CN1247746C - Method for mercapfining light oil - Google Patents
Method for mercapfining light oil Download PDFInfo
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- CN1247746C CN1247746C CN 03149940 CN03149940A CN1247746C CN 1247746 C CN1247746 C CN 1247746C CN 03149940 CN03149940 CN 03149940 CN 03149940 A CN03149940 A CN 03149940A CN 1247746 C CN1247746 C CN 1247746C
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Abstract
The present invention relates to a mercaptan removal method for light oil products, which comprises: light oil products contact hydrogen, and the reaction of the light oil products and hydrogen is generated under the conditions of the temperature of 60 to 300 DEG C. and the pressure of 0.1 to 1MPa when a catalyst exists; the light oil products with lower mercaptan are collected, wherein the catalyst which is precious metal in an eighth group, such as ruthenium, rhodium, palladium, osmium, iridium and platinum, is loaded on a porosity carrier; the light oil products can be kerosene, aviation jet fuel, gasoline, etc.; the porosity carrier is selected from aluminia, silicon dioxide, aluminosilicate, activated carbon, natural or artificial clay and alkaline earth oxide. The hydrogenation mercaptan removal course of the mercaptan removal method is carried out under the condition of dissolved hydrogen, and energy consumption and hydrogen consumption are markedly reduced.
Description
Technical field
The present invention relates to from light-end products, remove the method for mercaptan.
Technical background
For light-end products,, must carry out the refinement treatment of hydrogenation or non-hydrogenation if its mercaptan sulphur or total sulfur do not meet the specification requirement of commerical prod.The hydrogenating desulfurization of present industrial oil product, normally under the hydrofining condition of harshness, carry out, temperature of reaction height (general more than 300 ℃), reaction pressure height (more than the general 20atm), hydrogen to oil volume ratio big (general more than 100～200), the hydrogen consumption is big simultaneously, energy consumption is big, facility investment and process cost height.Generally need prevulcanized corresponding to the employed catalyzer of the hydrofining of this harshness.
USP3850744 and USP3870626 reported a kind of under lower pressure the hydrotreatment total sulfur content less than the straight run intermediate oil of 0.2w% to slough the wherein method of mercaptan sulfur.Raw materials used oil contains the mercaptan sulfur of 30ppm at least in this method, and used pressure is no more than 10.2kg/cm
2, 149～315 ℃ of used temperature, preferred 204～288 ℃, used hydrogen to oil volume ratio is 36～216, and is common 54～180, catalyst system therefor is to use in the unifining process of harshness and the alumina load type catalyzer of permanent deactivation.
CN1229838A has reported a kind of method for transformation of hydrocarbon ils.The employed temperature of reaction of the described hydro-sweetening process of this method is 150～260 ℃, reaction pressure is 0.3～1.5MPa, react used light oil volume ratio and be not less than 5, actual in 30, catalyst system therefor is Ni-Co-W or the Mo that loads on the alumina supporter, and active component content (in oxide compound) is about 10w%, and preferably contains the auxiliary agent of a kind of Mg of being selected from, F or P, its content is 0.01～8w%, preferred 0.2～5w%.This method can be taken off mercaptan sulfur content to mercaptan and acid number greater than the stock oil of 0.015mgKOH/g greater than 20ppm, acid number and be met in product specification requires, and promptly mercaptans content is less than 20ppm, and acid number is less than 0.015mgKOH/g.
In fact, or the oil product that a little exceed standard qualified for total sulfur only needs to remove the mercaptan that exceeds standard in the oil product, because oil hydrogenation mercaptan removal process is easier than hydrodesulfurization process, so oil hydrogenation mercaptan removal process can be carried out under comparatively gentle reaction conditions.Yet, existing oil hydrogenation mercaptan removal technique adopts all is base metal type catalyzer by the activated alumina load of higher degree, this type of activity of such catalysts constituent element content is higher, the catalyst preparation process complexity need be carried out under the reaction conditions of comparatively high temps, elevated pressures, higher hydrogen oil ratio usually.
Summary of the invention
Purpose of the present invention is exactly the above-mentioned defective that overcomes prior art, and a kind of method of light-end products mercaptan removal is provided, and this method can remove mercaptan and significantly not reduce total sulfur content under demulcent condition comparatively.
The method of light-end products mercaptan removal provided by the invention comprises: light-end products are contacted with hydrogen, make be rich in hydrogen oil product in the presence of catalyzer in 60～300 ℃, react under the condition of pressure 0.1～1MPa, and collect the light-end products that mercaptan has reduced.
The stock oil that the present invention uses is as light-end products such as kerosene, aviation jet fuel, gasoline, the contained total sulfur of oil product qualified (being not more than 0.2w%) or exceed standard a little (can make the total sulfur qualified), oil product mercaptan exceed standard (more than 20ppm) by removing wherein the mercaptan sulfur part.
The described oil product that is rich in hydrogen is meant under suitable temperature and pressure and hydrogen is fully contacted the stock oil that is rich in hydrogen that obtains with stock oil.Said suitable temperature is-20～80 ℃, preferred 0～50 ℃; Suitable pressure is 0.1～2.0MPa, and preferred 0.1～1.0MPa can increase the saturated amounts of hydrogen in the stock oil under said temperature and pressure.Molten hydrogen process can be static, and soon stock oil feeds in the molten hydrogen jar of having kept certain hydrogen pressure and gets final product.Molten hydrogen process also can be dynamic, promptly controls certain system pressure and hydrogen flowing quantity, and hydrogen is passed through from stock oil, helps making the hydrogen in the stock oil to reach capacity within a short period of time like this.Because the mercaptans content in the stock oil is generally lower, the inventive method adopts static molten hydrogen process can satisfy the needs of mercaptan removal.
The processing condition of described hydro-sweetening process comprise: temperature of reaction is 60～300 ℃, and preferred 100～260 ℃, reaction pressure is 0.1～1MPa, preferred 0.1～0.5MPa, reaction volume liquid hourly space velocity 0.5～10h
-1, preferred 2.0～6.0h
-1Because stock oil is the oil product that is rich in hydrogen, therefore no longer in reactor, additionally feed hydrogen.
Described hydrogenating desulfurization alcohol catalyst is the noble ruthenium Ru that is selected from group VIII in the periodic table of elements, rhodium Rh, palladium Pd, osmium Os, iridium Ir, the platinum Pt that loads on the porous carrier, preferred Pt is or/and Pd, with the catalyzer is weight basis, described reactive metal total content is 0.01～5w%, preferred 0.05～2w%.Described porous carrier is selected from aluminum oxide, silicon-dioxide, silico-aluminate, gac, natural or artificial clay, alkaline earth metal oxide etc., preferred gac.The basic materialization performance of described porous carrier is: the BET specific surface is 1～1500m
2/ g, preferred 100～1200m
2/ g, pore volume are 0.1～1.5ml/g, preferred 0.3～1.0ml/g.Described porous carrier can have different shape.
According to method provided by the invention, described hydrotreating catalyst adopts the dipping technique preparation, and promptly with the solution impregnation porous carrier that contains group VIII noble metals, catalyzer is prepared in roasting then.Concrete steps are as follows: the solution direct impregnation porous carrier that will contain group VIII noble metals, deposit 1～6hr under the room temperature, 100～150 ℃ of drying 1～6hr, 200～600 ℃ of roasting 2～6hr, roasting can be carried out in air or water vapour, also can in inert nitrogen gas atmosphere, carry out preferred 200～400 ℃ of maturing temperature.Described dipping method adopts conventional dipping method, can be saturated or the supersaturation dipping.The described solution that contains group VIII noble metals is selected from water-soluble or dissolves in the inorganic or organic compound of ammoniacal liquor, nitric acid or hydrochloric acid, as, contain the preferred Platinic chloride of solution (ammonium), the acid of chlorine palladium, the Palladous chloride of Pt or Pd.Described hydrotreating catalyst can carry out prevulcanized before use, also can be without prevulcanized, and catalyzer can directly use after roasting.
Employed catalyzer not only has good low temperature active in the method provided by the invention, and it is active and significantly do not reduce total sulfur to show excellent mercaptan removal in wide temperature range.Described oil product is through with after catalyzer provided by the invention contacts, and can obtain the product that total sulfur qualified (being not more than 0.2w%), mercaptan sulfur are not more than 20ppm.Compared with prior art, hydro-sweetening process provided by the invention is to carry out under the condition of molten hydrogen, has significantly reduced energy consumption and hydrogen consumption.
Catalyzer provided by the invention also has characteristics, and it is carrier that catalyzer can adopt various porous materials.Because to have adopted porous material is carrier, catalyzer can carry out the hydro-sweetening process under the condition of the precious metal of load very low levels.
Description of drawings
Accompanying drawing is the simplification process flow sheet of mercaptan removal method provided by the invention.
In the accompanying drawing, stock oil enters molten hydrogen jar 3 through pipeline 1 and fully contacts with the hydrogen from pipeline 2 that enters molten hydrogen jar 3, and the stock oil that is dissolved with hydrogen enters hydrogenator 5 through pipeline 4 at the bottom of the molten hydrogen jar and contacts with catalyzer.Reaction product enters liquid trap 7 through pipeline 6, and the tail gas that reaction produces is discharged through pipeline 8.Liquid product in the separator 7 enters stripping tower 10 through pipeline 9, and the reaction product behind the stripping flows out through pipeline 11, obtains product.
Embodiment
Concrete grammar below in conjunction with the molten hydrogen mercaptan removal of example explanation oil product of the present invention.
Catalyzer compositional analysis x-ray fluorescence spectrometry in the example, sulphur content is measured with microcoulomb method (SH/T 0253-9) in the oil, and mercaptan sulfur content is measured with potentiometric titration (GB 1792-88) in the oil, and oil product colourity is measured with GB 6540-86 method.
Employed stock oil is aviation jet fuel in the example, but the light-end products scope of mentioning not thereby limiting the invention, its essential property is as shown in table 1.
Table 1
| The stock oil title | Density g/ml | Total sulfur content ppm | Mercaptan sulfur content ppm | Colourity number | Boiling range ℃ |
| Aviation jet fuel | 0.7866 | 1472 | 105 | 9 | 157～230 |
Example 1～3
This example illustrates Hydrobon catalyst used in the method provided by the invention and preparation thereof.
Take by weighing according to final a certain amount of Platinic chloride or the Palladous chloride of determining of forming of catalyzer, after being dissolved in water, absorbent charcoal carrier (providing by Taiyuan, Shanxi Xinhua chemical plant) that 20～30 purposes are numbered AC or the gamma-aluminium oxide carrier (being provided by Chang Ling, Hunan catalyst plant) that is numbered AL are provided immediately, place 1hr, 120 ℃ of dry 4hr, 300～400 ℃ of roasting 4hr.Table 2 has provided the materialization data of AC absorbent charcoal carrier, and table 3 has been listed the maturing temperature and the composition of catalyzer.
Table 2
| Bearer number | Specific surface m 2/g | Pore volume ml/g |
| AC | 982 | 0.574 |
| AL | 223 | 0.41 |
Table 3
| Example number | The catalyzer numbering | Bearer number | Pt w％ | Pd w％ | Total content w% | Maturing temperature ℃ |
| 1 | C1 | AC | 0.095 | 0.095 | 360 | |
| 2 | C2 | AC | 0.8 | 0.8 | 360 | |
| 3 | C3 | AL | 1.0 | 1.0 | 400 |
Example 4～6
This example illustrates the mercaptan removal effect when different catalysts is formed in the method provided by the invention.
Aviation jet fuel carries out mercaptan removal refining (with reference to accompanying drawing) in the employing catalyzer his-and-hers watches 1.Be reflected on the 10ml hydrogenation micro-reactor and carry out loaded catalyst 10ml.Earlier with nitrogen purging entire reaction system, in molten hydrogen jar, feed hydrogen earlier before the reaction, feed stock oil again.The temperature of molten hydrogen jar is a room temperature, and pressure is consistent with reactive system.After the question response device is heated to temperature of reaction, molten hydrogen stock oil is fed reactor react.Reaction conditions is: 220 ℃ of temperature, pressure 0.5MPa, volume liquid hourly space velocity 2.0h
-1, reacting used hydrogen is general hydrogen.Tail gas is gone into accurate wet type airshed meter after by the back pressure micrometering valve and is read, and measures at any time to keep entire reaction system pressure unanimity with soap-foam flowmeter, and the pressure of promptly keeping in molten hydrogen jar, reactor and the reaction back liquid trap is consistent.The analysis in table 4 of reaction product.As can be seen from Table 4, employed catalyzer can be with mercaptan the stock oil of 105ppm take off to its mercaptans content in 5ppm, and significantly do not reduce total sulfur, the color of oil product is significantly improved behind the hydrogenation.
Table 4
| | 4 | 5 | 6 |
| The catalyzer numbering | C1 | C2 | C3 |
| Mercaptan sulfur content, | 3 | 2 | 2 |
| Total sulfur content, ppm | 1330 | 1330 | 1331 |
| Colourity, number | 30 | 30 | 30 |
Example 7～8
Mercaptan removal effect when this example illustrates differential responses temperature in the method provided by the invention.
Method according to example 4～6 is reacted, and is the temperature of reaction difference, and catalyst system therefor is C2.The analysis in table 5 of reaction product.
Table 5
| | 7 | 8 |
| Temperature of reaction, ℃ | 160 | 220 |
| Mercaptan sulfur content, ppm | 20 | 2 |
| Colourity, number | 30 | 30 |
Example 9～11
Mercaptan removal effect when this example illustrates differential responses pressure in the method provided by the invention.
Method according to example 4～6 is reacted, and is the reaction pressure difference, and reaction velocity is 2.0h
-1, catalyst system therefor is C2.The analysis in table 6 of reaction product.
Table 6
| | 9 | 10 | 11 |
| Reaction pressure, MPa | 0.5 | 0.3 | 0.1 |
| Mercaptan sulfur content, | 2 | 2 | 2 |
| Colourity, number | 30 | 30 | 30 |
Example 12
This example illustrates the mercaptan removal activity stability of catalyzer in the method provided by the invention.
React according to example 4～6 described methods, the catalyzer that just reacts used is C2, and the volume liquid hourly space velocity also has difference in the reaction process, and temperature of reaction is 240 ℃.Mercaptan analysis in table 9 in the reaction product.
Table 9
| Reaction times hr | Volume liquid hourly space velocity h -1 | Mercaptan sulfur content | Colourity number | |
| 1 | 2 | 2 | 30 | |
| 48 | 2 | 2 | 30 | |
| 105 | 2 | 2 | 30 | |
| 168 | 2 | 2 | 30 |
Claims (12)
1. the method for a light-end products mercaptan removal, comprise: light-end products are contacted with hydrogen, make be rich in hydrogen oil product in the presence of catalyzer in 60～300 ℃, react under the condition of pressure 0.1～1MPa, and collect the light-end products that mercaptan has reduced, wherein catalyzer is noble ruthenium, rhodium, palladium, osmium, iridium or the platinum that loads on the group VIII on the porous carrier.
2. in accordance with the method for claim 1, it is characterized in that said light-end products are kerosene, aviation jet fuel or gasoline.
3. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 100～260 ℃, reaction pressure is 0.1～0.5MPa, reaction volume liquid hourly space velocity 0.5～10h
-1
4. in accordance with the method for claim 1, it is characterized in that the reactive metal on the said catalyzer is palladium and/or platinum.
5. in accordance with the method for claim 1, it is characterized in that the catalyst activity total metal content is 0.01～5 heavy %.
6. in accordance with the method for claim 5, it is characterized in that the catalyst activity total metal content is 0.05～2 heavy %.
7. in accordance with the method for claim 1, it is characterized in that said porous carrier is aluminum oxide, silicon-dioxide, silico-aluminate, gac, natural or artificial clay or alkaline earth metal oxide.
8. in accordance with the method for claim 7, it is characterized in that said porous carrier is selected from gac.
9. in accordance with the method for claim 1, it is characterized in that the BET specific surface of said porous carrier is 1～1500m
2/ g, pore volume are 0.1～1.5ml/g.
10. in accordance with the method for claim 9, it is characterized in that the BET specific surface of said porous carrier is 100～1200m
2/ g, pore volume are 0.3～1.0ml/g.
11. in accordance with the method for claim 1, it is characterized in that the said oil product that is rich in hydrogen is meant and hydrogen is fully contacted with stock oil under 0.1～2.0MPa at-20～80 ℃, the oil product that is rich in hydrogen that obtains.
12. in accordance with the method for claim 11, it is characterized in that temperature is 0～50 ℃, pressure is 0.1～1.0MPa.
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|---|---|---|---|
| CN 03149940 CN1247746C (en) | 2003-07-31 | 2003-07-31 | Method for mercapfining light oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03149940 CN1247746C (en) | 2003-07-31 | 2003-07-31 | Method for mercapfining light oil |
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| CN1247746C true CN1247746C (en) | 2006-03-29 |
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| CN103666544B (en) * | 2012-09-21 | 2016-04-06 | 中国石油化工股份有限公司 | A kind of recapitalization generating oil hydrogenation treatment process |
| CN103666546B (en) * | 2012-09-21 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of aviation kerosene liquid-phase hydrogenatin process for purification |
| KR101838579B1 (en) | 2012-09-21 | 2018-03-14 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Hydrocarbon oil hydrotreating method |
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