CN1072034C - Mercaptan oxidation catalyst and preparation therefor - Google Patents
Mercaptan oxidation catalyst and preparation therefor Download PDFInfo
- Publication number
- CN1072034C CN1072034C CN97104441A CN97104441A CN1072034C CN 1072034 C CN1072034 C CN 1072034C CN 97104441 A CN97104441 A CN 97104441A CN 97104441 A CN97104441 A CN 97104441A CN 1072034 C CN1072034 C CN 1072034C
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- CN
- China
- Prior art keywords
- catalyst
- carrier
- amino
- silylating reagent
- phthalocyanine cobalt
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Abstract
The present invention provides a deodorizing catalyst of mercaptan oxidation or oil products for loading metal phthalocyanine by a solid alkaline oxide and a preparation method thereof. The catalyst is composed of a solid alkaline oxide carrier and amino phthalocyanine cobalt, wherein the solid alkaline oxide carrier is prepared by a functional group by the reaction of a silylation reagent with the general formula of (RO)<3>Si(CH<2>)<n>A; the amino phthalocyanine cobalt is connected with the carrier by a covalent bond; a-NH2 radical in the amino phthalocyanine cobalt and the silylation reagent on the carrier are connected together by the covalent bond by a chemical reaction with an A radical, wherein R is an alkyl radical of C1 to C4; n is from 1 to 6; A is a halogen or a base group with an epoxy radical. When the catalyst of the present invention is used for a mercaptan oxidation reaction, liquid alkali is not added; simultaneously, the catalyst has high catalytic activity and stability.
Description
The present invention relates to a kind of load-type metal phthalocyanine catalyst that is applicable to mercaptan oxidation or oil product deodorization and preparation method thereof.
Mercaptan is present in the oil products such as gasoline, kerosene, jet 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 corrosivity.Therefore, remove the mercaptan in the oil product or change mercaptan into disulfide by catalytic oxidation by extracting and be very important, this process is commonly called deodorization (sweetening) in petroleum refining industry.The at present industrial catalytic oxidation deodour method that generally adopts is the Merax technology of American UOP company exploitation, this technology is in strongly basic medium, with sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt is catalyst, be oxidant and the mercaptan oxidation in the oil product is become disulfide with the air, USP 2988500, USP 4913802, USP4290913 and USP 4337147 etc. are the descriptions to this kind technology.The shortcoming of this technology is to add liquid base, the separation and the discharging of spent lye is arranged, and will pollute environment.
In order to overcome above-mentioned shortcoming, Uop Inc. has developed a kind of new catalyst and the deodorizing technology (USP 5286372) of this catalyst of use again.This catalyst is loaded on a kind of solid base by metal complex and forms; Metal complex is metal phthalocyanine preferably, and said solid base can be solid solution, stratiform dihydroxide or their mixture of metal oxide, and it is both as solid base, again as the carrier of metal complex; Use the deodorizing technology of this catalyst not need to add liquid base, but this activity of such catalysts and stability are not ideal enough, in order to improve activity of such catalysts, can join a kind of father-in-law's compounds in the hydrocarbon raw material or be immersed on the carrier, and should add polar compound such as water and alcohol as the proton translocation medium.
The purpose of this invention is to provide metal phthalocyanine catalyst for mercaptol oxidization of a kind of solid base load and preparation method thereof, the mercaptan oxidation activity and the stability of this kind of gained catalyst are significantly improved.Catalyst for mercaptol oxidization provided by the present invention by with general formula be (RO)
3Si (CH
2)
nThe solid basic oxide carrier of the reaction of the silylating reagent of A and functionalization and covalent bond are connected in the amino phthalocyanine cobalt CoPc (NH on this carrier
2)
mForm, in the amino phthalocyanine cobalt-NH
2Silylating reagent on base and the carrier is by covalent bond connects together with the chemical reaction of A base; Wherein R is C
1～C
4Alkyl, the value of preferable methyl or ethyl n is 1～6, preferred 2～4; A is halogen or the group that has epoxy radicals; Pc is the symbol of general representative phthalocyanine basic structure; M is the amino number on the titanium cyanines cobalt phenyl ring, and its value is 1～4, and most preferred is 4.
Said solid basic oxide is USP 5,286 in the method provided by the present invention, and the general formula described in 372 is xMOyM '
2O
3Solid solution, wherein M is the divalent metal that is selected from Mg, Ni, Zn, Cu, Fe, Co, most preferred is Mg; M ' is for being selected from the trivalent metal of Al, Cr, Ga, and most preferred is Al; X/y is 1～15; Preferred 2～10; This oxide 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 in 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 1～50.
The weight of said silylating reagent in said carrier is 0.1～10 heavy % in the catalyst provided by the present invention, preferred 0.5～8 heavy %.
The content of said amino phthalocyanine cobalt in catalyst is 0.1～10 heavy % in the catalyst provided by the present invention, preferred 0.3～5 heavy %.
The preparation method of said catalyst for mercaptol oxidization provided by the present invention comprises: earlier with said silylating reagent (RO)
3Si (CH
2)
nA and said basic anhydride xMOyM
2' O
3In a kind of organic solvent that comprises toluene or dimethylbenzene in 60～110 ℃ of reactions 4～12 hours down, after filtration, obtain surface carrying after the washing, drying by functionalization; Said amino phthalocyanine cobalt is dissolved in a kind of polar solvent and with said carrier to descend to react 4～24 hours at 30～150 ℃, filters then, wash and drying.
The used said silylating reagent and the weight ratio of said basic anhydride are (0.005～0.15) in the method provided by the present invention: 1, preferred (0.002～0.6): 1.
The used said amido phthalocyanine cobalt and the weight ratio of said carrier are (0.001～0.1) in the method provided by the present invention: 1, preferred (0.005～0.1): 1.
Said polar solvent can be the solvent that methyl-sulfoxide, low-carbon alcohols, water etc. can dissolve amino phthalocyanine cobalt in the method provided by the present invention, wherein the organic solvent of preferred polarity.
Catalyst for mercaptol oxidization provided by the present invention is because the amino phthalocyanine cobalt of its active constituent is amino with silylating reagent generation condensation reaction and covalent bond is connected on the basic anhydride surface that silylating reagent is modified by it, thereby can stop of the gathering of amino phthalocyanine cobalt effectively at carrier surface, improved its decentralization on carrier, make activity of such catalysts and stability and carrier not the similar catalyst of surface modification compare and be significantly improved.
The following examples will the present invention is further illustrated, but not thereby limiting the invention.
In each embodiment and Comparative Examples, used raw material tetramino phthalocyanine cobalt CoPc (NH
2)
4Be according to document Polyhedron., 1987, the 6th volume, reported method prepares in the 1463rd page, (be called for short γ-GOPS) and 3-r-chloropropyl trimethoxyl silane and be the reagent available from Tokyo HuaCheng Industry Co., Ltd, all the other raw materials are commercially available chemically pure reagent to used glycidol ether propyl trimethoxy silicane.When carrying out the evaluation of mercaptan oxidation reactivity, the amount of oxygen (ml.min that reaction speed consumed with the unit interval
-1) expression or with unit interval unit cobalt center (micromole μ mol) consumption amount of oxygen (ml. μ mol
-1.min
-1) expression, the average response speed when wherein being 8ml with the oxygen expenditure amount when the n-octyl mercaptan amount is 1ml is as initial reaction speed V
o, transforming half with mercaptan is that the immediate reaction speed of oxygen expenditure amount when being 16.5ml (1.0ml 1-spicy thioalcohol need consume 33ml oxygen when being converted into disulfide fully under 35 ℃) is as half-reaction speed V
1/2, with V
1/2Ratio V with Vo
1/2/ Vo represents the stability of catalyst.
Embodiment 1
Present embodiment illustrates the preparation of used solid basic oxide in the catalyst provided by the invention, and this preparation is reference literature Appl.Catal., 1989, and the 54th volume, reported method is carried out in the 79th page.
Embodiment 1: with 128 gram Mg (NO
3)
26H
2O and 27 gram 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 68 gram KOH and 5 gram 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 50 ℃ in reaction temperature, and pH value is a stirring reaction under about 10 the condition.After above-mentioned two solution dropwise, under this reaction temperature, continue to stir 4 hours, filter then, be washed till filtrate with deionized water and be neutral, and after 80 ℃ of following dryings, obtain hydrotalcite-like layered dihydroxide, put it into again that roasting obtained solid basic oxide used in the catalyst of the present invention (the Mg/Al mol ratio is 5.0) after 8 hours in 500 ℃ the muffle furnace.
Embodiment 2,3: keep Mg (NO
3)
26H
2The consumption of O and other reaction conditions are constant, change Al (NO
3)
39H
2O, KOH and K
2CO
3Consumption be respectively (2) 38 grams, 73 grams and 7 grams and (3) 63 grams, 85 grams and 12 grams, to prepare the Mg/Al mol ratio respectively with quadrat method be two kinds of solid basic oxides of 3.0 and 10 by above-mentioned.
Embodiment 4～8
The present embodiment explanation preparation of the carrier of silylating reagent functionalization
The solid basic oxide of preparation adds in the 25ml toluene among the embodiment 1 that 2 grams are dry, add silylating reagent according to the amount in the table 1 respectively, 85 ℃ of following stirring reactions 8 hours, filter and successively use 100ml toluene and 50ml absolute methanol washing leaching cake then, after 80 ℃ of following dryings, obtain having the carrier of the functionalization of different modifying amount, its modification amount is meant that the silylating reagent key is connected in the percetage by weight (measuring with thermogravimetry) in the said functionalization carrier.
Table 1
*: chemical formula is
(be called for short the * * of γ-GOPS): chemical formula is (CH
3O)
3SiCH
2CH
2CH
2Cl
| Embodiment | The silylating reagent title | Silylating reagent consumption (mg) | Modification amount (heavy %) |
| 4 5 6 | The glycidol ether propyl trimethoxy silicane *The same | 30 65 120 | 1.1 2.6 5.1 |
| 7 8 | The 3-r-chloropropyl trimethoxyl silane **The same | 30 60 | 1.3 2.4 |
Embodiment 9
Present embodiment explanation Preparation of catalysts of the present invention (conventional method).
The carrier of the functionalization of preparation among the 1.0 gram embodiment 4～8 is joined 15ml be dissolved with a certain amount of CoPc (NH
2)
4In methyl-sulfoxide (DMSO) solution of (according to the load capacity decision),, filter after 10 hours at 85 ℃ of following stirring reactions, filter cake is colourless with anhydrous DMSO and methanol wash until filtrate successively, and is dry down at 80 ℃ then.With the gained sample with plasma emission spectroscopy (ICP) thus method is measured wherein that the content of Co calculates CoPc (NH in the catalyst
2)
4Load capacity.
Comparative Examples 1
The Preparation of catalysts of functionalization is carried out in the explanation of this Comparative Examples to carrier without silylating reagent.
With the Mg/Al mol ratio of embodiment 1 preparation is that 3.0 the solid basic oxide without the silylating reagent functionalization replaces the carrier among the embodiment 9, is dissolved with 10mg CoPc (NH with 15ml
2)
4Dimethyl sulfoxide solution prepare CoPc (NH according to the method for embodiment 9
2)
4Content is the comparative catalyst of 0.60 heavy %.
Embodiment 10～12
The mercaptan oxidation performance of present embodiment explanation catalyst of the present invention.
Mercaptan oxidation is reflected in the airtight double glazing flask that has an eudiometer tube and carries out.(method that its carrier is respectively embodiment 5 and embodiment 7 makes, and the Mg/Al mol ratio is 3.0, CoPc (NH in the catalyst according to two kinds of catalyst of the method for embodiment 9 preparation with 60mg respectively
2)
4Content be respectively 0.60 heavy % and 0.75 heavy %) and Comparative Examples 1 in the comparative catalyst pack in this reaction bulb, add the 5ml normal octane again, reaction system is full of with oxygen, add the 1.0ml n-octyl mercaptan then, begin to react.Reaction temperature is constant in 35.0 ± 0.1 ℃ in course of reaction, 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 (as previously described) that reaction is carried out in course of reaction.Listed result of the test in the table 2, this result shows that catalyst provided by the invention is compared its mercaptan oxidation activity with the comparative catalyst and stability all is significantly improved.
Table 2
| Carrier | Vo(ml/min) | V 1/2(ml/min) | V 1/2/Vo(％) | |
| Embodiment 10 | Embodiment 5 | 3.0 | 2.2 | 73.3 |
| Embodiment 11 | Embodiment 7 | 4.1 | ||
| Embodiment 12 (comparative catalyst) | Embodiment 1 | 1.7 | 0.4 | 23.5 |
Embodiment 13～17
Present embodiment illustrates the effect of the catalyst of the present invention of different hydride modified amounts.
Five kinds of carriers among the embodiment 4～8 are prepared into five kinds of catalyst according to the method among the embodiment 9, respectively these five kinds of catalyst are carried out the mercaptan oxidation activity rating according to the method for describing among the embodiment 10～12 then, the results are shown in Table 3 for it.Table 3 data show the amount of silylating reagent on the carrier influence this amount of activity of such catalysts guarantee the phthalocyanine cobalt fully key be connected under the prerequisite on the carrier more little favourable more to reactivity.
Table 3
| Carrier | CoPc (NH in the catalyst 2) 4Content (heavy %) | Vo(ml/min) | |
| Embodiment 13 | Embodiment 4 | 0.6 | 4.2 |
| Embodiment 14 | Embodiment 5 | 0.6 | 3.0 |
| Embodiment 15 | Embodiment 6 | 0.6 | 1.8 |
| Embodiment 16 | Embodiment 7 | 0.75 | 4.1 |
| Embodiment 17 | Embodiment 8 | 0.75 | 3.3 |
Embodiment 18～20
Present embodiment illustrates the effect of the catalyst of the present invention of different phthalocyanine cobalt contents.
The carrier that embodiment 5 is made is prepared with the method for describing among the embodiment 9 has different CoPc (NH
2)
4Three kinds of catalyst of content carry out the mercaptan oxidation activity rating with these three kinds of catalyst according to the method for describing among the embodiment 10～12, and different is that catalyst consumption changes 40mg into by 60mg when estimating, and the results are shown in Table 4 for it.
Table 4
| CoPc (NH in the catalyst 2) 4Content (heavy %) | Vo(ml/min) | |
| Embodiment 18 | 0.6 | 2.0 |
| Embodiment 19 | 1.8 | 3.2 |
| Embodiment 20 | 3.1 | 4.1 |
Embodiment 21～23
Present embodiment explanation has the effect of the prepared catalyst of the present invention of the carrier of different Mg/Al mol ratio.
The solid basic oxide with different Mg/Al mol ratio of preparation among the embodiment 1～3 is modified with silylating reagent according to the method for embodiment 5, be prepared into three kinds of its CoPc (NH by the method for describing among the embodiment 9 again
2)
4Content all is the catalyst of 0.6 heavy %, then with these three kinds of catalyst according to embodiment 10～12 in the same procedure described estimate, the results are shown in Table 5 for it.
Table 5
| The Mg/Al mol ratio | Vo(ml/min) | |
| Embodiment 21 | 3.0 | 3.0 |
| Embodiment 22 | 5.0 | 2.5 |
| Embodiment 23 | 10 | 2.1 |
Claims (8)
1. the catalyst for mercaptol oxidization of a solid base supported metal phthalocyanine is characterized in that this catalyst is by being (RO) with general formula
3Si (CH
2)
nThe solid basic oxide carrier of the reaction of the silylating reagent of A and functionalization and covalent bond are connected in the amino phthalocyanine cobalt CoPc (NH on this carrier
2)
mForm, in the amino phthalocyanine cobalt-NH
2Silylating reagent on base and the carrier is by covalent bond connects together with the chemical action of A base; Wherein R is C
1～C
4Alkyl; The value of n is 1～6, and A is halogen or the group that has epoxy radicals; M is the amino number on the titanium cyanines cobalt phenyl ring, and its value is 1～4; 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, M ' is for being selected from the trivalent metal of Al, Cr, Ga, x/y is 1～15; The weight of said silylating reagent in said carrier is 0.1～10 heavy %; The content of said amino phthalocyanine cobalt in catalyst is 0.3～5 heavy %.
2. according to the catalyst of claim 1, wherein R is a methyl.
3. according to the catalyst of claim 1, wherein n is 2～4.
4. according to the catalyst of claim 1, wherein m is 4.
5. according to the catalyst of claim 1, the weight of wherein said silylating reagent in said carrier is 0.5～8.0 heavy %.
6. according to the catalyst of claim 1, wherein said solid basic oxide is to be M by general formula
xM '
y(OH)
2x+2y(X)
Y/nZH
2The roasting and making according to a conventional method of the hydrotalcite-like layered dihydroxide of O, 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.
7. according to the catalyst of claim 1, wherein M is Mg, and M ' is Al, and x/y is 2～10.
8. any one Preparation of catalysts method in the claim 1～7 is characterized in that this method comprises: earlier weight ratio is (0.005～0.15): 1 said silylating reagent (RO)
3Si (CH
2)
nA and said basic anhydride xMOyM
2' O
3In a kind of organic solvent that comprises toluene and dimethylbenzene in 60～110 ℃ of reactions 4～12 hours down, after filtration, obtain the surface by the carrier of functionalization after the washing, drying; Said amino phthalocyanine cobalt is dissolved in a kind of polar solvent and with said carrier 30～150 ℃ of reactions 4～24 hours down, filter then, wash, drying, the weight ratio of wherein said amino phthalocyanine cobalt and said carrier is (0.001～0.1): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97104441A CN1072034C (en) | 1997-06-04 | 1997-06-04 | Mercaptan oxidation catalyst and preparation therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97104441A CN1072034C (en) | 1997-06-04 | 1997-06-04 | Mercaptan oxidation catalyst and preparation therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1200956A CN1200956A (en) | 1998-12-09 |
| CN1072034C true CN1072034C (en) | 2001-10-03 |
Family
ID=5167367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97104441A Expired - Lifetime CN1072034C (en) | 1997-06-04 | 1997-06-04 | Mercaptan oxidation catalyst and preparation therefor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1072034C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462145C (en) * | 2006-11-07 | 2009-02-18 | 北京三聚环保新材料股份有限公司 | Method for preparing catalyst for converting mercaptan in liquefied gas |
| CN100462146C (en) * | 2006-11-07 | 2009-02-18 | 北京三聚环保新材料股份有限公司 | Method for preparing catalyst for converting mercaptan in gasoline |
| CN100441297C (en) * | 2006-12-11 | 2008-12-10 | 南京大学 | Supported metal phthalocyanine photocatalyst and its preparing method |
| CN103031141B (en) * | 2011-09-29 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of method removing mercaptan in oils |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048543A (en) * | 1989-05-08 | 1991-01-16 | 美国环球油品公司 | The no caustic alkali sulfur method of sour hydrocarbon stream |
| US5286372A (en) * | 1992-04-02 | 1994-02-15 | Uop | Process for sweetening a sour hydrocarbon fraction using a solid base |
| US5401390A (en) * | 1992-09-23 | 1995-03-28 | Uop | Catalyst for sweetening a sour hydrocarbon fraction containing metal oxide solid solution and magnesium oxide |
| US5413704A (en) * | 1993-11-15 | 1995-05-09 | Uop | Process for sweetening a sour hydrocarbon fraction using a mixture of a supported metal chelate and a solid base |
| US5413701A (en) * | 1993-11-15 | 1995-05-09 | Uop | Process for sweetening a sour hydrocarbon fraction using a supported metal chelate and a solid base |
-
1997
- 1997-06-04 CN CN97104441A patent/CN1072034C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048543A (en) * | 1989-05-08 | 1991-01-16 | 美国环球油品公司 | The no caustic alkali sulfur method of sour hydrocarbon stream |
| US5286372A (en) * | 1992-04-02 | 1994-02-15 | Uop | Process for sweetening a sour hydrocarbon fraction using a solid base |
| US5401390A (en) * | 1992-09-23 | 1995-03-28 | Uop | Catalyst for sweetening a sour hydrocarbon fraction containing metal oxide solid solution and magnesium oxide |
| US5413704A (en) * | 1993-11-15 | 1995-05-09 | Uop | Process for sweetening a sour hydrocarbon fraction using a mixture of a supported metal chelate and a solid base |
| US5413701A (en) * | 1993-11-15 | 1995-05-09 | Uop | Process for sweetening a sour hydrocarbon fraction using a supported metal chelate and a solid base |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1200956A (en) | 1998-12-09 |
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