CN1978058A - Sulfur alcohol oxidation catalyst, its preparing and use - Google Patents
Sulfur alcohol oxidation catalyst, its preparing and use Download PDFInfo
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- CN1978058A CN1978058A CN 200510126054 CN200510126054A CN1978058A CN 1978058 A CN1978058 A CN 1978058A CN 200510126054 CN200510126054 CN 200510126054 CN 200510126054 A CN200510126054 A CN 200510126054A CN 1978058 A CN1978058 A CN 1978058A
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Abstract
The present invention provides a mercaptan oxidation catalyst. Said catalyst uses multiporous material as carrier, and uses metallophthalocyanine with positive ion group and metallophthalocyanine with negative ion group as active component. Said invention also provides a method for mercaptan oxidation, said method is characterized by that in the presence of oxygen gas and alkaline solution medium the hydrocarbon flow is contacted with the invented catalyst. Besides, said invention also provides the preparation method of said catalyst and its concrete steps.
Description
Technical field
The present invention relates to a kind of catalyst that is used for mercaptan oxidation, specifically, be a kind of be carrier with the porous material, be the catalyst of active component to the type metal phthalocyanine with negative ions.The invention still further relates to the method for described Preparation of catalysts method and catalysis mercaptan oxidation.
Background technology
Mercaptan is present in the hydrocarbon fluids such as natural gas, liquefied petroleum gas, gasoline, kerosene, jet fuel, diesel oil widely.The existence of mercaptan can bring diversified serious problems, as stench, corrosion etc.Therefore removing mercaptan from various process material or fluid is very important.Usually, the industrial process that the method for mercaptan by catalytic oxidation is converted into disulphide is called deodorization.The at present industrial a kind of deodour method that generally adopts is the Merox catalytic oxidation technology of American UOP company exploitation.Merox catalytic oxidation technology is divided into liquid-liquid catalyst system and catalyzing and fixed-bed process again.Liquid-liquid catalyst system and catalyzing is that the liquid base (mainly referring to caustic alkali) that will contain sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt catalyst contacts (as with adverse current or and the mode of stream) and mercaptan oxidation that will be wherein is a disulphide with petroleum distillate under the oxidation of air.Fixed-bed process be with metal phthalocyanine loaded on solid carrier, by intermittently or annotate the mode of alkali and bubbling air continuously and petroleum distillate is carried out deodorization handle.For example propose among the USP2988500 metal phthalocyanine (preferred sulfonated phthalocyanine cobalt) is loaded on a kind of active carbon, in the presence of a kind of alkaline solution (being generally caustic alkali), distillate is contacted and deodorization under oxidizing condition with the metal phthalocyanine catalyst of load; Propose to use NH among the USP4913802
4OH is as alkaline solution; Propose among USP4290913 and the USP4337147 with metal phthalocyanine loaded on carriers such as clay or oxide as catalyst, the usefulness quaternary ammonium compound can improve the deodorization activity as alkaline solution.
CN1200958A (application number 97112307.1) has reported a kind of supported phthalocyaanine cobalt mercaptan oxidation catalyst, described catalyst is by loading on being made up of with the formed ion-pair complex of quaternary ammonium salt phthalocyanine cobalt with cation group sulfonate phthalocyanine cobalt with anion group or carboxylate phthalocyanine cobalt of a kind of solid basic oxide surface, and wherein said solid basic oxide is that general formula is xMOyM '
2O
3Solid solution, wherein M is the divalent metal that is selected from Mg, Ni, Zn, Cu, Fe, Co, preferred Mg; M ' is for being selected from the trivalent metal of Al, Cr, Ga, preferred Al; X/y is 1～15, preferred 2～10; It is to be M by general formula
xM '
y(OH)
2x+2y(X)
Y/nZH
2The hydrotalcite-like layered dihydroxide of O is according to a conventional method at 300～750 ℃, preferred 450～600 ℃ of following roastings and making, and wherein X is for being selected from CO
3 2-, NO
3 -With the anion of halogen, n is the valence state of X, and z is about 1～50 (CN1200958A Instructions Page 2 the 3rd～8 row).Described catalyst is owing to used negative ions to type phthalocyanine cobalt complex, compare with the single phthalocyanine cobalt compound of employing, active and the stability of its mercaptan oxidation is significantly improved, and is carrier owing to having adopted solid base, need not add liquid base when mercaptan oxidation.Yet, this catalyst activity stability (be not more than 20ppm in the mercaptan sulfur content after catalyst treatment, activity stability has only about 480h) far below industrial be the liquid caustic soda system of catalyst with the Titanium cyanines; Simultaneously, in CN1200958A, also do not put down in writing the regeneration effect behind the catalysqt deactivation, industrial being difficult to used.
Summary of the invention
Therefore, the objective of the invention is to overcome the deficiencies in the prior art, the catalyst that is used for mercaptan oxidation that aims to provide a kind of activity and good stability and be easy to regenerate.The inventor finds after deliberation, when disclosed this catalyst of CN1200958A is used for the catalysis mercaptan oxidation, solid basic oxide specific surface after high-temperature roasting as carrier is little, is difficult to stable absorption and this big molecule chelate of dispersed metal titanium cyanines, causes the unstable properties of this catalyst.Based on this discovery, the inventor has designed a kind of new catalyst that is used for mercaptan oxidation, this catalyst is carrier with the porous material, with metal phthalocyanine with cation group and the metal phthalocyanine with anion group is active component, and wherein said porous material does not comprise following substances: general formula is xMOyM '
2O
3Solid basic oxide, wherein M is the divalent metal that is selected from Mg, Ni, Zn, Cu, Fe, Co; M ' is for being selected from the trivalent metal of Al, Cr, Ga; X/y is 1～15; It is to be M by general formula
xM '
y(OH)
2x+2y(X)
Y/nZH
2The hydrotalcite-like layered dihydroxide of O makes 300～750 ℃ of following roastings according to a conventional method, and wherein X is for being selected from CO
3 2-, NO
3 -With the anion of halogen, n is the valence state of X, and z is 1～50.
Another object of the present invention provides the method for the described catalyst of preparation, comprise that metal phthalocyanine that will have the cation group and the metal phthalocyanine with anion group mix, are dissolved at least a being selected from the following solution: alkali hydroxide soln, alkaline earth metal hydroxide solution and ammoniacal liquor, use aforesaid porous material dipping then.
Another purpose of the present invention is the application of catalyst of the present invention in the mercaptan oxidation process.
Another purpose of the present invention is the method for catalysis mercaptan oxidation, is included under the existence of oxygen and alkaline solution medium, and hydrocarbon stream is contacted with catalyst of the present invention.
The specific embodiment
Catalyst for mercaptol oxidization of the present invention is carrier with the porous material, is active component with metal phthalocyanine with cation group and the metal phthalocyanine with anion group, and wherein said porous material does not comprise following substances: general formula is xMOyM '
2O
3Solid basic oxide, wherein M is the divalent metal that is selected from Mg, Ni, Zn, Cu, Fe, Co; M ' is for being selected from the trivalent metal of Al, Cr, Ga; X/y is 1～15; It is to be M by general formula
xM '
y(OH)
2x+2y(X)
Y/nZH
2The hydrotalcite-like layered dihydroxide of O makes 300～750 ℃ of following roastings according to a conventional method, and wherein X is for being selected from CO
3 2-, NO
3 -With the anion of halogen, n is the valence state of X, and z is 1～50.
In the present invention, described porous material is to be selected from the porous material that contains aluminium, silicon, alkaline-earth metal, transition metal, rare earth metal and carbon, but does not comprise following substances: general formula is xMOyM '
2O
3Solid basic oxide, wherein M is the divalent metal that is selected from Mg, Ni, Zn, Cu, Fe, Co; M ' is for being selected from the trivalent metal of Al, Cr, Ga; X/y is 1～15; It is to be M by general formula
xM '
y(OH)
2x+2y(X)
Y/nZH
2The hydrotalcite-like layered dihydroxide of O makes 300～750 ℃ of following roastings according to a conventional method, and wherein X is for being selected from CO
3 2-, NO
3 -With the anion of halogen, n is the valence state of X, and z is 1～50.As an example, described porous material is for example following at least a for being selected from: aluminium oxide, silica, alumino-silicate, calcium oxide, magnesia, titanium oxide, natural and artificial clay, natural and artificial zeolite, from the carbonaceous material of mineral material (as coal and oil etc.), vegetable material (as wood chip, shell fruit stone etc.) and synthetic resin etc. etc., preferred carbonaceous material, preferred especially active carbon.
Preferably, the specific area of described porous material is higher than 300m
2/ g preferably is higher than 400m
2/ g especially preferably is higher than 500m
2/ g.For example, the specific area of porous material of the present invention is 300～1,500m
2Between/the g, preferably 350～1,200m
2Between/the g, particularly preferably in 400～1,000m
2Between/the g.
In a preferred embodiment, described porous material is non-alkaline porous material.In the present invention, " non-alkaline porous material " means any porous material, as long as it shows as neutrality or acidity generally; In other words, although may have basic site in some part in the porous material,,, then belong to the category of the non-alkaline porous material among the present invention as long as this porous material presents acidity or neutral character generally.The example of described non-alkaline porous material has, but be not limited to: aluminium oxide, silica, alumino-silicate, titanium oxide, natural and artificial clay, natural and artificial zeolite, from carbonaceous material of mineral material (as coal and oil etc.), vegetable material (as wood chip, shell fruit stone etc.) and synthetic resin etc. etc., preferred carbonaceous material, preferred especially active carbon.
In one embodiment, described metal phthalocyanine is selected from magnesium phthalocyanine, titanium phthalocyanines, hafnium phthalocyanine, vanadyl phthalocyanine, tantalum phthalocyanine, molybdenum phthalocyanine, manganese phthalocyanine, iron-phthalocyanine, cobalt phthalocyanine, platinum phthalocyanine, palladium phthalocyanine, copper phthalocyanine, silver-colored phthalocyanine, zinc phthalocyanine, tin phthalocyanine, preferred cobalt phthalocyanine and vanadyl phthalocyanine, preferred especially cobalt phthalocyanine.
In a preferred embodiment, described metal phthalocyanine with anion group is selected from sulfonate, the carboxylate of metal phthalocyanine, the sulfonate of preferred cobalt phthalocyanine comprises a kind of in the tetrasulfonate (four sulfonated phthalocyanine cobalts) of trisulfonate (three sulfonated phthalocyanine cobalts), cobalt phthalocyanine of disulfonate (two sulfonated phthalocyanine cobalt), the cobalt phthalocyanine of monosulfonate (single sulfonated phthalocyanine cobalt), the cobalt phthalocyanine of cobalt phthalocyanine or several mixture arbitrarily wherein.
In another preferred embodiment, described metal phthalocyanine with cation group is selected from quaternary ammonium salt, the compounds of metal phthalocyanine, the quaternary ammonium salt of preferred cobalt phthalocyanine, and general formula is CoPc[N (R
1R
2R
3) A]
a, wherein Pc is the symbol of expression phthalocyanine basic structure, R
1, R
2, R
3Be the identical or different alkyl with 1～3 carbon atom, A is a halide anion, preferred I
-, a is quaternized degree, its value is 1～4, preferred a=4.
In one embodiment, the described content of metal phthalocyanine on catalyst with cation group is 0.05～9.95 heavy % (promptly being the percentage by weight of benchmark with the total catalyst weight), preferred 0.05～4.95 heavy %; The described content of metal phthalocyanine on catalyst with anion group is 0.05～9.95 heavy %, preferred 0.05～4.95 heavy %.
In another embodiment, the total content of two kinds of metal phthalocyanines on catalyst is 0.1～10 heavy %, preferred 0.1～5.0 heavy %.
The method of the aforesaid catalyst for mercaptol oxidization of preparation of the present invention comprises: will have the metal phthalocyanine of cation group and have the metal phthalocyanine mixed dissolution of anion group in the hydroxide solution or ammoniacal liquor of alkali metal or alkaline-earth metal, preferred sodium hydroxide solution or ammoniacal liquor use the porous material dipping then.Can adopt the mode of spray dipping, incipient impregnation or excessive dipping.Wherein said porous material does not comprise following substances: general formula is xMOyM '
2O
3Solid basic oxide, wherein M is the divalent metal that is selected from Mg, Ni, Zn, Cu, Fe, Co; M ' is for being selected from the trivalent metal of Al, Cr, Ga; X/y is 1～15; It is to be M by general formula
xM '
y(OH)
2x+2y(X)
Y/nZH
2The hydrotalcite-like layered dihydroxide of O makes 300～750 ℃ of following roastings according to a conventional method, and wherein X is for being selected from CO
3 2-, NO
3 -With the anion of halogen, n is the valence state of X, and z is 1～50.
In a preferred embodiment, preparation process is carried out in catalytic reactor, emits excesses of basic solution behind the dipping (for example flooding 24 hours).In another preferred embodiment, preparation process is carried out outside catalytic reactor, dipping back dry (as dry or thermal current in drying or vacuum drying).
In a preferred embodiment, described porous material is aforesaid non-alkaline porous material.
Catalyst of the present invention can be used for the oxidation of mercaptan.Therefore, the invention provides the application of aforementioned catalyst in oxidation mercaptan process.
The present invention also provides a kind of method of oxidation mercaptan, is included under the existence of oxygen and alkaline solution medium, and hydrocarbon stream is contacted with catalyst of the present invention, reacts.
In a preferred embodiment, this method is included under the existence of oxygen and alkaline solution medium, is 20～100 ℃ in temperature, and preferred 30～60 ℃, liquid hourly space velocity (LHSV) is 1～8h
-1, preferred 1～4h
-1Condition under, mercaptan is contacted with catalyst of the present invention, react.Described oxygen is from the air or oxygen that feeds, and perhaps the oxygen that dissolves naturally in the hydrocarbon stream also can be the suitable mixed gas that contains oxygen.In particularly preferred embodiments, the pressure of the gas of feeding (gauge pressure) is 1～15kg/cm
2, preferred 1～8kg/cm
2
In one embodiment, described alkaline solution medium is selected from the hydroxide solution of alkali metal, alkaline-earth metal, preferred NaOH and/or potassium hydroxide solution.In another embodiment, the adding of described alkaline solution medium is carried out with continuous or mode intermittently.
In a preferred embodiment, the method for described mercaptan oxidation also can be carried out in the presence of polar compound and/or compounds; Described polar compound is water or low-carbon alcohols, or the mixture of the two arbitrary proportion, wherein low-carbon alcohols particular methanol or ethanol; Described compounds is selected from quaternary ammonium compounds, rattle compounds, Arsenic compounds, antimony compounds, oxygen compounds and sulfonium compounds etc., is respectively N, P, As, Sb, O and S etc. as cationic atom, preferred quaternary ammonium compounds; Described polar compound and/or the compounds content in pending hydrocarbon stream is between 10～10000ppm.
Catalyst for mercaptol oxidization of the present invention is compared with the catalyst of prior art, and activity is with good stability and be easy to regeneration, can be used for the catalytic oxidation process of mercaptan.
The following examples will the present invention is described further, but do not limit protection scope of the present invention therefrom.In each embodiment, except as otherwise noted, used reagent is commercially available chemicals.
Embodiment 1
Used four seasons ammonium salt phthalocyanine cobalt CoPc[N (CH in the present embodiment explanation catalyst of the present invention
3)
3I]
4Synthetic, this is synthetic to be reference literature J.Mol.Catal., 1994, Vol.87, reported method is carried out among the P161.
With 0.15gCoPc (NH
4)
4(reference literature Polyhedron, 1987,6:1463 is synthetic) and be dissolved in 50mlN, in the dinethylformamide (DMF), add 1.0ml 2 then, 6-lutidines and 20ml CH
3The I reaction.After 2 days, in reactant liquor impouring 300ml ether, there is precipitation to separate out.Filter, with the washing precipitation of 200ml ether.Then, sediment is added 500ml H
2Among the O, heat 1h down, filter pressure reducing and steaming H at 90 ℃
2O.With DMF and ether recrystallization, get navy blue quaternary ammonium phthalocyanine cobalt product.
Embodiment 2
Used tetrasulfonic acid sodium phthalocyanine cobalt CoPc (SO in the present embodiment explanation catalyst of the present invention
3Na)
4Synthetic.
Under ice-water bath, will slowly join in the oleum (constituting) of 30g 30% under 2.0g phthalocyanine cobalt (CoPc) stirring by 20g 50% oleum and 10g 98% concentrated sulfuric acid, after treating the dissolving of phthalocyanine cobalt, react 48h down at 30～35 ℃, then above-mentioned reactant liquor is added dropwise to hydrolysis in the 200ml frozen water, filter out sediment, with the above-mentioned sediment of NaOH aqueous solution dissolving neutralization, after the pressure reducing and steaming water, use 50ml methyl alcohol and 50ml acetone recrystallization again, use the 200ml absolute ethanol washing, after the drying, obtain tetrasulfonic acid sodium phthalocyanine cobalt CoPc (SO
3Na)
4(with elementary analysis and infrared spectrum characterization).
Embodiment 3～4
Present embodiment explanation Preparation of catalysts of the present invention.
According to total load amount of phthalocyanine cobalt on the catalyst (by 1 heavy %) and sulfonated phthalocyanine cobalt CoPc (SO wherein
3Na)
4With quaternary ammonium phthalocyanine cobalt CoPc[N (CH
3)
3I]
4Ratio (1: 1 in molar ratio), take by weighing a certain amount of sulfonated phthalocyanine cobalt and quaternary ammonium phthalocyanine cobalt mixed dissolution respectively in an amount of ammoniacal liquor (5 heavy %), equal-volume or excessive dipping 20～40 purpose active carbon AC1, AC2 (provided by Taiyuan, Shanxi Xinhua chemical plant, its fundamental property sees Table 1).Standing over night, in 45 ℃ of dryings 8 hours, the negative ions that makes activated carbon supported phthalocyanine cobalt total load amount and be 1 heavy % was to type phthalocyanine cobalt catalyst product (seeing Table 2) under the vacuum.
Table 1
| The active carbon numbering | Specific surface (m 2/g) | Pore volume (ml/g) |
| AC1 | 967 | 0.523 |
| AC2 | 453 | 0.503 |
Table 2
| The embodiment numbering | Catalyst numbering of the present invention | The active carbon numbering | CoPc(SO 3Na) 4With CoPc[N (CH 3) 3I] 4Mol ratio |
| 3 | 1 | AC1 | 1∶1 |
| 4 | 2 | AC2 | 1∶1 |
Comparative Examples 1
This Comparative Examples provides the comparative catalyst of a kind of nonionic to type.
Flood active carbon AC1 described in the embodiment 3 with the tetrasulfonic acid sodium phthalocyanine cobalt among the embodiment 2 according to the method described in the embodiment 3, in 45 ℃ of dryings 8 hours, making the sulfonated phthalocyanine cobalt load capacity was the phthalocyanine cobalt catalyst product (being comparative catalyst 1) of the activated carbon supported nonionic of 1.0 heavy % under the vacuum.
Comparative Examples 2
It is a kind of according to the prepared comparative catalyst of CN1200958A that this Comparative Examples provides.
According to the document Appl.Catal. that CN1200958A provided, 1989, the 54th volume, the content in the 79th page prepares the used solid basic oxide of comparative catalyst, floods sulfonated phthalocyanine cobalt CoPc (SO with this solid basic oxide then
3Na)
4With quaternary ammonium phthalocyanine cobalt CoPc[N (CH
3)
3I]
4
With 128g Mg (NO
3)
26H
2O and 38g Al (NO
3)
39H
2The O mixed dissolution is made into the aqueous solution that the cation total concentration is 1M in the 600ml deionized water.With 73gKOH and 7g K
2CO
3Mixed dissolution is made solution in 550ml water.Under agitation above-mentioned two kinds of solution being splashed in the beaker simultaneously, is that 50 ℃, pH value are stirring reaction under about 10 the condition in reaction temperature.After above-mentioned two solution dropwise, under this temperature, continue to stir 4h, filter then, be washed till solution with deionized water and be neutral, and after 80 ℃ of following dryings, obtain hydrotalcite-like layered dihydroxide, put it into again in 500 ℃ the muffle furnace, behind the roasting 8h, obtain solid basic oxide used in this Comparative Examples catalyst (Mg/Al mol ratio 5.0), recording its BET specific surface is 205m
2/ g.
Total load amount according to phthalocyanine cobalt on the catalyst reaches wherein sulfonated phthalocyanine cobalt CoPc (SO
3Na)
4With quaternary ammonium phthalocyanine cobalt CoPc[N (CH
3)
3I]
4Proportion requirement, with the gained solid basic oxide according to the described methods dipping of the embodiment among the CN1200958A 3 sulfonated phthalocyanine cobalt CoPc (SO
3Na)
4With quaternary ammonium phthalocyanine cobalt CoPc[N (CH
3)
3I]
4, preparing solid basic oxide load phthalocyanine cobalt total load amount is the ion pair type catalyst (sulfonated phthalocyanine cobalt CoPc (SO of 1 heavy %
3Na)
4With quaternary ammonium phthalocyanine cobalt CoPc[N (CH
3)
3I]
4Mol ratio be 1: 1).
Embodiment 5
Present embodiment explanation catalyst of the present invention and comparative catalyst's effect.
In microreactor, be respectively charged into each 10ml of catalyst of the present invention and comparative catalyst, soak beds, emit unnecessary alkali lye after spending the night, be warming up to 40 ℃ and carry out hydrocarbon stream deodorization reaction with 15 heavy % sodium hydroxide solutions.Used hydrocarbon stream is that mercaptan sulfur content is a kind of No. 3 jet fuel cuts (density (20 ℃) 0.7870kg/m of 92ppm
3, 158～232 ℃ of boiling ranges), liquid hourly space velocity (LHSV) is 2h
-1
Table 3 has provided catalyst of the present invention and comparative catalyst's effect, and data are feedstock oil mercaptan sulfur content (ppm) after catalyst treatment in the table 3.The removal of mercaptans effect of catalyst of the present invention obviously is better than the comparative catalyst as can be seen.Comparative catalyst 2 its catalytic activity after annotating alkali lye as the solid base load obviously reduces, this is by metal phthalocyanine run off from the solid base carrier behind dipping by lye and cause (compare with active carbon, the less solid base carrier of surface area is a little to the adsorptivity difference of metal phthalocyanine).
Table 3
| Time, h | 5 | 24 | 48 | 72 |
| Catalyst 1 of the present invention | 2 | 2 | 3 | 3 |
| Catalyst 2 of the present invention | 2 | 3 | 4 | 4 |
| The comparative catalyst 1 | 4 | 4 | 5 | 6 |
| The comparative catalyst 2 | 2 | 4 | 6 | 9 |
Embodiment 6
Present embodiment explanation catalyst of the present invention and the comparative catalyst regeneration effect after accelerating inactivation (when raw material and mercaptan sulfur content after catalyst contacts are promptly looked catalysqt deactivation greater than the 20ppm of No. 3 jet fuel standard codes).
Accelerate the inactivation experiment: in microreactor, be respectively charged into catalyst 1 of the present invention and comparative catalyst 2 each 10ml, soak beds (except the comparative catalyst 2) with 15 heavy % sodium hydroxide solutions, emit unnecessary alkali lye after spending the night, be warming up to 40 ℃ and carry out the deodorization reaction.Still the mercaptan sulfur content with embodiment 3 is No. 3 jet fuel cuts (density (20 ℃) 0.7870kg/m of 92ppm
3, 158～232 ℃ of boiling ranges) and be raw material, liquid hourly space velocity (LHSV) is from 10h
-1Beginning is 9h when raw material changes air speed when mercaptan sulfur content surpasses 20ppm after catalyst treatment
-1, drop to 2h so successively
-1, surpass 20ppm again up to mercaptan sulfur content and promptly stop experiment.
Accelerate after experiment finishes, with remaining oil plant in the 15 heavy % sodium hydroxide solutions displacement beds, and soak bed 24h, bleed off unnecessary alkali lye then, be warming up to 40 ℃, oil-feed, the experiment of repetition embodiment 5.
Table 4 has provided catalyst of the present invention and comparative catalyst's regeneration effect, and data are feedstock oil mercaptan sulfur content (ppm) after catalyst treatment in the table 4.Removal of mercaptans effect behind the catalyst regeneration of the present invention as can be seen is basic identical with fresh catalyst, even and the catalyzed by solid base system also is difficult to regeneration by outer filling alkali after accelerating inactivation.
Table 4
| Time, h | 5 | 24 | 48 |
| Catalyst 1 of the present invention | 3 | 3 | 3 |
| The comparative catalyst 2 | 4 | 14 | 25 |
Claims (31)
1, a kind of catalyst for mercaptol oxidization, this catalyst are carrier with the porous material, are active component with metal phthalocyanine with cation group and the metal phthalocyanine with anion group, and wherein said porous material does not comprise following material: general formula is xMOyM '
2O
3Solid solution, wherein M is the divalent metal that is selected from Mg, Ni, Zn, Cu, Fe, Co; M ' is for being selected from the trivalent metal of Al, Cr, Ga; X/y is 1～15; It is to be M by general formula
xM '
y(OH)
2x+2y(X)
Y/nZH
2The hydrotalcite-like layered dihydroxide of O makes 300～750 ℃ of following roastings according to a conventional method, and wherein X is for being selected from CO
3 2-, NO
3 -With the anion of halogen, n is the valence state of X, and z is 1～50.
According to the catalyst of claim 1, it is characterized in that 2, described porous material is to be selected from the porous material that contains aluminium, silicon, alkaline-earth metal, transition metal, rare earth metal and carbon.
3, according to the catalyst of claim 2, it is characterized in that, described porous material be selected from following at least a: aluminium oxide, silica, alumino-silicate, calcium oxide, magnesia, titanium oxide, natural and artificial clay, natural and artificial zeolite, from the carbonaceous material of mineral material, vegetable material and synthetic resin.
According to the catalyst of claim 1, it is characterized in that 4, the specific area of described porous material is higher than 300m
2/ g.
According to the catalyst of claim 1, it is characterized in that 5, described porous material is non-alkaline porous material.
6, according to the catalyst of claim 1, it is characterized in that, described porous material be selected from following at least a: aluminium oxide, silica, alumino-silicate, titanium oxide, natural and artificial clay, natural and artificial zeolite, from the carbonaceous material of mineral material, vegetable material and synthetic resin.
According to the catalyst of claim 6, it is characterized in that 7, described porous material is an active carbon.
8, according to the catalyst of one of claim 1～7, it is characterized in that described metal phthalocyanine is selected from magnesium phthalocyanine, titanium phthalocyanines, hafnium phthalocyanine, vanadyl phthalocyanine, tantalum phthalocyanine, molybdenum phthalocyanine, manganese phthalocyanine, iron-phthalocyanine, cobalt phthalocyanine, platinum phthalocyanine, palladium phthalocyanine, copper phthalocyanine, silver-colored phthalocyanine, zinc phthalocyanine, tin phthalocyanine.
9, catalyst according to Claim 8 is characterized in that, described metal phthalocyanine is selected from cobalt phthalocyanine and vanadyl phthalocyanine.
According to the catalyst of one of claim 1～7, it is characterized in that 10, described metal phthalocyanine with anion group is selected from sulfonate, the carboxylate of metal phthalocyanine.
11, according to the catalyst of claim 10, it is characterized in that described metal phthalocyanine with anion group is selected from a kind of in the tetrasulfonate of trisulfonate, cobalt phthalocyanine of disulfonate, the cobalt phthalocyanine of monosulfonate, the cobalt phthalocyanine of cobalt phthalocyanine or several mixture arbitrarily wherein.
12, according to each catalyst of claim 1～7, it is characterized in that described metal phthalocyanine with cation group is selected from quaternary ammonium salt, the compounds of metal phthalocyanine.
According to the catalyst of claim 12, it is characterized in that 13, described metal phthalocyanine with cation group is that general formula is CoPc[N (R
1R
2R
3) A]
aThe quaternary ammonium salt of cobalt phthalocyanine, wherein Pc is the symbol of expression phthalocyanine basic structure, R
1, R
2, R
3Be the identical or different alkyl with 1～3 carbon atom, A is a halide anion, and a is quaternized degree, and its value is 1～4.
According to the catalyst of claim 13, it is characterized in that 14, A is I
-, a=4.
15, according to each catalyst of claim 1～7, it is characterized in that, the described content of metal phthalocyanine on catalyst with cation group is 0.05～9.95 heavy %, and the described content of metal phthalocyanine on catalyst with anion group is 0.05～9.95 heavy %.
16, according to the catalyst of claim 15, it is characterized in that, the described content of metal phthalocyanine on catalyst with cation group is 0.05～4.95 heavy %, and the described content of metal phthalocyanine on catalyst with anion group is 0.05～4.95 heavy %.
According to the catalyst of claim 16, it is characterized in that 17, the total content of two kinds of metal phthalocyanines on catalyst is 0.1～5.0 heavy %.
18, a kind of method of mercaptan oxidation is included under the existence of oxygen and alkaline solution medium, and each catalyst of the claim 1～17 of hydrocarbon stream and catalytic amount is contacted, and reacts.
19, according to the method for the mercaptan oxidation of claim 18, it is characterized in that, in the presence of oxygen and alkaline solution medium, is 20～100 ℃ in temperature, and liquid hourly space velocity (LHSV) is 1～8h
-1Condition under, each catalyst of the claim 1～17 of mercaptan and catalytic amount is contacted, react.
20, according to the method for the mercaptan oxidation of claim 19, it is characterized in that described temperature is 30～60 ℃, described liquid hourly space velocity (LHSV) is 1～4h
-1
21, according to the method for claim 18,19 or 20 mercaptan oxidation, it is characterized in that described alkaline solution medium is selected from the hydroxide solution of alkali metal, alkaline-earth metal.
22, according to the method for the mercaptan oxidation of claim 21, it is characterized in that described alkaline solution medium is NaOH and/or potassium hydroxide solution.
According to the method for claim 18,19 or 20 mercaptan oxidation, it is characterized in that 23, described oxygen is from the air or oxygen that feeds, perhaps the oxygen that dissolves naturally in the hydrocarbon stream.
24, according to the method for the mercaptan oxidation of claim 23, it is characterized in that the pressure of the air of described feeding is 1～15kg/cm
2
25, according to the method for claim 18,19 or 20 mercaptan oxidation, it is characterized in that described method is carried out in the presence of polar compound and/or compounds; Described polar compound is water or low-carbon alcohols, or the mixture of the two arbitrary proportion; Described compounds is selected from quaternary ammonium compounds, rattle compounds, Arsenic compounds, antimony compounds, oxygen compounds and sulfonium compounds; Described polar compound and/or the compounds content in pending hydrocarbon stream is between 10～10000ppm.
26, according to the method for the mercaptan oxidation of claim 25, it is characterized in that described low-carbon alcohols is methyl alcohol and/or ethanol, described compounds is a quaternary ammonium compounds.
27, a kind of each method of catalyst of claim 1～17 for preparing, comprise metal phthalocyanine that will have the cation group and metal phthalocyanine mixed dissolution in the hydroxide solution or ammoniacal liquor of alkali metal or alkaline-earth metal, use the porous material dipping then with anion group; Wherein said porous material does not comprise following substances: general formula is xMOyM '
2O
3Solid solution, wherein M is the divalent metal that is selected from Mg, Ni, Zn, Cu, Fe, Co; M ' is for being selected from the trivalent metal of Al, Cr, Ga; X/y is 1～15; It is to be M by general formula
xM '
y(OH)
2x+2y(X)
Y/nZH
2The hydrotalcite-like layered dihydroxide of O makes 300～750 ℃ of following roastings according to a conventional method, and wherein X is for being selected from CO
3 2-, NO
3 -With the anion of halogen, n is the valence state of X, and z is 1～50.
28, according to the method for claim 27, it is characterized in that, with the metal phthalocyanine mixed dissolution in sodium hydroxide solution or ammoniacal liquor.
According to the method for claim 27 or 28, it is characterized in that 29, preparation process is carried out in catalytic reactor, emit excesses of basic solution behind the dipping.
According to the method for claim 27 or 28, it is characterized in that 30, preparation process is carried out outside catalytic reactor, dry behind the dipping or vacuum drying.
According to the method for claim 27 or 28, it is characterized in that 31, described porous material is non-alkaline porous material.
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| CN101862681A (en) * | 2010-06-26 | 2010-10-20 | 大连理工大学 | Catalyst and method for oxidatively removing thiophene sulfocompounds thereof |
| CN101862681B (en) * | 2010-06-26 | 2013-01-30 | 大连理工大学 | Catalyst and method for oxidatively removing thiophene sulfocompounds thereof |
| CN103374382A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Method for deodorizing light oil |
| CN103374382B (en) * | 2012-04-26 | 2015-05-20 | 中国石油化工股份有限公司 | Method for deodorizing light oil |
| CN104707595A (en) * | 2013-12-12 | 2015-06-17 | 鲁学文 | Uses of Mn-Al-based hydrotalcite-like compound as mercaptan removing catalyst |
| CN104707595B (en) * | 2013-12-12 | 2017-07-04 | 苏庆平 | Houghite based on Mn Al as mercaptan-eliminating catalyst purposes |
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| CN105344379B (en) * | 2015-10-26 | 2017-08-11 | 湘潭大学 | A kind of hydrotalcite load FePC visible ray fenton catalyst and its preparation method and application |
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| CN115634683A (en) * | 2022-10-31 | 2023-01-24 | 南京工业大学 | Supported three-component monatomic solid base catalyst, and preparation and application thereof |
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