11 sorbent materials-4 100 1.0 5 24 65.7
12 sorbent materials-5 100 1.0 5 10 85.7
13 sorbent materials-6 100 1.0 5 17 75.7
14 sorbent materials-7 100 1.0 5 25 64.3
Table 3
Sulfur compound feed sulphur content (ppm) absorption back sulphur content (ppm)
C2-C
6H
4-C
4H
3S 4.5 -
C3-C
6H
5-C
4H
3S 13.4 -
C4-C
6H
5-C
4H
3S 3.4 -
C5，C6-C
6H
5-C
4H
3S 4.7 -
4-CH
3-2-C
6H
5-C
4H
3S 4.6 -
4-C
2H
5-2-C
6H
5-C
4H
3S 5.6 2.1
4，6-DMDBT 2.4 0.5
1，3-DMDBT 16.8 3.2
2，3-DMDBT 4.4 -
C3-DBT 5.1 -
C4-DBT 4.0 -
C5-DBT，C6-DBT 2.9 -
Other are 7 4.0 years old
Total sulfur content 70 10
Embodiment 15-17
These examples are chosen and have been added 4 of 80ppm, and the above-mentioned diesel oil of 6-dimethyl Dibenzothiophene is as the adsorption desulfurize raw material, and its total sulfur content is 150ppm.According to the described method of embodiment 8-14 it is carried out adsorption desulfurize, the results are shown in table 4.
Table 4
Temperature, pressure air speed absorption back sulphur contains desulfurization degree
The embodiment sorbent material
(℃) (MPa) (h
-1) amount (ppm) (heavy %)
15 sorbent materials-1 100 0.5 4 42 72.0
16 sorbent materials-2 100 0.5 4 37 75.3
17 sorbent materials-5 100 0.5 4 30 80.0
Embodiment 18-21
These embodiment illustrate and adopt slurry bed reactor to implement result of the present invention.
Catalytic diesel oil and 1 gram particle degree after the hydrogenating desulfurization that adding 100ml is identical with example 8-14 in 0.3 liter slurry bed reactor are the sorbent material-5 of 40-60 micron; the protection of the above inflated with nitrogen of liquid level separates sorbent material after stirring 10 minutes under the condition of 300 rev/mins of normal pressures, rotating speed with diesel oil.The analytical results of sulphur content is listed in table 5 in the diesel oil of absorption back.
Table 5
Absorption back sulphur content desulfurization degree
The embodiment temperature (℃)
(ppm) (heavy %)
18 20 20 71.4
19 40 15 78.6
20 60 10 85.7
21 80 9 87.1
Claims (7)
1, a kind of desulfurizing method by adsorption that contains the diesel oil of organic sulfide impurity, comprise diesel oil contacted with a kind of sorbent material and carry out adsorption desulfurize, it is characterized in that said sorbent material for being the amorphous alloy adsorbent of main active component with nickel, said contact is carried out in fluidized-bed or slurry bed reactor under the condition of room temperature-150 ℃, normal pressure-2.0 MPa.
2, according to the process of claim 1 wherein that said organic sulfide is mercaptan, thioether, thiophene, thionaphthene, dibenzothiophene and derivative thereof.
3, according to the process of claim 1 wherein that said diesel oil is the diesel oil after the hydrogenating desulfurization, wherein contained organic sulfide is mainly thionaphthene, dibenzothiophene and derivative thereof, and its content is counted 20-500ppm with elementary sulfur weight.
4, according to the method for claim 1, wherein said is only to locate to occur a diffuse maximum at 45 ° in the X-ray diffractogram of amorphous alloy adsorbent of main active component in 2 θ are 20-80 ° scope with nickel, and the aluminium of the nickel that consists of 20-95 weight % of this sorbent material, 1-80 weight %, the iron of 0-40 weight % and 0-20 weight % are selected from a kind of metal among copper, molybdenum, cobalt, chromium and the tungsten.
5, said when carrying out adsorption desulfurize in fluidized-bed reactor according to the process of claim 1 wherein, volume space velocity is 2-40h during liquid
-1
6, said when carrying out adsorption desulfurize in slurry bed reactor according to the process of claim 1 wherein, absorbent concentration is 0.5-20 weight %, and the residence time is 0.5-60 minute.
7, according to the method for claim 6, absorbent concentration is 0.5-10 weight %, and the residence time is 2-30 minute.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021260168A CN1179021C (en) | 2002-08-09 | 2002-08-09 | A kind of diesel oil adsorption desulfurization method |
| GB0404217A GB2397069B (en) | 2001-08-16 | 2002-08-12 | A process for adsorptive desulfurization of light oil distillates |
| PCT/CN2002/000559 WO2003016436A1 (en) | 2001-08-16 | 2002-08-12 | A process for adsorptive desulfurization of light oil distillates |
| DE10297118.8T DE10297118B4 (en) | 2001-08-16 | 2002-08-12 | Process for the adsorptive desulphurisation of light oil distillates |
| JP2003521746A JP3939695B2 (en) | 2001-08-16 | 2002-08-12 | Method for adsorptive desulfurization of diesel oil fraction |
| US10/217,479 US6875340B2 (en) | 2001-08-16 | 2002-08-14 | Process for adsorptive desulfurization of light oil distillates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021260168A CN1179021C (en) | 2002-08-09 | 2002-08-09 | A kind of diesel oil adsorption desulfurization method |
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| Publication Number | Publication Date |
|---|---|
| CN1473910A CN1473910A (en) | 2004-02-11 |
| CN1179021C true CN1179021C (en) | 2004-12-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021260168A Expired - Lifetime CN1179021C (en) | 2001-08-16 | 2002-08-09 | A kind of diesel oil adsorption desulfurization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622096B (en) * | 2016-11-18 | 2019-06-14 | 上海迅凯新材料科技有限公司 | Isopropanol deep desulfuration and the nickel-based sorbent of deodorization and its preparation method and application |
| CN110760337B (en) * | 2018-07-27 | 2022-12-13 | 中国石油化工股份有限公司 | A desulfurization method and equipment for aromatic raw materials |
| WO2023197558A1 (en) | 2022-04-12 | 2023-10-19 | 中国石油天然气股份有限公司 | Oil modification catalyst and preparation method therefor, oil modification method, and oil adsorptive desulfurization modification system |
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- 2002-08-09 CN CNB021260168A patent/CN1179021C/en not_active Expired - Lifetime
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