CN1072034C - Mercaptan oxidation catalyst and preparation therefor - Google Patents
Mercaptan oxidation catalyst and preparation therefor Download PDFInfo
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- 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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- silylating reagent
- amino
- cobalt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title abstract description 18
- 230000003647 oxidation Effects 0.000 title abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- XJGIDGNLXAJIOA-UHFFFAOYSA-N 2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(36),2,4,6,8,10(40),11,13,15,17,19,21(38),22,24,26,28,30,32,34-nonadecaen-37-amine Chemical compound Nn1c2nc3nc(nc4[nH]c(nc5nc(nc1c1ccccc21)c1ccccc51)c1ccccc41)c1ccccc31 XJGIDGNLXAJIOA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000007306 functionalization reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 238000007796 conventional method Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004332 deodorization Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- -1 amido phthalocyanine cobalt Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
本发明提供了一种由固体碱性氧化物负载金属酞菁的硫醇氧化或油品脱臭催化剂及其制备方法，该催化剂由与通式为(RO)3Si(CH2)nA的硅烷化试剂反应而官能团化的固体碱性氧化物载体和共价键连在该载体上的氨基酞菁钴所组成，氨基酞菁钴中的-NH2基与载体上的硅烷化试剂通过与A基的化学反应而共价键连在一起；其中R为C1～C4的烷基，n为1～6，A为卤素或带有环氧基的基团。本发明的催化剂在用于硫醇氧化反应时不用外加液体碱同时又具有较高的催化活性和稳定性。The invention provides a catalyst for mercaptan oxidation or oil product deodorization supported by a solid basic oxide of metal phthalocyanine and its preparation method. The catalyst is composed of a silane with the general formula (RO) 3 Si(CH 2 ) n A It is composed of a solid basic oxide support functionalized by the reaction of a reagent and covalently bonded cobalt aminophthalocyanine on the support. Groups are covalently bonded together through chemical reactions; where R is an alkyl group of C 1 to C 4 , n is 1 to 6, and A is a halogen or a group with an epoxy group. The catalyst of the invention does not need to add liquid alkali when it is used in the mercaptan oxidation reaction and has high catalytic activity and stability at the same time.
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 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97104441A Expired - Lifetime CN1072034C (en) | 1997-06-04 | 1997-06-04 | Mercaptan oxidation catalyst and preparation therefor |
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| CN100462145C (en) * | 2006-11-07 | 2009-02-18 | 北京三聚环保新材料股份有限公司 | Preparation method of catalyst for conversion of mercaptan contained 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 | A kind of supported metal phthalocyanine photocatalyst and preparation method thereof |
| RU2381067C1 (en) * | 2008-10-21 | 2010-02-10 | Федеральное государственное унитарное предприятие "Государственный научный центр "Научно-исследовательский институт органических полупродуктов и красителей" (ФГУП "ГНЦ "НИОПИК") | Catalyst and method of homogeneous oxidative demercaptanisation of oil and oil products |
| RU2381066C1 (en) * | 2008-10-21 | 2010-02-10 | Федеральное государственное унитарное предприятие "Государственный научный центр "Научно-исследовательский институт органических полупродуктов и красителей" (ФГУП "ГНЦ "НИОПИК") | Catalyst and method of oxidising sodium sulphide |
| 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 |
| CN115970759B (en) * | 2022-10-27 | 2025-08-12 | 中国石油化工股份有限公司 | Efficient catalytic oxidation desulfurizing agent and preparation method and application thereof |
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 | Caustic-free desulfurization of sulfur-containing hydrocarbon streams |
| 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 |
| 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 |
| 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 |
-
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 | Caustic-free desulfurization of sulfur-containing hydrocarbon streams |
| 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 |
| 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 |
| 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 |
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| CN1200956A (en) | 1998-12-09 |
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