CN1458228A - Fraction oil oxidation desulfurizing catalyst and its preparation - Google Patents
Fraction oil oxidation desulfurizing catalyst and its preparation Download PDFInfo
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Abstract
The fraction oil oxidizing and desulfurizing contains VIB, and VIII, IVB or VB metal oxide loaded onto porous acid carrier, and has VIB metal content 10-30 wt%, and VIII, IVB or VB metal content 1-8 wt%. The preparation process of the catalytic includes preformation of the transitional acid carrier, once soaking the carrier in the solution of the said metals, drying and roasting. The catalyst is used for the oxidation and desulfurization of sulfur containing hydrocarbon fraction oil in the presence of oxidant and alcohol, and is especially suitable for the oxidation and desulfurization process of light oil products.
Description
1, technical field:
The present invention relates to a kind of fraction oil oxidation desulfurizing catalyst and preparation method thereof.More particularly, be to have in the presence of oxygenant, the alcohol about a kind of, oxidation is present in the Catalysts and its preparation method of the organosulfur in the sulfur-bearing hydrocarbon-fraction oil 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 the new standard of all kinds of hydrocarbon-fraction oil in succession, and it has all carried out strict regulation and restriction to sulphur content, benzene content, aromaticity content, olefin(e) centent and oxygen level.
As everyone knows, the reduction of the sulphur content of all kinds of hydrocarbon-fraction oil, 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 middle runnings also increases to some extent, now ME120X technologies that adopt non-hydrogen more, its adopts sulfonation phthalein mountain valley with clumps of trees and bamboo cobalt catalyst 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.
ZL91111731.8 discloses hydrocarbon-fraction oil two step process for sweetening, wherein a step is in the presence of the selectivity hydrogenolysis catalyst, the more dysoxidizable uncle's mercaptan of hydrogenolysis, another step is that uncle mercaptan and/or secondary mercaptan react in the presence of oxide catalyst and basic component with a kind of oxygenant and oxidized, understands the generation waste lye in its process.
CN1048543 discloses the oxidation-desulfurizing catalyst and the method for the sulfur-bearing hydrocarbon-fraction of the more dysoxidizable mercaptan of a kind of processing, its catalyzer is a kind of a kind of metallo-chelate that is dispersed on the big surface adsorption carrier, the metalphthelein mountain valley with clumps of trees and bamboo 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, the sulfur-bearing hydrocarbon-fraction 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.
3, summary of the invention:
The purpose of this invention is to provide a kind of oxidation-desulfurizing catalyst of handling the sulfur-bearing hydrocarbon-fraction and preparation method thereof.Thereby the simplification technological process avoids producing waste lye, improves the quality of products in desulfurization.
As previously mentioned, no matter sulfur removal technology of the prior art is the hydrogen addition technology desulfurization, or oxidation sweetening, all has shortcoming not fully up to expectations.The present inventor is surprised to find that on porous support and introduces group vib and group VIII or IVB family, VB family metal, and adjust ratio between several components, can be in the presence of no caustic alkali, oxidation is present in organosulfur in the sulfur-bearing hydrocarbon-fraction oil effectively in the presence of oxygenant and alcohol.
The invention provides a kind of fraction oil oxidation desulfurizing catalyst, wherein contain the group vib that loads on the porous support and group VIII or IVB, VB family metal.With the catalyzer is benchmark, and the content of described group vib metal is 10%～30% (m/m), is preferably 15%～25% (m/m), and the content of group VIII or IVB, VB family metal is 1%～8% (m/m), is preferably 2%～5% (m/m).Said group vib metal is preferably molybdenum and/or tungsten; The group VIII metal is preferably nickel, and IVB, VB family metal are preferably zirconium and vanadium.
Catalyzer provided by the invention can also add auxiliary agent, and described auxiliary agent is selected from one or more in the oxide compound of bismuth, palladium or phosphorus, is benchmark with the catalyzer, and in element, the content of described auxiliary agent is 0.01%～5% (m/m), preferred 0.2%～3% (m/m).
The porous support that catalyzer of the present invention is used, it can be any porous support that can be used for preparing catalyzer, as: silicon oxide, aluminum oxide, titanium oxide, Thorotrast, zirconium white or wherein any two or more mixture, be preferably the silica-alumina carrier, its silica (molecular ratio) 10～50, preferred 20～40; The titanium dioxide-aluminum oxide carrier, its titanium oxide/aluminum oxide (molecular ratio) 5～15, preferred 7～10; Alumina supporter, preferred gama-alumina.
Preparation of catalysts method provided by the invention comprises the aqueous solution dipping porous support with the soluble compound of above-mentioned metal, and drying, roasting obtain catalyzer of the present invention.
Preparation of catalysts step of the present invention comprises:
(1) porous acid carrier precursor is through moulding, drying, in the presence of air, in 450～650 ℃ of roastings 1～6
Hour make porous support.(2) the porous acid carrier that obtains with aqueous solution dipping (1) step of group vib and group VIII or IVB, VB family metallic compound, after 100～120 ℃ of dryings, 400～550 ℃ of roastings 2～8 hours obtain catalyzer of the present invention.
It is 10%～30% (m/m) that the consumption of wherein said group vib and group VIII or IVB, VB family metallic compound should make the content of the group vib metal oxide in the final catalyzer, preferred 15%～25% (m/m).The content 1%～8% (m/m) of group VIII or IVB, VB family metal oxide, preferred 2%～5% (m/m).
Described dipping can adopt general pickling process, preferred saturated pickling process.
Described group vib metallic compound is preferably the compound of molybdenum and/or tungsten, the group VIII metallic compound is the compound of nickel, can be in its aqueous solution compound one or more, preferably be respectively ammonium tungstate, ammonium metawolframate and/or ammonium molybdate, nickel compound can be selected from its water-soluble nitrate, acetate, carbonate, subcarbonate, preferred nickelous nitrate and/or nickel acetate.IVB, VB family metallic compound are preferably the metallic compound of zirconium and vanadium, preferably zirconium nitrate and ammonium meta-vanadate.
Method for preparing catalyst provided by the invention can also comprise with one or more the aqueous solution in bismuth-containing, palladium and the phosphorus compound and floods described porous acid carrier, carries out before described being immersed in (2) step, dipping is after 100～120 ℃ of dryings, 400～550 ℃ of roastings.The consumption of described bismuth, palladium and phosphorus compound should make and contain 0.01%～5% (m/m) (in element) in the final catalyzer, preferred 0.2%～3% (m/m).
Bismuth, palladium and phosphorus compound are selected from one or more in its water-soluble cpds, the wherein preferred Bismuth trinitrate of bismuth compound, bismuth oxide, the preferred Palladous nitrate of palladium compound, one or more in phosphorus compound preferably phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, the primary ammonium phosphate.
Catalyzer provided by the invention is in the presence of oxygenant and alcohol, and can be used for boiling range is the oxidation removal of organic sulfur from of 40～325 ℃ sulfur-bearing hydrocarbon-fraction, and being specially adapted to boiling range is the oxidation sweetening process of 40～210 ℃ light fractions.
Said oxygenant can be any oxygenant that is applicable to the oxidation sweetening process, is preferably in aqueous hydrogen peroxide solution, hydrogen/oxygen mixture and the ozone one or more, is preferably aqueous hydrogen peroxide solution.
Alcohol in the oxidation sweetening process of the present invention is selected from the C1～C10 alkanol of linearity or collateralization, and one or more in C5～C8 cycloalkanol and C7～C12 aryl alcohol particularly preferably are the alkyl alcohol of C1～C6.
Above-mentioned alkylol cpd add-on can be 5%～50% (m/m) of sulfur-bearing hydrocarbon-fraction oil.
Catalyzer provided by the invention is used for sulfur-bearing hydrocarbon-fraction oil oxidation sweetening 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 sulfur-bearing hydrocarbon-fraction oil oxidation sweetening 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 sulfur-bearing hydrocarbon-fraction oil oxidation sweetening process 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 sulfur-bearing hydrocarbon-fraction stock oil character with to the requirement of hydrocarbon-fraction processed oil quality: during operate continuously: temperature of reaction-20～180 ℃, preferred 10 ℃～80 ℃; Liquid hourly space velocity 0.5～2.0h
-1, preferred 1.0 h
-1The vapour pressure of solution when reaction pressure is temperature of reaction.During periodical operation: temperature of reaction-20～180 ℃, 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, alkene in the sulfur-bearing hydrocarbon-fraction oil and oxygen, pure initial ring oxidation, alkoxide reaction, and generate glycol monoether or glycol bis ether compounds, this compounds can obviously improve the octane value of gasoline products.Simultaneously, sulfur-bearing, nitrogenous compounds such as the mercaptan in the sulfur-bearing hydrocarbon-fraction oil (comprising extremely dysoxidizable uncle's mercaptan), thioether, pyrroles, pyridine are oxidized to polar material and are removed.Thereby foreign matter contents such as alkene, sulphur, nitrogen in the hydrocarbon-fraction oil have been reduced.Remedy the big deficiency of hydrodesulfurization loss of octane number, overcome the shortcoming that there is waste lye in other oxidation desulfurizing method.
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 the support of the catalyst that the present embodiment explanation provides
The silica-alumina carrier is to adopt to become continuously the preparation of glue method, in preparation process, can adjust proportioning raw materials, obtains the carrier of different silica (molecular ratio).The silica-alumina bead carrier Z1 (molecular ratio is 25) that chooses, its physico-chemical property sees Table 1.
Embodiment 2
The preparation of the support of the catalyst that the present embodiment explanation provides
(titanium oxide/alumina molecule ratio is 8 to take by weighing 500 gram titanium dioxide-aluminum oxide powder, Nanjing Nan Hua company catalyst plant is produced), add a small amount of extrusion aid and less water, fully mediate evenly, be squeezed into bar shaped, dried 4 hours for 120 ℃, 550 ℃ of roastings 4 hours, the bar shaped carrier that obtains is cut into the 3-8 millimeter, makes carrier Z2, carrier Z2 physico-chemical property sees Table 1.
Embodiment 3
The preparation of the support of the catalyst that the present embodiment explanation provides
Take by weighing 1000 gram aluminium hydrate powder (content 70% (m/m), pseudo-boehmite scolder 85% (m/m), Shandong Aluminum Plant produces), add a small amount of extrusion aid and less water, fully mediate evenly, be squeezed into bar shaped, 120 ℃ of oven dry 4 hours, 600 ℃ of roastings 4 hours are cut into the 3-8 millimeter with the bar shaped carrier that obtains, make gamma-aluminium oxide carrier Z3, carrier Z3 physico-chemical property sees Table 1.
Embodiment 4～6
The following examples explanation preparation that contains the support of the catalyst of auxiliary component provided by the invention
Take by weighing Bismuth trinitrate [Bi (NO
3)
35H
2O] 7.2 grams, add deionized water and be made into 95 milliliters of Bismuth trinitrate aqueous solution, with the Bismuth trinitrate aqueous solution for preparing dipping 150 gram carrier Z3, then in 120 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours will make carrier Z4, and carrier Z4 physico-chemical property sees Table 1.
Adopt same quadrat method, take by weighing 22 milliliters of phosphoric acid (concentration 85.6%) and Palladous nitrate [Pd (NO respectively
3)
2] 1 gram, add deionized water respectively and be made into 95 milliliters of phosphate aqueous solutions and palladium nitrate aqueous solution, with the phosphate aqueous solution for preparing and palladium nitrate aqueous solution dipping 150 gram carrier Z3, then in 120 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours will make phosphorous carrier Z5, contain palladium carrier Z6.Auxiliary agent content (in element) among carrier Z4, Z5, the Z6.Carrier Z5, Z6 physico-chemical property see Table 1.
Table 1 example number 123456 bearer number Z1 Z2 Z3 Z4 Z5 Z6 auxiliary agent kinds---Bi P Pd auxiliary agent content % (m/m)---1.9 1.5 0.3 specific surface/m2G
-1256 272 283 272 278 279 pore volumes/mlg
-10.4 0.4 0.441 0.4 0.4 0.4
Embodiment 7～16
The following examples illustrate catalyzer provided by the invention and preparation thereof
Take by weighing quantitative nickelous nitrate [Ni (NO respectively
3)
26H
2O], ammonium meta-vanadate or zirconium nitrate [Zr (NO
3)
45H
2O] and ammonium molybdate [(NH
4) Mo
7O
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 95 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 2.
Table 2 example number 789 10 11 12 13 14 15 16 catalyst numbering C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 bearer number Z1 Z2 Z3 Z3 Z3 Z3 Z4 Z5 Z6 Z3 zirconium nitrate---14.6-----ammonium metavanadate-----6.2----nickel nitrate consumption/g 15.6 14.2 15.9 17.8--16.4 16.6 16.6 23.4 ammonium molybdate consumptions/g--45.5-------AMT consumption/ml 56.5 48.0-61.5 55.3 56.6 56.5 60.0 61.0 67.0ZrO2/ % (m/m)----2.6-----V
2O
5/ % (m/m)-----3.1----urge NiO/% (m/m) 2.4 2.2 2.5 2.7--2.4 2.6 2.6 3.5 to change WO
3/ % (m/m) 20.7 17.2-22.8 19.7 20.8 20.5 21.5 21.9 24.9 contain Bi/% (m/m)------1.5--amount P/% (m/m)------1.2--Pd/% (m/m)--------0.2-
Comparative Examples 1
Measure 68 milliliters of described AMT solution of example 6-12, add deionized water and be made into 95 milliliters and contain ammonium metatungstate aqueous solution, with the above-mentioned solution impregnation for preparing 150 gram carrier Z3 4 hours, 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtain reference catalyst, it is numbered C11, and C11 contains WO
325.1% (m/m).
Embodiment 17～224
The following examples illustrate that catalyzer provided by the invention is used for the activity of sulfur-bearing hydrocarbon-fraction oil oxidation sweetening.
Table 3 is depicted as FCC sulfur-bearing hydrocarbon-fraction oil properties.With the full distillation gasoline of sulfur-bearing is raw material, estimates C1～C9 catalyst desulfurizing activity.Be reflected on 300 milliliters of fixed-bed reactor and carry out continuously.100 milliliters of loaded catalysts.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.
Table 3 raw material oil properties
The full distillation gasoline aviation kerosene of stock oil title FCC straight-run diesel oil
Stock oil numbering 1# 2# 3#
d
4 20 0.7388 0.7864 0.8216
Boiling range ℃
IBP 34 162 177
10％ 57 171 204
50％ 102 184 254
90％ 163 209 290
FBP 182 228 320
Bromine number/gBr (100g)
-10.61--
Mercaptan sulfur content/μ gg
-1123 89 34
Total sulfur content/μ gg
-11,520 1,470 1345
Table 4
Example number 17 18 19 20 21 22 21 22 23 24 relatively
Example 1
Catalyzer numbering C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11
Bromine number 0.47 0.56 0.54 0.46 0.49 0.51 0.44 0.52 0.50 0.42 0.49
/gBr·(100g)
-1
Mercaptan sulfur content 5.7 9.6 8.9 4.5 4.6 4.9 4.0 7.5 8.3 4.2 3.2
/μg·g
-1
Product total sulfur content 276 432 404 242 236 251 221 364 374 227 293
/μg·g
-1
Embodiment 25～26
The following examples illustrate that catalyzer provided by the invention is used for the activity of sulfur-bearing hydrocarbon-fraction oil oxidation sweetening.
Press the activity of the method evaluate catalysts C4 of embodiment 17～24, used stock oil is respectively aviation kerosene shown in the table 3 and straight-run diesel oil.Reaction conditions and product property see Table 5.
Table 5
Example number 25 26
Stock oil numbering 2# 3#
Temperature of reaction/℃ 90 100
Reaction pressure/MPa 0.6 0.6
Liquid hourly space velocity/h
-11.0 1.0
Mercaptan sulfur content/μ gg
-16.5-
Product total sulfur content/μ gg
-1345 184
Claims (10)
1. fraction oil oxidation desulfurizing catalyst, it is characterized in that containing in the catalyzer group vib and group VIII, IVB family or the VB family metal that load on the porous support, with the catalyzer is benchmark, the content of described group vib metal is 10m%～30m%, and the content of group VIII, IVB family or VB family metal is 1m%～8m%.
2. according to the described catalyzer of claim 1, base is characterised in that said group vib metal is molybdenum and/or tungsten; The group VIII metal is a nickel; IVB family metal is a zirconium; VB family metal is a vanadium.
3. according to the described catalyzer of claim 1, it is characterized in that containing in the catalyzer auxiliary agent, auxiliary agent is selected from one or more in the oxide compound of bismuth, palladium or phosphorus, and in element, the content of described auxiliary agent in catalyzer is 0.01m%～5m%.
4. according to the described catalyzer of claim 1, it is characterized in that said porous support is silicon oxide, aluminum oxide, titanium oxide, Thorotrast, zirconium white or wherein any two or more mixture.
5. according to the described catalyzer of claim 4, it is characterized in that said porous support is the silica-alumina carrier, wherein silica is 10～50; Titanium dioxide-aluminum oxide carrier, its titanium oxide/aluminum oxide are 5～15 and/or alumina supporter.
6. described Preparation of catalysts method of claim 1 is characterized in that its preparation process comprises:
(1), porous acid carrier precursor makes porous support through moulding, drying, roasting;
(2), the porous support that obtains with the aqueous solution of group vib and group VIII, IVB family or VB family metallic compound dipping (1) step, after 100～120 ℃ of dryings, 400～550 ℃ of roastings 2～8 hours obtain catalyzer of the present invention.
7. according to the described preparation method of claim 6, it is characterized in that flooding described porous support with one or more the aqueous solution in bismuth-containing, palladium and the phosphorus compound, carries out before described being immersed in (2) step, dipping is after 100～120 ℃ of dryings, 400～550 ℃ of roastings.
8. the application of the described catalyzer of claim 1 in the fraction oil oxidation desulfurizing process: it is characterized in that in the presence of oxygenant and alcohol under the oxidation sweetening condition, being that 40～325 ℃ sulfur-bearing hydrocarbon-fraction is oily with boiling range contacts with catalyzer of the present invention.
9. according to the described application of claim 8, it is characterized in that said alcohol, be selected from the C1～C10 alkanol of linearity or collateralization, one or more in C5～C8 cycloalkanol and C7～C12 aryl alcohol.
10. according to the described application of claim 8, it is characterized in that said oxidation sweetening condition is: temperature of reaction-20～180 ℃; Liquid hourly space velocity 0.5～2.0h
-1The vapour pressure of solution when reaction pressure is temperature of reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108325563A (en) * | 2018-04-02 | 2018-07-27 | 广东石油化工学院 | A kind of catalyst for the sulfur content reducing FCC petroleum distillates |
| CN108467745A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The method of nitride in molecular sieve catalytic oxidation removal oil product |
| CN108467746A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The method of sulfide in molecular sieve catalytic oxidation removal oil product |
| CN108525658A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of the catalyst system and sulfur-bearing hydrocarbon oxidation sweetening of sulfur-bearing hydrocarbon oxidation sweetening |
| CN108525660A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | A kind of method of sulfur-bearing hydrocarbon oxygenation desulfurization |
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| CN101962567B (en) * | 2010-09-30 | 2013-09-18 | 西安科技大学 | Method for catalytically oxidizing sulfocompound in petroleum product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108467745A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The method of nitride in molecular sieve catalytic oxidation removal oil product |
| CN108467746A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The method of sulfide in molecular sieve catalytic oxidation removal oil product |
| CN108525658A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of the catalyst system and sulfur-bearing hydrocarbon oxidation sweetening of sulfur-bearing hydrocarbon oxidation sweetening |
| CN108525660A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | A kind of method of sulfur-bearing hydrocarbon oxygenation desulfurization |
| CN108525660B (en) * | 2017-03-03 | 2022-05-17 | 中国石油化工股份有限公司 | Method for oxygen-adding and desulfurizing sulfur-containing hydrocarbon |
| CN108325563A (en) * | 2018-04-02 | 2018-07-27 | 广东石油化工学院 | A kind of catalyst for the sulfur content reducing FCC petroleum distillates |
| CN110252384A (en) * | 2019-06-20 | 2019-09-20 | 大连理工大学 | A kind of sub-nanometer cluster transition metal oxide/MCM-41 composite material, preparation method and applications |
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Granted publication date: 20050608 |