CN1255510C - Catalyst for oxidating desulfating reducing olefine of gasoline and its preparation process and application - Google Patents
Catalyst for oxidating desulfating reducing olefine of gasoline and its preparation process and application Download PDFInfo
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- CN1255510C CN1255510C CN 03134005 CN03134005A CN1255510C CN 1255510 C CN1255510 C CN 1255510C CN 03134005 CN03134005 CN 03134005 CN 03134005 A CN03134005 A CN 03134005A CN 1255510 C CN1255510 C CN 1255510C
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Abstract
The present invention discloses an oxidation, desulfurization and olefin reduction catalyst for gasoline and a preparation method thereof. The catalyst uses alumina as a carrier and metal of the VIB group and the VIII group as active components, and adds boron and/or vanadium as an auxiliary agent. In the process of preparing the catalyst, the alumina carrier is firstly immersed in compound water solution containing the auxiliary agent, and then is immersed in compound water solution containing the metal of the VIB group and the VIII group after drying and calcining. The catalyst is used for the processes of oxidation, desulfurization and olefin reduction of FCC gasoline under the condition with oxidants and alcohol. Compared with the prior art, the method reduces the contents of impurities, such as sulfur, nitrogen, etc., in the FCC gasoline, simultaneously reduces the content of olefin, solves the problem of high loss of octane numbers in a hydrodesulphurization method, and overcomes the defects that the olefin can not be reduced in other oxidation and desulfurization methods.
Description
1, technical field
The present invention relates to a kind of gasoline reforming catalyst and preparation method thereof and the application in catalytic cracking (FCC) gasoline oxidation desulfurating and reducing olefinic hydrocarbon process.More particularly, be to have in the presence of oxygenant, the alcohol about a kind of, oxidation is present in the organosulfur in the FCC gasoline and the Catalysts and its preparation method and the application of alkene effectively.
2, background technology
Along with the raising of people's environmental consciousness, the emission from vehicles pollution problems more and more comes into one's own.Europe, the United States, Japan and China have proposed national new gasoline standard in succession, and it is more reasonable that reformulated gasoline is mainly reflected on the composition, not only limits the content of benzene, aromatic hydrocarbons and alkene, and reduce sulphur content major objective especially.
As everyone knows, the reduction of the sulphur content of gasoline, olefin(e) centent and nitrogen content, usual method is to adopt hydrogenation saturation technique and hydrogenating desulfurization, denitride technology.For example, CN1244568A and CN1244569A, but there is the shortcoming that investment is big, running cost is big in the method for hydrotreatment.Increase in China along with Middle East high-sulfur crude oil amount of finish, the organosulfur of gasoline fraction also increases to some extent, the non-MEROX technology mercaptan removal that faces oxygen of many now employings, its adopts cobalt sulfonated phthalocyanine and activator, and mercaptan oxidation is become disulphide, and product need washing, dehydration of salt, carclazyte decolouring, though operation at normal temperatures, but abraum salt, useless carclazyte have produced new pollution, and this technology has strict restriction to the acid number of raw material, and adaptability to raw material is poor.As being that first just gasoline cuts into the weight cut among the US5318690, wherein the MEROX technology mercaptan removal of non-hydrogen is adopted in lighting end; Hydrodesulfurization is adopted in last running, owing to contain a large amount of relatively alkene in the last running, understands some alkene by saturated in hydrogenating desulfurization, and institute is so that octane value descends to some extent.
CN1048543A discloses the desulfurization catalyst and the method for more dysoxidizable mercaptan in a kind of energy oxidation of gasoline, its catalyzer is a kind of a kind of metallo-chelate that is dispersed on the big surface adsorption carrier, metal phthalocyanine on normally a kind of activated carbon, its method is in the presence of ammonium hydroxide and a kind of quaternary ammonium salt and oxygenant, gasoline contacts with catalyzer, though having salkali waste, this technological process do not produce, but because the absorption property and the intensity of activated carbon are relatively poor, so exist processing efficiency low as carrier with it, effect is relatively poor, intensity difference, problems such as the life-span is short, and do not have the effect of falling alkene.
CN1415702A discloses a kind of gasoline oxidation desulfurization nitrogen, has fallen the process of alkene, in the presence of the organic compound such as alcohols of oxygenant and hydroxyl, use epoxidation catalyst and alkoxylating catalyst, make alkene in the gasoline and oxygen, pure initial ring oxidation, alkoxylation and generate glycol monoether or glycol bis ether compounds, sulfur-bearing, nitrogenous compounds such as the mercaptan in the gasoline, thioether, heterocycle sulphur, pyrroles, pyridine are oxidized to polar material and remove from gasoline.Also specifically provide used oxygenant in this patent and generally be selected from aqueous hydrogen peroxide solution, hydrogen/oxygen mixture and ozone etc., provided concrete consumption in the embodiment, used alcohols is C1～C10 alkanol, C5～C8 cycloalkanol and the C7～C12 aryl-triacontanol of linearity or collateralization, the alkanol of preferred C1～C6, its consumption is 5%～50% of a gasoline reaction raw materials weight.It is FCC gasoline that this patent gives raw material, the reaction conditions when oxygenant is aqueous hydrogen peroxide solution.
3, summary of the invention
The purpose of this invention is to provide the gasoline oxidation desulfurating and reducing olefinic hydrocarbon Catalysts and its preparation method that a kind of gasoline octane rating did not lose and can fall alkene.Another purpose is the application of this catalyzer in the full distillation gasoline desulfurating and reducing olefinic hydrocarbon of FCC process, and this technological process is simple, no waste lye, at gasoline desulfur, alkene falls and in, octane value slightly improves.
Gasoline oxidation desulfurating and reducing olefinic hydrocarbon catalyzer provided by the invention, carrier is an aluminum oxide, and reactive metal is group vib and group VIII metal, and auxiliary agent is boron and/or vanadium.Weight with catalyzer is benchmark, the oxide content of described group vib metal is 10.0%～30.0%, be preferably 15.0%～25.0%, the oxide content of group VIII metal is 1.0%～8.0%, be preferably 2.0%～5.0%, the oxide content of described auxiliary agent is 0.5%～5.0%, preferred 1.0%～3.0%.Said group vib metal is preferably molybdenum and/or tungsten; The group VIII metal is preferably nickel.
The character of gasoline oxidation desulfurating and reducing olefinic hydrocarbon catalyzer of the present invention is as follows: specific surface is 150～350m
2/ g, preferred 250～300m
2/ g.Pore volume is 0.30～0.60ml/g, preferred 0.35～0.45ml/g.
The used alumina supporter of catalyzer of the present invention is η-aluminum oxide and/or gama-alumina, preferred gama-alumina.
Preparation of catalysts step of the present invention comprises:
(1), the alumina supporter precursor is through moulding, drying, in the presence of air, makes alumina supporter in 1～6 hour in 450～650 ℃ of roastings.
(2), with the ammonia soln of boron-containing compound and/or the described alumina supporter of aqueous solution impregnation steps (1) of vanadium-containing compound, dipping is after 4～8 hours, 400～550 ℃ roastings of 100～120 ℃ of dryings 4～8 hours must contain the auxiliary agent alumina supporter;
(3), contain the auxiliary agent alumina supporter, through 100～120 ℃ of dryings after 4～8 hours, 400～550 ℃ of roastings 4～8 hours obtain catalyzer of the present invention with what the aqueous solution impregnation steps (2) of group vib and group VIII metallic compound obtained.
It is 10.0wt%～30.0wt% that the consumption of wherein said group vib and group VIII metal compound should make the content of the group vib metal oxide in the final catalyzer, preferred 15.0wt%～25.0wt%; Content 1.0wt%～the 8.0wt% of group VIII metal oxide, preferred 2.0wt%～5.0wt%.
Described dipping can adopt general pickling process, preferred saturated pickling process.
Described group vib metallic compound is preferably molybdate compound and/or Tungstenic compound, the group VIII metallic compound is a nickel compound containing, can be in its water-soluble cpds one or more, wherein molybdate compound is preferably ammonium molybdate, Tungstenic compound is preferably ammonium tungstate and/or ammonium metawolframate, nickel compound containing can be selected from one or more in its water-soluble nitrate, acetate, carbonate, the subcarbonate, preferred nickelous nitrate and/or nickel acetate.
The consumption of described boron-containing compound and/or vanadium-containing compound should make in the final catalyzer and contain 0.5wt%～5.0wt%, preferred 1.0wt%～3.0wt% (in oxide compound).
Boron-containing compound and vanadium-containing compound are selected from one or more in its water-soluble cpds, boron-containing compound preferred boric acid wherein, preferred metavanadic acid amine of vanadium-containing compound and/or Vanadium Pentoxide in FLAKES.
Catalyzer provided by the invention oxygenant and alcohol in the presence of, can be used for FCC gasoline oxidation sweetening, olefin hydrocarbon falls, FCC gasoline wherein can be full cut, also can be lighting end or last running.
Said oxygenant can be any oxygenant that is applicable to the gasoline oxidation desulfurization, falls olefin hydrocarbon, is preferably in aqueous hydrogen peroxide solution, hydrogen/oxygen mixture and the ozone one or more, is preferably aqueous hydrogen peroxide solution.
Oxidation sweetening of the present invention, fall alcohol used in the olefin hydrocarbon, be selected from the C of linearity or collateralization
1～C
10Alkyl alcohol, C
5～C
8Cycloalkanol and C
7～C
12In the aryl alcohol one or more particularly preferably are C
1～C
6Alkyl alcohol.
Above-mentioned alkylol cpd add-on accounts for 5%～50% of FCC gasoline weight.
Catalyzer provided by the invention is used for FCC gasoline oxidation desulfurating and reducing olefinic hydrocarbon process in the presence of oxygenant and alcohol, the reaction conditions that is adopted (temperature, pressure, reaction times and feed way) changes along with the type of raw materials such as oxygenant, alcohol, in principle, the reactivity of system increases along with the length of pure carbochain or the increase of molecule and reducing.
Catalyzer provided by the invention is used for FCC gasoline oxidation desulfurating and reducing olefinic hydrocarbon process, can carry out with intermittent type or fixed bed continous way on laboratory scale and technical scale, and reaction can be carried out preferred liquid phase in gas phase, liquid phase or supercritical phase.
Catalyzer provided by the invention is used for the desulfurization of FCC gasoline oxidation, falls olefin hydrocarbon in the presence of oxygenant and alcohol, the reaction conditions that is adopted (temperature, pressure, reaction times and feed way) can be adjusted in following ranges according to the character of FCC gasoline with to the requirement of processed oil quality, during operate continuously: temperature of reaction-20～150 ℃, preferred 10 ℃～80 ℃; Liquid hourly space velocity 0.5～2.0h
-1, preferred 1.0h
-1The vapour pressure of solution when reaction pressure is temperature of reaction.During periodical operation: temperature of reaction-20～150 ℃, preferred 10 ℃～80 ℃; 0.1～10.0 hour reaction times, preferred 0.5～6 hour; The vapour pressure of solution when reaction pressure is temperature of reaction.
Compared with prior art, in the presence of catalyzer provided by the invention, part alkene in the FCC gasoline fraction and oxygen, pure initial ring oxidation, alkoxide reaction, and generation glycol monoether or glycol bis ether compounds, this compounds can obviously improve the octane value of gasoline products, has also reduced the content of alkene simultaneously.Sulfur-bearing, nitrogenous compounds such as the mercaptan in the FCC gasoline fraction (comprising extremely dysoxidizable uncle's mercaptan), thioether, thiophene-based, pyrroles, pyridine are oxidized to polar material and are removed, thereby have reduced foreign matter contents such as sulphur, nitrogen in the FCC gasoline fraction.Method of the present invention remedied the big deficiency of hydrodesulfurization loss of octane number, overcome the shortcoming that alkene can not fall in other oxidation desulfurizing method.
Gasoline oxidation desulfurating and reducing olefinic hydrocarbon catalyzer of the present invention also can be used for the high gasoline of other sulphur content height, olefin(e) centent such as coker gasoline etc.
4, embodiment
Below in conjunction with embodiment the present invention is done further detailed explanation; it should be noted; following examples are not limiting the scope of the invention; those skilled in the art is in conjunction with specification sheets of the present invention and can do suitable expansion in full, and these expansions all should be protection scope of the present invention.
Embodiment 1
The preparation of present embodiment explanation support of the catalyst Z1 of the present invention
Take by weighing 1000 gram aluminium hydrate powder (butt 70wt%, pseudo-boehmite content 85wt%, Shandong Aluminum Plant produces), add a small amount of extrusion aid and less water, fully mediate evenly, be squeezed into bar shaped, dried 4 hours for 120 ℃, 600 ℃ of roastings 4 hours are cut into 5 millimeter with the bar shaped carrier that obtains, and make gamma-aluminium oxide carrier Z1.
Embodiment 2
Present embodiment is contain the alumina supporter Z2 of auxiliary agent boron, the preparation of Z3 provided by the invention
(1) measures 100 milliliters of ammonia solns that contain ammonia 9wt%, add boric acid 11 grams, solution is placed 50 ℃ of water-baths, heated 2 hours, naturally cooling is with the boric acid ammonia soln for preparing dipping 150 gram carrier Z1, then in 120 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours will make the alumina supporter Z2 that contains auxiliary agent boron.
(2) use the same method, measure 100 milliliters two parts of ammonia solns that contain ammonia 8wt% respectively, add boric acid 25 grams and 32 grams respectively, dipping 150 restrains carrier Z1, will make alumina supporter Z3, the Z4 that contains auxiliary agent boron.
Embodiment 3
Present embodiment is the preparation that contains auxiliary agent vanadium alumina supporter Z5, Z6 provided by the invention
(1) take by weighing ammonium meta-vanadate 10 gram, add deionized water and be made into 100 ml water solution, with the ammonium metavanadate aqueous solution dipping 150 gram carrier Z1 that prepare, then in 120 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours will make and contain auxiliary agent vanadium alumina supporter Z5.
(2) use the same method, take by weighing ammonium meta-vanadate 15 grams, add deionized water and be made into 100 ml water solution, the ammonium metavanadate aqueous solution dipping 150 that usefulness prepares restrains carrier Z1, will make to contain auxiliary agent vanadium alumina supporter Z6.
Embodiment 4～10
The following examples illustrate catalyzer provided by the invention and preparation thereof
Take by weighing quantitative nickelous nitrate [Ni (NO respectively
3)
26H
2O] and ammonium molybdate [(NH
4) M
O7O
244H
2] or ammonium metatungstate aqueous solution (be called for short AMT solution, concentration is 56 gram WO
3/ 100ml solution) add deionized water after the mixing, be made into 100 milliliters of aqueous solution that contain nickelous nitrate and ammonium molybdate or ammonium metawolframate, respectively with the above-mentioned solution for preparing, dipping 150 gram carrier Z1～Z6 4 hours, 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, used material consumption is listed in table 1.
Table 1
| Example number | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| The catalyzer numbering | C1 | C2 | C3 | C4 | C5 | C6 | C7 |
| Bearer number | Z1 | Z1 | Z2 | Z4 | Z5 | Z3 | Z6 |
| Nickelous nitrate consumption/g | 29.2 | 12.5 | 16.4 | 28.5 | 16.6 | 17.5 | 23.0 |
| Ammonium molybdate consumption/g | 50.2 | - | - | - | - | 50.0 | 53.0 |
| AMT consumption/ml | - | 73.0 | 56.0 | 45.0 | 60.0 | - | - |
| Catalyst content/wt% NiO WO 3 MoO 3 B 2O 3 V 2O 5 | 4.6 - 18.1 - - | 1.8 27.8 - - - | 2.4 20.5 - 1.1 - | 4.3 15.6 - 4.2 - | 2.6 21.5 - - 1.8 | 2.7 - 18.3 3.2 - | 3.8 - 19.1 - 2.5 |
| Catalyst property specific surface/m 2.g -1Pore volume/ml.g -1 | 286 0.40 | 278 0.42 | 284 0.41 | 282 0.40 | 279 0.39 | 281 0.43 | 289 0.38 |
Embodiment 11～17
The following examples illustrate that catalyzer provided by the invention is used to estimate the activity that alkene falls in the full distillation gasoline oxidation sweetening of FCC.
Table 2 is depicted as the character of FCC full distillate oil.With the full distillation gasoline of FCC is raw material, and oxygenant is a hydrogen peroxide, and used alcohol is methyl alcohol, and operate continuously on microreactor is estimated C1～C7 catalyst desulfurizing, fallen the alkene activity.60 ℃ of temperature of reaction, reaction pressure 0.6MPa, liquid hourly space velocity 1.0h
-1Wherein sulphur content adopts the microcoulomb method to measure, and mercaptans content adopts titration measuring, and olefin(e) centent adopts the FIA method to measure.
Table 2 raw material oil properties
| The stock oil title | The full distillation gasoline of FCC |
| d 4 20 | 0.7388 |
| Boiling range/℃ IBP 10% 50% 90% EBP | 34 57 102 163 182 |
| Olefin(e) centent/v% | 54.2 |
| Mercaptan sulfur content/μ gg -1 | 133 |
| Total sulfur content/μ gg -1 | 1540 |
| RON | 92.3 |
Table 3 C1～C7 catalyst desulfurizing, the active evaluation result of alkene is fallen
| Example number | 11 | 12 | 13 | 14 | 15 | 16 | 17 |
| The catalyzer numbering | C1 | C2 | C3 | C4 | C5 | C6 | C7 |
| Olefin(e) centent/v% | 47.5 | 43.2 | 41.3 | 42.5 | 45.1 | 45.9 | 45 |
| Mercaptan sulfur content/μ gg -1 | 5.2 | 3.5 | 2.9 | 3.2 | 4.8 | 4.9 | 4.7 |
| Product total sulfur content/μ gg -1 | 302 | 189 | 168 | 180 | 192 | 289 | 282 |
| RON | 92.4 | 92.7 | 93.1 | 92.4 | 92.6 | 92.5 | 92.1 |
Claims (11)
1, a kind of method of FCC gasoline oxidation desulfurating and reducing olefinic hydrocarbon, under the effect of catalyzer and oxygenant and alcohol, FCC gasoline carries out oxidation sweetening and falls olefine reaction, it is characterized in that, described catalyzer is carrier with the gama-alumina, reactive metal is group vib and group VIII metal, auxiliary agent is selected from boron and/or vanadium, weight with catalyzer is benchmark, the content of described group vib metal oxide is 10%～30%, the content of group VIII metal oxide is 1%～8%, and the oxide content of described auxiliary agent is 0.5%～5%, and the specific surface of catalyzer is 150～350m
2/ g, pore volume are 0.30～0.60ml/g;
Wherein said alcohol is selected from the C of linearity or collateralization
1～C
10Alkyl alcohol, C
5～C
8Cycloalkanol and C
7～C
12In the aryl alcohol one or more.
2, in accordance with the method for claim 1, the specific surface that it is characterized in that described catalyzer is 250～300m
2/ g, pore volume are 0.35～0.45ml/g.
3, in accordance with the method for claim 1, it is characterized in that said group vib metal is molybdenum and/or tungsten; The group VIII metal is a nickel.
4, in accordance with the method for claim 1, it is characterized in that, be benchmark with the weight of catalyzer, and the oxide content of described group vib metal is 15%25%, the oxide content of group VIII metal is 2%～5%, and the oxide content of auxiliary agent is 1%～3%.
5, in accordance with the method for claim 1, it is characterized in that described catalyzer prepares by following steps:
(1), the alumina supporter precursor makes alumina supporter through moulding, drying and roasting;
(2), with the described alumina supporter of impregnation steps (1) in the aqueous solution of the ammonia soln of boron-containing compound and/or vanadium-containing compound, dipping is after 100～120 ℃ of dryings 4～8 hours, 400～550 ℃ of roastings 4～8 hours must contain the auxiliary agent alumina supporter;
(3), contain the auxiliary agent alumina supporter, through 100～120 ℃ of dryings after 4～8 hours, 400～550 ℃ of roastings 4～8 hours obtain final catalyzer with what the aqueous solution impregnation steps (2) of group vib and group VIII metallic compound obtained.
6, in accordance with the method for claim 5, it is characterized in that boron-containing compound is a boric acid, vanadium-containing compound is metavanadic acid amine and/or Vanadium Pentoxide in FLAKES.
7, in accordance with the method for claim 5, it is characterized in that described group vib metallic compound is molybdate compound and/or Tungstenic compound, the group VIII metallic compound is a nickel compound containing.
8, in accordance with the method for claim 7, it is characterized in that described molybdate compound is an ammonium molybdate, Tungstenic compound is ammonium tungstate and/or ammonium metawolframate, and nickel compound containing is nickelous nitrate and/or nickel acetate.
9, in accordance with the method for claim 1, it is characterized in that said oxygenant is one or more in aqueous hydrogen peroxide solution, hydrogen/oxygen mixture and the ozone.
10, in accordance with the method for claim 1, it is characterized in that said oxygenant is an aqueous hydrogen peroxide solution, described alcohol is C
1～C
6Alkyl alcohol.
11, in accordance with the method for claim 1, the reaction conditions that it is characterized in that the desulfurization of FCC gasoline oxidation and fall alkene is: during operate continuously, and temperature of reaction-20～180 ℃, liquid hourly space velocity 0.5～2.0h
-1During periodical operation, temperature of reaction-20～180 ℃, 0.1～10.0 hour reaction times.
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|---|---|---|---|
| CN 03134005 CN1255510C (en) | 2003-09-15 | 2003-09-15 | Catalyst for oxidating desulfating reducing olefine of gasoline and its preparation process and application |
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|---|---|---|---|
| CN 03134005 CN1255510C (en) | 2003-09-15 | 2003-09-15 | Catalyst for oxidating desulfating reducing olefine of gasoline and its preparation process and application |
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|---|---|
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| CN1255510C true CN1255510C (en) | 2006-05-10 |
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| CN101554590B (en) * | 2008-12-10 | 2011-06-29 | 上海泰禾(集团)有限公司 | Preparation method of catalyst for preparing isophthalodinitrile |
| CN103120945B (en) * | 2011-11-18 | 2015-04-08 | 中国石油化工股份有限公司 | Catalyst for hydrofining inferior oil product and preparation method thereof |
| CN107573516B (en) * | 2017-09-11 | 2020-06-02 | 东北石油大学 | Preparation method of vanadium modified metal organic framework material |
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