CN1268548A - Method (B) for oxidation of thioalcohole in petroleum fraction - Google Patents
Method (B) for oxidation of thioalcohole in petroleum fraction Download PDFInfo
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- CN1268548A CN1268548A CN99103270A CN99103270A CN1268548A CN 1268548 A CN1268548 A CN 1268548A CN 99103270 A CN99103270 A CN 99103270A CN 99103270 A CN99103270 A CN 99103270A CN 1268548 A CN1268548 A CN 1268548A
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- mercaptan
- oxidation
- phthalocyanine
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Abstract
An oxidation method of mercaptan in petroleum cut fraction is proceeded in the existence of oxygen to make petroleum cut fraction react with metallic phthalocyanine catalyst which uses gamma Al2O3 with loaded MgO as carrier. The invented oxidation method uses new type solid alkaline material as catalyst carrier so that during the oxidation of mercaptan in petroleum cut fraction, it has no need of adding liquid alkali to achieve high activity and stability.
Description
The present invention relates to the method for oxidation of mercaptan in a kind of petroleum cuts, exactly, is the method for oxidation of mercaptan in a kind of petroleum cuts of working load shaped metal phthalocyanine catalyst.
Mercaptan is present in the petroleum productss such as gasoline, kerosene, rocket engine fuel widely.The existence of mercaptan not only makes oil product produce stench, and the stability of oil product is descended, and mercaptan itself also has corrodibility.Therefore, remove the mercaptan in the oil product or by catalyzed oxidation mercaptan is converted into disulphide by extracting and be very important, this process is commonly called deodorization in petroleum refining industry.The at present industrial a kind of deodour method that generally adopts is the Merox catalyzed oxidation technology of American UOP company exploitation.This technology is in liquid base (mainly referring to caustic alkali) medium, is catalyzer with sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt, under the effect of aerial oxygen, the mercaptan oxidation in the oil product is become disulphide.The shortcoming of this technology is to add liquid base, has the separation and the emission problem of waste lye, is unfavorable for environment protection.
In order to overcome above-mentioned shortcoming, American UOP company has developed a kind of catalyzer again and has used the deodorizing technology (US5,286,372) of this catalyzer.This catalyzer is made of a kind of solid alkali loaded metal title complex, and metal complexes is metal phthalocyanine preferably, and solid alkali can be solid solution, stratiform dihydroxide or their mixture of metal oxide.Use the deodorizing technology of this catalyzer need not add liquid base, needed alkalescence is provided by the solid alkali carrier in the reaction process.
The objective of the invention is on the basis of existing technology, providing a kind of is the method for oxidation of mercaptan in the petroleum cuts of support of the catalyst with the novel solid base material.
Method for oxidation provided by the invention is in the presence of oxygen, with the γ-Al with load MgO of petroleum cuts and catalytic amount
2O
3For the metal phthalocyanine catalyst contact of carrier, react.
Specifically, method for oxidation provided by the invention is in the presence of oxygen, is 20～80 ℃ in temperature, and preferred 30～60 ℃, liquid hourly space velocity is 1～8h
-1, preferred 1～4h
-1Condition under, with the γ-Al with load MgO of mercaptan and catalytic amount
2O
3For the metal phthalocyanine catalyst contact of carrier, react.
The source of used oxygen can be the air or oxygen that feeds, and also can be natural dissolved oxygen in the oil product.Extra if desired bubbling air, the pressure of air can be 1～7kg/cm
2, preferred 1～5kg/cm
2But, because the mercaptans content in the petroleum cuts is lower, dissolved oxygen roughly can satisfy the needs of mercaptan oxidation in the oil product of depositing naturally, therefore, and generally speaking needn't extra again aerating oxygen or air.
In order to improve activity of such catalysts, method provided by the invention can also be carried out in the presence of polar compound, and this polar compound can be water or low-carbon alcohol, or the mixture of the two arbitrary proportion, wherein low-carbon alcohol particular methanol or ethanol.The content of polar compound in pending distillate is between 10～10000ppm.
Employed catalyzer is the γ-Al with load MgO among the present invention
2O
3Metal phthalocyanine catalyst for carrier.In the support of the catalyst, the charge capacity of MgO is 5～25% of a carrier gross weight, preferred 10～20%.With the catalyzer gross weight is benchmark, and the charge capacity of metal phthalocyanine on catalyzer is 0.1～8.0 heavy %, preferred 0.5～5.0 heavy %.
Said metal phthalocyanine is a phthalocyanine cobalt class title complex, one or both mixtures in the sulfonate of promptly poly-phthalocyanine cobalt or phthalocyanine cobalt, carboxylate salt, the quaternary ammonium salt, and the sulfonate of preferred phthalocyanine cobalt is sulfonated phthalocyanine cobalt.
γ-Al with load MgO
2O
3For the metal phthalocyanine catalyst of carrier prepares as follows:
1. with γ-Al
2O
3In magnesium nitrate aqueous solution, flood, drying, roasting obtains Al
2O
3Load MgO type solid alkali.
2. above-mentioned solid alkali is flooded in the polar organic solvent that is dissolved with the phthalocyanine cobalt, drying promptly obtains said catalyzer.
Specifically, said catalyzer can prepare as follows:
1. with γ-Al
2O
3Immerse in the magnesium nitrate aqueous solution of capacity,,, obtain Al 400～570 ℃ of roastings 2～8 hours 100～150 ℃ of dryings 2～12 hours
2O
3Load MgO type solid alkali.
2. above-mentioned solid alkali is immersed in the polar organic solvent that is dissolved with the phthalocyanine cobalt of capacity, flood 2～4 times, absorb until the whole suppressed by vector of solvent.Each dipping finishes and descended dry 3～5 hours in 20～50 ℃ in vacuum, gets final product.
Wherein said polar organic solvent be for dissolving the organic solvent of phthalocyanine cobalt, can be molten or not molten ammonia be selected from one of methyl alcohol, ethanol, Virahol or tetrahydrofuran (THF), or two or more mixed solvent wherein.
The method for oxidation of mercaptan in the petroleum fractions provided by the invention is owing to use γ-Al of novel solid base material-load MgO
2O
3As support of the catalyst, during mercaptan in the petroleum oxidate cut, need not add liquid base and can have higher active and stable.
Fig. 1 is when using mercaptan oxidation method provided by the invention, and the mercaptan sulfur content in the jet fuel is curve over time.
The present invention will be further described below in conjunction with embodiment and accompanying drawing.
In each embodiment and Comparative Examples, used raw material all is commercially available chemically pure reagent except that specifying.
Embodiment 1
Present embodiment is γ-Al
2O
3The preparation of load MgO type solid alkali carrier.
Take by weighing the magnesium nitrate (Mg (NO of 90 grams
3)
26H
20), add the 80ml water dissolution after, the dipping 100 the gram γ-Al
2O
3(Chang Ling, Hunan catalyst plant provides), then 120 ℃ of dried overnight, 500 ℃ of roastings 4 hours adopt X-ray diffraction (XRD) phase quantivative approach to measure, and obtaining the MgO charge capacity is the solid alkali carrier of carrier gross weight 12.3%.
Embodiment 2
Present embodiment is γ-Al
2O
3The preparation of load MgO type solid alkali carrier.
Take by weighing 128 the gram magnesium nitrates, add the 80ml water dissolution after, the dipping 100 the gram γ-Al
2O
3, below operation is with embodiment 1, and obtaining the MgO charge capacity is the solid alkali carrier of carrier gross weight 16.6%.
Embodiment 3～6
This group embodiment is a Preparation of catalysts.
Feed ammonia in ethanol, can obtain containing the ethanolic soln of ammonia 0.5 heavy % after the dissolving, the ethanolic soln that will contain ammonia mixes by 1: 1 volume ratio with methyl alcohol, obtains the mixing solutions of methyl alcohol-ethanol-ammonia.According to the needs of charge capacity, the treated sulfonated phthalocyanine cobalt (being provided by the Shijiazhuang City, Hebei Province refinery) that does not contain insolubles of Different Weight is dissolved in 45ml methyl alcohol-ethanol-ammonia solution, obtain containing the dipping solution of sulfonated phthalocyanine cobalt.The 10 gram solid alkali carriers that make with embodiment 1 and embodiment 2 divide and flood this solution three times respectively, and each solution usage 15ml, each dipping finish through 40 ℃ of dryings of vacuum 8 hours.The gained sample is measured wherein Co content with plasma emission spectroscopy (ICP) method, thereby calculate the charge capacity of sulfonated phthalocyanine cobalt in the catalyzer, the results are shown in Table 1.
Table 1
| Embodiment | The solid alkali carrier | Phthalocyanine cobalt charge capacity, heavy % |
| ?3 | Embodiment 1 | ?1.0 |
| ?4 | Embodiment 2 | ?0.5 |
| ?5 | Embodiment 2 | ?1.0 |
| ?6 | Embodiment 2 | ?2.0 |
Comparative Examples 1
It is a kind of according to US 5,286 that this Comparative Examples provides, 372 report institute synthetic solid basic oxides.
With 128g magnesium nitrate (Mg (NO
3)
26H
2O) and 27g aluminum nitrate (Al (NO
3)
39H
2O) mixed dissolution is made into the aqueous solution that the positively charged ion total concn is 1M in the 600ml deionized water.68g potassium hydroxide and 5g salt of wormwood mixed dissolution are made solution in 550ml water.Under agitation above-mentioned two kinds of solution being splashed in the beaker simultaneously, is 50 ℃ in temperature of reaction, and pH value is approximately stirring reaction under 10 the condition.After above-mentioned two solution dropwise, under this temperature of reaction, continue to stir 4 hours, filter then, be washed till filtrate with deionized water and be neutral, and it is dry down at 80 ℃, obtain hydrotalcite-like layered dihydroxide, put it in 500 ℃ the muffle furnace roasting again 8 hours, obtain the Mg/Al mol ratio and be 5.0 solid basic oxide.
Comparative Examples 2
It is the comparative catalyst of carrier with Comparative Examples 1 synthetic solid basic oxide that this Comparative Examples provides a kind of.
According to embodiment 3 described method for preparing catalyst, preparing the sulfonated phthalocyanine cobalt charge capacity is the catalyzer of 1.0 heavy %, is said comparative catalyst.
Embodiment 7～8
This group embodiment illustrates the reactive behavior of method for oxidation provided by the invention to bright sulfur alcohol.
In an airtight double glazing flask that has an eudiometer, catalyzer and the 5ml n-Octanol with 100mg embodiment 3 and embodiment 5 preparations joins in the reaction flask respectively, and reaction system is full of with oxygen, adds the 1.0ml octyl mercaptan then, begins reaction.Temperature of reaction is constant in 35.0 ± 0.1 ℃ in reaction process, and vigorous stirring is to guarantee that being reflected at the power school district carries out.The consumption of throughput tracheae record oxygen writes down the degree that reaction is carried out in reaction process, time that speed of response is spent with consumption 8ml oxygen and the average response speed that calculates is represented.Experimental result sees Table 2.
Table 2
| Sequence number | Catalyzer | Phthalocyanine cobalt charge capacity, heavy % | Speed of response, ml/min |
| Embodiment 7 | Embodiment 3 | ?1.0 | ?4.4 |
| Embodiment 8 | Embodiment 5 | ?1.0 | ?4.5 |
| Comparative Examples 3 | Comparative Examples 2 | ?1.0 | ?2.1 |
Comparative Examples 3
The catalyzer that this Comparative Examples explanation is made by Comparative Examples 2 is to the reactive behavior of bright sulfur alcohol.
According to embodiment 7 or 8 described methods, in reaction flask, add the catalyzer of Comparative Examples 2 preparations, reaction result is listed in table 2.
The result shows that method for oxidation provided by the invention has higher reactive behavior than the method for using the comparative catalyst.
Embodiment 9
The present embodiment explanation is used when having the catalyzer of different sulfonated phthalocyanine cobalt charge capacity, the effect of mercaptan oxidation method provided by the invention.
The mercaptan oxidation reaction is undertaken by the method among the embodiment 8, and experimental result sees Table 3.The result shows that phthalocyanine cobalt charge capacity is high more, and speed of response is fast more.
Table 3
| Catalyzer | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Phthalocyanine cobalt charge capacity, heavy % | ????0.5 | ????1.0 | ????2.0 |
| Speed of response, ml/min | ????1.8 | ????4.5 | ????6.0 |
Present embodiment illustrates method for oxidation provided by the invention active and stable to mercaptan in the petroleum cuts.
With 10ml embodiment 5 make catalyzer pack in the fixed-bed reactor, be heated to after 40 ℃ that to inject boiling range continuously with pump be that 157～230 ℃, mercaptan sulfur content are No. 3 jet fuels of Iran of 100ppm, keeping temperature is 40 ℃, liquid hourly space velocity is 2.0h
-1, under normal pressure, removing the mercaptan in the oil product, the oxygen that reacts used is the natural dissolved oxygen in the stock oil.The content of mercaptan sulfur is according to the method potentiometric determination of GB1792-88 in the oil product, and reaction result is seen Fig. 1.
Comparative Examples 4
The catalyzer that this Comparative Examples explanation is made by Comparative Examples 2 is active and stable to mercaptan in the petroleum cuts.
According to embodiment 10 described methods, the catalyzer of the Comparative Examples of in reactor, packing into 2 preparations, reaction result is seen Fig. 1.
In Fig. 1, the reaction result that the catalyzer that the reaction result that the catalyzer that curve a represents to use embodiment 5 to make obtains, curve b are represented to use Comparative Examples 2 to make obtains.
As can be seen from Figure 1, method for oxidation provided by the invention is compared with the method for using the comparative catalyst, has better mercaptan oxidation activity and activity stability.
Claims (10)
1. the method for oxidation of mercaptan in the petroleum cuts is characterized in that, in the presence of oxygen, with the γ-Al with load MgO of petroleum cuts and catalytic amount
2O
3For the metal phthalocyanine catalyst contact of carrier, react.
2. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 20～80 ℃, liquid hourly space velocity is 1～8h
-1
3. according to claim 1 or 2 described methods, it is characterized in that temperature of reaction is 30～60 ℃, liquid hourly space velocity is 1～4h
-1
4. in accordance with the method for claim 1, the charge capacity that it is characterized in that MgO is 5～25% of a carrier gross weight.
5. according to claim 1 or 4 described methods, the charge capacity that it is characterized in that MgO is 10～20 heavy % of carrier gross weight.
6. in accordance with the method for claim 1, it is characterized in that the charge capacity of said metal phthalocyanine on catalyzer is 0.1～8.0 heavy %.
7 according to claim 1 or 6 described methods, it is characterized in that the charge capacity of said metal phthalocyanine on catalyzer is 0.5～5.0 heavy %.
8. in accordance with the method for claim 1, it is characterized in that said metal phthalocyanine is a phthalocyanine cobalt class title complex.
9. in accordance with the method for claim 8, it is characterized in that phthalocyanine cobalt class title complex is one or more mixtures in the sulfonate of poly-phthalocyanine cobalt or phthalocyanine cobalt, carboxylate salt, the quaternary ammonium salt.
10. in accordance with the method for claim 9, it is characterized in that phthalocyanine cobalt class title complex is the sulfonate of phthalocyanine cobalt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99103270 CN1115381C (en) | 1999-03-30 | 1999-03-30 | Method (B) for oxidation of thioalcohole in petroleum fraction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99103270 CN1115381C (en) | 1999-03-30 | 1999-03-30 | Method (B) for oxidation of thioalcohole in petroleum fraction |
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| Publication Number | Publication Date |
|---|---|
| CN1268548A true CN1268548A (en) | 2000-10-04 |
| CN1115381C CN1115381C (en) | 2003-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99103270 Expired - Fee Related CN1115381C (en) | 1999-03-30 | 1999-03-30 | Method (B) for oxidation of thioalcohole in petroleum fraction |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005092106A1 (en) * | 2004-03-26 | 2005-10-06 | Beijing University Of Chemical Technology | Use of supported nanoscale mgo as disinfecting material |
| CN102125846A (en) * | 2010-12-24 | 2011-07-20 | 中国石油大学(北京) | Mercaptan etherification catalyst |
-
1999
- 1999-03-30 CN CN 99103270 patent/CN1115381C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005092106A1 (en) * | 2004-03-26 | 2005-10-06 | Beijing University Of Chemical Technology | Use of supported nanoscale mgo as disinfecting material |
| CN102125846A (en) * | 2010-12-24 | 2011-07-20 | 中国石油大学(北京) | Mercaptan etherification catalyst |
| CN102125846B (en) * | 2010-12-24 | 2012-11-21 | 中国石油大学(北京) | Mercaptan etherification catalyst |
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| Publication number | Publication date |
|---|---|
| CN1115381C (en) | 2003-07-23 |
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