CN100497542C - Method for selective hydrogenation and removing benzene for gasoline - Google Patents
Method for selective hydrogenation and removing benzene for gasoline Download PDFInfo
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- CN100497542C CN100497542C CNB2005101260632A CN200510126063A CN100497542C CN 100497542 C CN100497542 C CN 100497542C CN B2005101260632 A CNB2005101260632 A CN B2005101260632A CN 200510126063 A CN200510126063 A CN 200510126063A CN 100497542 C CN100497542 C CN 100497542C
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Abstract
A selective hydrogenation to remove the benzene of gasoline is that the benzene selective hydrogenation reaction of the gasoline in the mixture of load solid catalyst, the additive and the water. The active component of the load solid catalyst is the ruthenium and the Fe, the carrier is the zirconia or the zirconia with the transition metal oxide. The method can remove the benzene in gasoline and keep the other arene, so it has the high benzene hydrogenation selectivity.
Description
Technical field
The present invention is a kind of method of selective hydrogenation and removing benzene for gasoline.Specifically, be to make the benzene in the gasoline change into hexanaphthene, thereby reduce the method for benzene content in the gasoline by selective hydrogenation.
Background technology
Along with the increasingly stringent of environmental requirement, more and more stricter to the restriction of benzene content in the motor spirit, but the aromatic hydrocarbons in the gasoline is very big to the contribution of octane value.Therefore how optionally to remove the benzene in the gasoline and keep other aromatic hydrocarbons, become the emphasis of people's research to remove octane value that the bigger benzene of gasoline poisoning can obviously not reduce gasoline simultaneously again.
Suitably the initial boiling point of control reformer feed can reduce the content of benzene in the gasoline, but can not guarantee not contain in the gasoline benzene fully.Have only method could guarantee not contain fully in the gasoline benzene by back end hydrogenation.There are many sophisticated relevant benzene hydrogenations to become the technology of hexanaphthene.These technology extract the benzene in the gasoline earlier, make it saturated by hydrogenation again, so technology are higher than complexity and cost.If benzene extraction not, then its used catalyzer does not have the benzene selective hydrogenating function, can make other aromatic hydrogenation in benzene hydrogenation, thereby the octane value of gasoline is declined to a great extent.Therefore develop gasoline selective hydrogenation technique and catalyst system and become the key that reduces benzene content in gasoline.
USP5,254,763 disclose a kind of benzene selective hydrogenation catalyst and technology, and this method is a raw material with gasoline, makes benzene hydrogenation wherein change into hexanaphthene.This method is carried out hydrogenation after water, gasoline and the organometallic compound that contains ruthenium are mixed, the described organometallic compound that contains ruthenium is water-soluble, and in the aromatic hydrocarbons that gasoline contains, benzene has than high water-soluble of other aromatic hydrocarbons, thereby can make benzene soluble in water and described hydrogenation catalyst contact reacts generate hexanaphthene, hexanaphthene dissolves in the gasoline more again.Other aromatic hydrocarbons in the gasoline is insoluble in water, thereby is difficult to carry out hydrogenation reaction.But the catalyzer that uses in this method is homogeneous catalyst, and not high to the selectivity of benzene hydrogenation.
Summary of the invention
The method that the purpose of this invention is to provide a kind of selective hydrogenation and removing benzene for gasoline, but the benzene in this method effective elimination gasoline.
Gasoline selective hydrogenation provided by the invention takes off the method for benzene, comprises gasoline is carried out the benzene selective hydrogenation reaction in the presence of supported solid catalyzer, additive and water.
The present invention is under hydro condition, the gasoline that aromaticity content is higher carries out selective hydrogenation in the presence of solid catalyst, additive and water, making benzene selective hydrocracking wherein is hexanaphthene, thereby remove the benzene in the gasoline, the inventive method is used solid catalyst in the reaction of selective hydrogenation and removing benzene for gasoline, make the benzene hydrogenation selectivity be able to further raising.
Embodiment
The inventive method is carried out selective hydrogenation with stop bracket gasoline in the presence of solid catalyst, additive and water, make the benzene selective in the gasoline be hydroconverted into hexanaphthene, makes the stop bracket gasoline that does not contain benzene.
The temperature of reaction of described gasoline selective hydrogenation is 90～200 ℃, preferred 100～160 ℃, and pressure is 3.0～8.0MPa, preferred 3.0～6.0MPa, and the volume ratio of water and gasoline is 0.5～20:1 in the reaction system, preferred 1.0～5.0:1.
Supported solid catalyzer of the present invention comprises ruthenium and the iron that is carried on the inorganic oxide carrier, in the catalyzer is that the ruthenium content that benchmark calculates is 1～20 quality % with the carrier, and preferred 5～15 quality %, iron level are 0.1～3.0 quality %.The boron that also can further comprise 0.1～3.0 quality % in the described supported solid catalyzer.
Described inorganic oxide carrier is preferably Powdered, and carrier is selected from zirconium white, aluminum oxide or silicon oxide, preferred zirconium white.Described carrier can also be the mixture of zirconium white and transition metal oxide, preferred 2～20 quality % of the content of transition metal oxide, more preferably 2～15 quality % in the mixture.Described transition metal oxide is lanthanide metal oxide or yttrium oxide, preferred yttrium oxide.
Solid catalyst of the present invention can prepare with two kinds of methods, and a kind of is the precipitator method, and another kind is a reduction method.The precipitator method are that the solution stirring with powder carrier, active ingredient Ru and Fe compound mixes, 40～100 ℃, preferred 60～90 ℃ to wherein adding excessive precipitator, reacted 0.5～6 hour, after naturally cooling to room temperature, leaving standstill, supernatant liquid is removed in centrifugation, obtain the sedimentary slurry of carrier and active ingredient, be washed to solution and be neutral.Solids and proper amount of deionized water are added in the reactor, use hydrogen reducing at 120～180 ℃, after being cooled to room temperature, open reactor, with the reduzate centrifugation, remove clear liquid and obtain the catalyzer slurry, use absolute ethanol washing again, displace the deionized water in the slurry, be drying to obtain catalyzer under the decompression.Described precipitation agent is selected from the aqueous solution of sodium hydroxid, potassium hydroxide, lithium hydroxide, ammoniacal liquor or urea, preferred sodium hydroxide solution.
The method that adopts reduction method to prepare solid catalyst is: the solution stirring of powder carrier, active component Ru and Fe compound is mixed, basic solution or formaldehyde solution with sodium borohydride under the room temperature are reduced, reduzate is through centrifugation, remove clear liquid, obtain the catalyzer slurry, be neutral, use washing with alcohol again with deionized water wash to solution, displace the deionized water in the slurry, be drying to obtain catalyzer under the decompression.The aqueous solution of the sodium hydroxide of the preferred sodium borohydride of basic solution of sodium borohydride, wherein concentration sodium hydroxide is 5～15 quality %, the concentration of sodium borohydride is 0.5～5.0 quality %.Described formaldehyde solution concentration is 0.5～5.0 quality %.
Ruthenium compound described in the above-mentioned method for preparing catalyst is selected from ruthenium chloride, ruthenium bromide or nitric acid ruthenium, preferred ruthenium chloride.Iron cpd is selected from iron(ic) chloride, iron nitrate, iron protochloride, Iron nitrate, preferred iron(ic) chloride, iron protochloride.
The mixture preparation method of described zirconium white and transition metal oxide is included in the soluble salt solution of zirconium oxychloride and transition metal, 60～100 ℃ of stirrings add precipitant solution down and fully react, leave standstill aging after-filtration, the gained solids is promptly got the mixture of zirconium white and transition metal oxide with absolute ethanol washing after drying, roasting.Preferred 200～500 ℃ of described maturing temperature, suitable roasting time is 3～6 hours.Described precipitation agent is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor or urea, preferred sodium hydroxide; Preferred its nitrate of the soluble salt of transition metal, muriate or vitriol.Described transition metal is lanthanide series metal or yttrium.
In the described gasoline selective hydrogenation process of the inventive method, except that need have solid catalyst and water, also additive need be arranged.Additive is selected from zinc compound, preferred zinc chloride, zinc sulfate, zinc phosphate or zinc hydroxide.Described additive is water-soluble, and its concentration in water is 0.3～1.0 mol, preferred 0.4～0.8 mol.
Gasoline of the present invention is the gasoline fraction that catalytic reforming produces, and wherein aromaticity content is greater than 50 quality %, and benzene content is 5.0～10 quality %.
Gasoline selective hydrogenation reaction of the present invention may be carried out batchwise, and also can carry out continuously.During rhythmic reaction solid catalyst, additive and water are added in the reactor, feeding hydrogen to pressure is that 3.0～8.0MPa, temperature are 90～200 ℃, feed gasoline then and fully react, and after the decrease temperature and pressure, gasoline behind the taking-up hydrogenation.Solid catalyst, additive, deionized water and gasoline all adopt the mode of continuously feeding to add reactor during continuous reaction, and gasoline is discharged reactor continuously behind the hydrogenation.Behind the described hydrogenation vapour W/O, additive and solid catalyst with can be recycled after gasoline separates.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Adopt hydrogen reduction method to prepare solid catalyst of the present invention.
Get 35 gram zirconia powders, 12.3 gram RuCl
33H
2O (purity is 99.99%, and ruthenium content is 37%), 1.13 gram FeCl
24H
2O and 80 ml deionized water together add in the beaker, stir and be warming up to 80 ℃, continue to stir 0.5 hour.Adding concentration is that the sodium hydroxide solution of 20 quality % reacts, and stirs 1 hour, and 25 ℃ left standstill aging 24 hours.Supernatant liquid is removed in centrifugation, and the gained solid is with deionized water wash 2～3 times, to the pH value of solution value be 6～8.To wash back solids and 500 ml deionized water is added in the tank reactor, it at hydrogen pressure reduction 4 hours under the condition of 400 rev/mins of 5.0MPa, 150 ℃, stir speed (S.S.), the centrifuging reduzate, and with absolute ethanol washing 3 times, drying is 12 hours under 35 ℃ of decompressions, get the supported solid catalyst A, its composition sees Table 1.
Example 2
(1) preparation contains La
2O
3Zirconia composite
50 gram zirconium oxychlorides and 1.14 gram lanthanum nitrates are dissolved in 1000 ml deionized water, are warming up to 80 ℃ and stirred 2 hours, add 100 ml concns fast and be the NaOH solution reaction 4 hours of 25 quality %.Stop to stir, resultant was left standstill aging 24 hours in 25 ℃.Filter, with solids with absolute ethanol washing 3 times, 35 ℃ of drying under reduced pressure 12 hours, 500 ℃ of roastings 4 hours obtain the Powdered 5.0 quality %La that contain
2O
3ZrO
2Complexes carrier.
(2) preparation catalyzer
Method by example 1 prepares solid catalyst, and different is that the zirconia powder that contains lanthanum trioxide 5 quality % that adopted for 35 gram (1) steps made is preparing carriers solid catalyst B, and its composition sees Table 1.
Example 3
Adopting sodium borohydride is that reductive agent prepares solid catalyst.
Get 35 gram zirconia powders, 12.3 gram RuCl
33H
2O (purity is 99.99%, and ruthenium content is 37%), 1.13 gram FeCl
24H
2O and 80 ml deionized water together add in the beaker, stir 1 hour.Stir and drip down by 6.85 gram NaBH
4, the solution that is made into of 1.4 gram NaOH and 75 ml deionized water, stop to stir, reactant was left standstill 12 hours, supernatant liquid is removed in centrifugation, and the gained solid is with deionized water wash 1～2 time, to the pH value of solution value be 6～8, use absolute ethanol washing again 3 times, drying is 12 hours under 35 ℃ of decompressions, gets supported solid catalyzer C, and its composition sees Table 1.
Example 4
(1) preparation contains the zirconia composite of yttrium oxide
Method by 2 (1) steps of example prepares the zirconium white that contains yttrium oxide, and different is to replace lanthanum nitrates to react with 1.37 gram Yttrium trinitrates, makes the zirconia composite that contains yttrium oxide 5.0 quality %.
(2) preparation catalyzer
Method by example 3 prepares solid catalyst, and different is to go on foot the 5.0 quality %Y that contain that make with 35 grams (1)
2O
3Zirconium white be preparing carriers catalyzer D, its composition sees Table 1.
Example 5
In batch reactor, add solid catalyst, the 40 gram ZnSO of 10 gram the present invention preparations
47H
2O is additive, 280 ml deionized water, and feeding hydrogen to still internal pressure then is 5.0MPa, is warming up to 140 ℃, and the control stir speed (S.S.) is 900 rev/mins, adds 140 milliliters of gasoline and carries out benzene hydrogenation, and the reaction times is 2 hours.Described gasoline hydrocarbon composition sees Table 2, and reaction result sees Table 3.
By table 3 data as can be known, the benzene hydrogenation selectivity of the solid catalyst that the inventive method is used is all more than 82%, and toluene conversion is low, and substantially C does not take place
8The hydrogenation reaction of above aromatic hydrocarbons.
Table 1
Table 2
Table 3
Claims (10)
1, a kind of method of selective hydrogenation and removing benzene for gasoline, comprise gasoline carried out the benzene selective hydrogenation reaction that in the presence of supported solid catalyzer, additive and water described supported solid catalyzer comprises ruthenium and the iron that is carried on the inorganic oxide carrier.
2, in accordance with the method for claim 1, it is characterized in that described hydrogenation reaction temperature is 90～200 ℃, pressure is 3.0～8.0MPa, and the volume ratio of water and gasoline is 0.5～20:1 in the reaction system.
3, in accordance with the method for claim 1, it is characterized in that described hydrogenation reaction temperature is 100～160 ℃, pressure is 3.0～6.0MPa, and the volume ratio of water and gasoline is 1.0～5.0:1 in the reaction system.
4, in accordance with the method for claim 1, it is characterized in that in the catalyzer with the carrier being that the ruthenium content that benchmark calculates is 1～20 quality %, iron level is 0.1～3.0 quality %.
5, in accordance with the method for claim 4, it is characterized in that described inorganic oxide carrier is Powdered, is selected from zirconium white, aluminum oxide or silicon oxide.
6, in accordance with the method for claim 4, it is characterized in that described inorganic oxide carrier is selected from the mixture of zirconium white and transition metal oxide, the content of transition metal oxide is 2～20 quality % in the mixture, and described transition metal oxide is lanthanide metal oxide or yttrium oxide.
7, in accordance with the method for claim 4, it is characterized in that described supported solid catalyzer also comprises the boron of 0.1～3.0 quality %.
8, in accordance with the method for claim 1, it is characterized in that described additive is a zinc compound, the concentration of additive in water is 0.3～1.0 mol.
9, in accordance with the method for claim 8, it is characterized in that described zinc compound is selected from zinc chloride, zinc sulfate, zinc phosphate or zinc hydroxide.
10, in accordance with the method for claim 1, it is characterized in that aromaticity content is greater than 50 quality % in the described gasoline, benzene content is 5.0～10 quality %.
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| CNB2005101260632A CN100497542C (en) | 2005-11-30 | 2005-11-30 | Method for selective hydrogenation and removing benzene for gasoline |
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| CN100497542C true CN100497542C (en) | 2009-06-10 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9908824B2 (en) | 2014-01-29 | 2018-03-06 | Uop Llc | Methods for selectively hydrogenating benzene with supported organometallic catalysts and systems and methods for reducing benzene in gasoline using such catalysts |
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2005
- 2005-11-30 CN CNB2005101260632A patent/CN100497542C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 降低汽油中苯含量工艺技术的探讨. 王桂芝.化工技术经济，第NO.1期. 2002 |
| 降低汽油中苯含量工艺技术的探讨. 王桂芝.化工技术经济，第NO.1期. 2002 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9908824B2 (en) | 2014-01-29 | 2018-03-06 | Uop Llc | Methods for selectively hydrogenating benzene with supported organometallic catalysts and systems and methods for reducing benzene in gasoline using such catalysts |
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