CN105268473A - Hydrocarbon oil desulphurization catalyst, and preparation method thereof, and hydrocarbon oil desulphurization method - Google Patents

Hydrocarbon oil desulphurization catalyst, and preparation method thereof, and hydrocarbon oil desulphurization method Download PDF

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CN105268473A
CN105268473A CN201410276260.1A CN201410276260A CN105268473A CN 105268473 A CN105268473 A CN 105268473A CN 201410276260 A CN201410276260 A CN 201410276260A CN 105268473 A CN105268473 A CN 105268473A
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molecular sieve
zsm
catalyst
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CN105268473B (en
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宋烨
林伟
田辉平
龙军
王磊
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a hydrocarbon oil desulphurization catalyst, a preparation method thereof, and a hydrocarbon oil desulphurization method. The hydrocarbon oil desulphurization catalyst comprises a carrier and an active ingredient; the carrier comprises aluminium oxide, a silicon oxide source, zinc oxide, and P and Fe modified ZSM-5 molecular sieve; the active ingredient comprises nickel and/or cobalt; wherein in the P and Fe modified ZSM-5 molecular sieve, mass ratio of P2O5/Fe2O3 is 1-4:1, mass ratio of the active ingredient/the P and Fe modified ZSM-5 molecular sieve is 0.5-4:1, and acid content ratio of B acid/L acid of the catalyst is 0.3-0.8:1. The hydrocarbon oil desulphurization catalyst is capable of realizing desulphurization and generating hydrogen at the same time, and reducing hydrocarbon oil desulphurization hydrogen consuming cost; the hydrocarbon oil desulphurization catalyst possesses higher stability and desulphurization activity, excellent wear resistance, and long service life.

Description

A kind of method of desulfurization of hydrocarbon oil Catalysts and its preparation method and desulfurization of hydrocarbon oil
Technical field
The present invention relates to a kind of method of desulfurization of hydrocarbon oil Catalysts and its preparation method and desulfurization of hydrocarbon oil, particularly, relate to a kind of desulfurization of hydrocarbon oil catalyst, the method preparing desulfurization of hydrocarbon oil catalyst and the desulfurization of hydrocarbon oil catalyst obtained by the method, and use this desulfurization of hydrocarbon oil catalyst to carry out the method for desulfurization of hydrocarbon oil.
Background technology
Along with people are to the pay attention to day by day of environmental protection, environmental regulation is also day by day strict, and the sulfur content reducing gasoline and diesel oil is considered to one of most important measure improving air quality.Most of sulphur in China's gasoline products come from hot-working petroleum blending component, as catalytically cracked gasoline.Therefore in hot-working petroleum, the minimizing of sulfur content contributes to the sulfur content reducing China's gasoline products.The existing gasoline products standard GB17930-2011 " motor petrol " of China required on December 31st, 2013, and in gasoline products, sulfur content must drop to 50 μ g/g.And the gasoline product quality standard in future will be stricter.In this case, catalytically cracked gasoline has to pass through deep desulfuration gasoline products just can be made to meet the requirement of environmental protection.
At present, the process for deep desulphurization of oil product mainly contains selective catalytic hydrogenation desulfurization and catalytic hydrogenation adsorption desulfurize two kinds of methods.Catalytic hydrogenation adsorption desulfurize (S-Zorb) be certain temperature, pressure and face hydrogen condition under realize the sulfur compounds adsorption in hydrocarbon ils to remove, this technology has desulfurization depth high, has broad application prospects.
CN1488728A provides a kind of aromatization catalyst for catalytic gasoline and application process thereof, and with the percentage by weight of catalyst for benchmark, it consists of: bullion content is 0.1%-1.0%, K type zeolite content is 50.0%-90.0%, wherein K 2o content is 1.0%-5.0%; Surplus is binding agent.This catalyst can be applied in the hydrodesulfurization of catalytic gasoline.Thus while reaching desulfurization and reduction olefin(e) centent, the anti-knock index of product loses less object.
CN1290977C provides and a kind ofly produces by catalytically cracked gasoline the catalyst that low-sulfur, the technique of low alkene clean gasoline and this technique uses.Present invention process adopts hydrofinishing/aromatisation process integration, and wherein aromatisation adopts the little crystal grain hydrogen type molecular sieve catalyst comprising IA race metal, magnesium-yttrium-transition metal and lanthanide rare metal oxide, and molecular sieve is that grain size is within the scope of 20nm-800nm.It is short that this invention catalyst has duct, acid suitable, can reduce cracking reaction, improve the yield of gasoline, decrease the carbon deposit of catalyst simultaneously.Invented technology adopts hydrofinishing/aromatisation process FCC gasoline, and reaching in desulfurization with while reducing olefin(e) centent, the anti-knock index loss of product is less; Meanwhile, the alkadienes of unifining process easy coking under being stripped of high temperature, improves the stability with the aromatization catalyst of octane value recovering function.
CN1227334C provides a kind of ultrafine particle zeolite aromatized catalyst and preparation method thereof and the application in full cut FCC gasoline hydrofinishing/aromatisation group technology.With the weight of catalyst for benchmark, the composition of this catalyst comprises: transition metal oxide and lanthanide rare metal oxide content sum are 1.0wt%-10.0wt%, ultrafine particle zeolite content is 50.0wt%-90.0wt%, surplus is inorganic oxide adhesive, and the grain size of ultrafine particle zeolite is 20nm-800nm.This catalyst anti-coking performance is strong, good stability, and while the sulfur content reducing FCC gasoline and olefin(e) centent, can ensure that the anti-knock index loss of gained gasoline product is less.
CN101433821A provides a kind of catalyst reducing sulfur content in hydrocarbon oils, comprises rare earth faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; By above-mentioned rare earth faujasite and carrier mixture preshaped be porous heat-resistant solid particle, then introduce metal active constituent on this solid particle, prepare described catalyst.
CN101434854A provides a kind of catalyst reducing sulfur content of light hydrocarbon oil, comprises P Modification rare earth faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; By preshaped with carrier mixture after P Modification for above-mentioned rare earth faujasite be porous heat-resistant solid particle, then introduce metal active constituent on this solid particle, prepare described catalyst.
Although said method adds and selects that shape zeolite is conducive to isomerization, aromatisation increases octane number, lack enough desulphurizing activated.
CN1355727A provides a kind of novel absorbent composition containing zinc oxide, silica, aluminium oxide and nickel or cobalt, and provides the preparation method of this catalyst.First the method prepares the carrier containing zinc oxide, silica, aluminium oxide, then introduces nickel by dipping.This catalyst can be used for removing sulphur from cracking gasoline or diesel fuel.
CN1208124C provides and adopts promoter metals such as cobalt and nickel dipping to comprise the catalyst carrier of zinc oxide, expanded perlite and aluminium oxide, then reduction accelerator at appropriate temperatures, for the preparation of the catalyst removing cracking gasoline medium sulphide content.
Above-mentioned catalyst can realize ultra-deep desulfurization under hydro condition, and product sulfur levels can be reduced to below 10ppm, but it is large to consume amounts of hydrogen, and is difficult to the loss of octane number of avoiding olefins hydrogenation to bring.Reach 3,540 ten thousand tons/year to the total working ability of 2014 China S-Zorb in the end of the year, account for more than 40% of domestic gasoline aggregate consumption.Industrial data according to enterprise is added up, and in S-Zorb device, the cost of hydrogen consumption accounts for this device total operating cost more than 40%.
As can be seen here, because hydrogen acquisition cost is huge and the huge hydrogen gas consumption of existing catalytic hydrogenation adsorption desulfurize technology, the quality upgrading of the practical application of this technology and popularization and gasoline products is made to face huge obstacle, therefore, need to provide one can overcome in catalytic hydrogenation adsorption desulfurize technology, the method that hydrogen gas consumption is large.
Summary of the invention
The object of the invention is, in order to overcome the defect that in existing catalytic hydrogenation adsorption desulfurize technology, hydrogen gas consumption is large, to provide a kind of method of desulfurization of hydrocarbon oil Catalysts and its preparation method and desulfurization of hydrocarbon oil.
To achieve these goals, the invention provides a kind of desulfurization of hydrocarbon oil catalyst, this catalyst comprises carrier and active component, and described carrier comprises the ZSM-5 molecular sieve of aluminium oxide, silica source, zinc oxide and P and Fe modification, and described active component comprises nickel and/or cobalt; Wherein, in the ZSM-5 molecular sieve of described P and Fe modification, P 2o 5/ Fe 2o 3mass ratio be 1-4:1, the mass ratio of the ZSM-5 molecular sieve of described active component and described P and Fe modification is 0.5-4:1, and the acid molar ratio of the B acid/L acid of described catalyst is 0.3-0.8:1.
Present invention also offers the preparation method of desulfurization of hydrocarbon oil catalyst of the present invention, the method comprises: (1) is under the condition of exchange reaction, ZSM-5 molecular sieve and the solution of phosphorus-containing compound, the solution of iron containing compounds are carried out exchange reaction, obtains the ZSM-5 molecular sieve of P and Fe modification; (2) ZSM-5 molecular sieve of P and Fe modification alumina binder, silica source, zinc oxide, step (1) obtained, water and acidic liquid are mixed to get carrier pulp, described carrier pulp is carried out shaping, first dry and the first roasting, obtain carrier; (3) introduce the compound containing active component on the carrier and carry out second dry and the second roasting, obtaining catalyst precarsor; (4) described catalyst precarsor is reduced in a hydrogen atmosphere, obtain desulfurization of hydrocarbon oil catalyst.
The present invention also provides the desulfurization of hydrocarbon oil prepared by method of the present invention catalyst.
Present invention also offers a kind of method of desulfurization of hydrocarbon oil, the method comprises: under the condition of facing H-H reaction, by hydrocarbon oil containing surphur and desulfurization of hydrocarbon oil catalyst exposure provided by the invention.
In the composition of desulfurization of hydrocarbon oil catalyst provided by the invention, carrier part contains the ZSM-5 molecular sieve of P and Fe modification, and wherein P and Fe is (respectively with P 2o 5and Fe 2o 3meter) there is extra fine quality ratio between content; Also extra fine quality ratio is had in addition between active component and this modified molecular screen, this catalyst also shows the acid molar ratio of specific B acid/L acid, this not only makes carrying out catalytic hydrogenation adsorption desulfurize, during as S-Zorb technique, the stability that can have and high desulphurizing activated, more effectively the sulphur in hydrocarbon ils can be adsorbed onto on desulfurization of hydrocarbon oil catalyst in desulfurization of hydrocarbon oil process, obtain the hydrocarbon ils that sulfur content is lower; The more important thing is and can increase production hydrogen when carrying out this technique, as promoted the reaction such as cycloalkane dehydroaromatizationof, n-alkane dehydrocyclization in hydrocarbon ils, to produce while hydrogen and to generate antiknock component, reduce the consumption of this technique added hydrogen supply, reduce the operational applications cost of this technique, the quality of the sulfur-free gasoline of production is also improved.In addition desulfurization of hydrocarbon oil catalyst provided by the invention has better abrasion resistance properties, and in sweetening process, catalyst attrition is lower, longer service life.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of desulfurization of hydrocarbon oil catalyst, this catalyst comprises carrier and active component, and described carrier comprises the ZSM-5 molecular sieve of aluminium oxide, silica source, zinc oxide and P and Fe modification, and described active component comprises nickel and/or cobalt; Wherein, in the ZSM-5 molecular sieve of described P and Fe modification, P 2o 5/ Fe 2o 3mass ratio be 1-4:1, the mass ratio of the ZSM-5 molecular sieve of described active component and described P and Fe modification is 0.5-4:1, and the acid molar ratio of the B acid/L acid of described catalyst is 0.3-0.8:1.
Preferably, in the ZSM-5 molecular sieve of described P and Fe modification, P 2o 5/ Fe 2o 3mass ratio be 1.5-3.5:1; More preferably, in the ZSM-5 molecular sieve of described P and Fe modification, P 2o 5/ Fe 2o 3mass ratio be 1.8-3:1.When in the ZSM-5 molecular sieve of described P and Fe modification, modified component P and Fe is aforementioned proportion, the acid activity center that desulfurization of hydrocarbon oil catalyst is suitable can be provided, promote the reaction such as cycloalkane dehydroaromatizationof, n-alkane dehydrocyclization in hydrocarbon ils, produce hydrogen while generating antiknock component, effectively reduce the hydrogen consumption in sweetening process.
Preferably, the mass ratio of the ZSM-5 molecular sieve of described active component and described P and Fe modification is 0.6-2.5:1; More preferably, the mass ratio of the ZSM-5 molecular sieve of described active component and described P and Fe modification is 0.7-2:1.When having this specific relation between the ZSM-5 molecular sieve of described active component and described P and Fe modification, the facilitation of described active component to the reaction such as cycloalkane dehydroaromatizationof, n-alkane dehydrocyclization in hydrocarbon ils can be improved, be conducive to volume increase hydrogen and generate antiknock component simultaneously, effectively can reduce the quality that hydrogen consumption also promotes to improve gasoline products.
Preferably, the acid molar ratio of the B acid/L acid of described catalyst is 0.35-0.6:1.Wherein, concrete assay method infrared acidity assay method (90-92 page) disclosed in " catalyst analysis " (publishing house of Northeastern University published in July, 2000) of B acid and L acid measures, specific as follows: the preparation of (I) sample: to get levigate rear sample (granularity is less than 200 orders) 10mg, being pressed into diameter is that 13mm thin slice is placed in cell for infrared absorption, that gets that 100mg sample (sheet) loads quartz spring lower end again hangs in cup, system pump down to 1 × 10 -2pa, is heated to 500 DEG C of constant temperature 1 hour, purification sample, removes the adsorbate and water that cover on specimen surface; (II) drop to room temperature in the above-mentioned condition of finding time, Adsorption of Pyridine 5min, be then warmed up to 160 DEG C, balance 1h, the pyridine of desorption physical absorption, records the infrared spectrogram of gained under above-mentioned condition, the bands of a spectrum 1545cm that wherein B acid is corresponding -1, the bands of a spectrum 1455cm that L acid is corresponding -1, thus, the acid molar ratio of B acid/L acid when obtaining 160 DEG C.In the present invention, the acid molar ratio of the B acid/L acid of described catalyst is the acid molar ratio of the B acid/L acid of this catalyst 160 DEG C time.When catalyst provided by the invention has the acid molar ratio in this scope, suitable acid activity center can be provided, promote the reaction such as cycloalkane dehydroaromatizationof, n-alkane dehydrocyclization in hydrocarbon ils, hydrogen is produced while generating antiknock component, hydrogen consumption in effective reduction sweetening process, and cracking reaction is less.
In the present invention, with the gross weight of described carrier for benchmark, alumina content is 3.5-40 % by weight, and zinc oxide content is 12-94 % by weight, and described silica source content is 6-47 % by weight, and the ZSM-5 molecular sieve content of described P and Fe modification is 5-41 % by weight; Preferably, alumina content is 7-29 % by weight, and zinc oxide content is 29-82 % by weight, and described silica source content is 12-35 % by weight, and the ZSM-5 molecular sieve content of described P and Fe modification is 7-35 % by weight; More preferably, alumina content is 9-17 % by weight, and zinc oxide content is 47-70 % by weight, and described silica source content is 12-25 weight 14-30, and the ZSM-5 molecular sieve content of described P and Fe modification is 9-30 % by weight.Described carrier can also comprise other routines can as the component of carrier, such as laminated clay column, titanium oxide, zirconia, tin oxide etc.
According to the present invention, under preferable case, with the gross weight of this catalyst for benchmark, the ZSM-5 molecular sieve content that zinc oxide content is 10-80 % by weight, alumina content is 3-35 % by weight, described silica source content is 5-40 % by weight, described active component content is 5-30 % by weight and described P and Fe modification is 4-35 % by weight; With the gross weight of the ZSM-5 molecular sieve of described P and Fe modification for benchmark, with P in the ZSM-5 molecular sieve of described P and Fe modification 2o 5the P content of meter is 1-8 % by weight, with Fe 2o 3the Fe content of meter is 0.3-5 % by weight.
In the present invention, preferably, with the gross weight of this catalyst for benchmark, the ZSM-5 molecular sieve content that zinc oxide content is 25-70 % by weight, alumina content is 6-25 % by weight, described silica source content is 10-30 % by weight and described P and Fe modification is 6-30 % by weight; More preferably, with the gross weight of this catalyst for benchmark, the ZSM-5 molecular sieve content that zinc oxide content is 40-60 % by weight, alumina content is 8-15 % by weight, described silica source content is 12-25 % by weight and described P and Fe modification is 8-25 % by weight.
In the present invention, preferably, with the gross weight of this catalyst for benchmark, described active component content 8-25 % by weight; More preferably, described active component content is 12-20 % by weight.
In the present invention, preferably, with the gross weight of the ZSM-5 molecular sieve of described P and Fe modification for benchmark, with P in the ZSM-5 molecular sieve of described P and Fe modification 2o 5the P content of meter is 2-6 % by weight, with Fe 2o 3the Fe content of meter is 0.5-4 % by weight; More preferably, with P in the ZSM-5 molecular sieve of described P and Fe modification 2o 5the P content of meter is 2.5-5 % by weight, with Fe 2o 3the Fe content of meter is 1-2 % by weight.
According to the present invention, under preferable case, the SiO of described ZSM-5 molecular sieve 2: Al 2o 3mol ratio be 10-70:1; Preferably, the SiO of described ZSM-5 molecular sieve 2: Al 2o 3mol ratio be 15-60:1; More preferably, the SiO of described ZSM-5 molecular sieve 2: Al 2o 3mol ratio be 20-40:1.The ZSM-5 molecular sieve with above-mentioned molar ratio range is more conducive to desulfurization of hydrocarbon oil and produces high-octane gasoline products.
In the present invention, ZSM-5 molecular sieve containing P and Fe modification in the component of desulfurization of hydrocarbon oil catalyst, the reaction selectivity of the active component in this catalyst can be helped improve, promote this catalyst fecund hydrogen when carrying out catalytic hydrogenation adsorption desulfurize, such as promote the reactions such as cycloalkane dehydroaromatizationof, n-alkane dehydrocyclization, thus the consumption of added hydrogen in minimizing sweetening process, reduce the cost of desulfurization operations.
In the present invention, the ZSM-5 molecular sieve of described P and Fe modification can have following anhydrous chemical expression, counts with the weight of oxide: (0-0.2) Na 2o (1-15) Al 2o 3(1-8) P 2o 5(0.3-5) Fe 2o 3(55-90) SiO 2.Preferably, anhydrous chemical expression, counts with the weight of oxide: (0-0.1) Na 2o (1.5-12) Al 2o 3(2-6) P 2o 5(0.5-4) Fe 2o 3(60-85) SiO 2; More preferably, anhydrous chemical expression, counts with the weight of oxide: (0-0.05) Na 2o (2-10) Al 2o 3(2.5-5) P 2o 5(1-2) Fe 2o 3(70-80) SiO 2.
In the present invention, described aluminium oxide can for providing cementation between each component in described desulfurization of hydrocarbon oil catalyst.Under preferable case, described aluminium oxide is at least one in gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide; Preferably, described aluminium oxide is gama-alumina.
According to the present invention, described silica source can for providing cementation between each component in described desulfurization of hydrocarbon oil catalyst.Under preferable case, the natural crystal that described silica source can be greater than 45 % by weight for silica or silica content.Preferably, described silica source can be at least one in diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
Present invention also offers the preparation method of desulfurization of hydrocarbon oil catalyst of the present invention, the method comprises: (1) is under the condition of exchange reaction, ZSM-5 molecular sieve and the solution of phosphorus-containing compound, the solution of iron containing compounds are carried out exchange reaction, obtains the ZSM-5 molecular sieve of P and Fe modification; (2) ZSM-5 molecular sieve of P and Fe modification alumina binder, silica source, zinc oxide, step (1) obtained, water and acidic liquid are mixed to get carrier pulp, described carrier pulp is carried out shaping, first dry and the first roasting, obtain carrier; (3) introduce the compound containing active component on the carrier and carry out second dry and the second roasting, obtaining catalyst precarsor; (4) described catalyst precarsor is reduced in a hydrogen atmosphere, obtain desulfurization of hydrocarbon oil catalyst.
According to the present invention, step (1) is for providing the ZSM-5 molecular sieve of P and Fe modification.Under preferable case, the process of step (1) described exchange reaction comprises: the solution of ZSM-5 molecular sieve and phosphorus-containing compound, under the condition of the first exchange reaction, reacts, obtains the ZSM-5 molecular sieve of P modification by (A); (B) under the condition of the second exchange reaction, the ZSM-5 molecular sieve of described P modification and the solution of iron containing compounds are carried out the reaction of more than 2 times, obtain the ZSM-5 molecular sieve of P and Fe modification.
In the present invention, the ZSM-5 molecular sieve of P and Fe modification can be denoted as P-Fe-ZSM-5 molecular sieve, and the ZSM-5 molecular sieve of P modification can be denoted as P-ZSM-5 molecular sieve.
In step of the present invention (A), can stir at 80-90 DEG C for the solution of the phosphorus-containing compound by ZSM-5 molecular sieve and amount of calculation and dry particularly, under 500-600 DEG C of condition, calcination process 1-3h obtains P-ZSM-5 molecular sieve.
In step of the present invention (B), particularly can by solid-liquid weight ratio 3-6:1, by the P-ZSM-5 molecular sieve obtained and concentration be 5 % by weight iron containing compounds at 80-90 DEG C, exchange 1-3h and filter, exchange more than 2 times again, until the target reaching Fe is measured, more namely calcination process 2h obtains P-Fe-ZSM-5 molecular sieve at 500-600 DEG C.
In the present invention, the process of described exchange reaction can repeatedly be carried out, and in P-Fe-ZSM-5 molecular sieve, P content is with P 2o 5count 1-8 % by weight, Fe content with Fe 2o 3count 0.3-5 % by weight; Preferably, P content is with P 2o 5count 2-6 % by weight, Fe content with Fe 2o 3count 0.5-4 % by weight; More preferably, P content is with P 2o 5count 2.5-5 % by weight, Fe content with Fe 2o 3count 1-2 % by weight.
In the present invention, phosphorus-containing compound can be at least one among phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate, and preferred described phosphorus-containing compound is ammonium phosphate.The solution of described phosphorus-containing compound can be preferably the aqueous solution.
In the present invention, iron containing compounds can be at least one in ferric sulfate, ferric nitrate, iron chloride, and preferred described iron containing compounds is ferric nitrate.The solution of described iron containing compounds can be preferably the aqueous solution.
According to the present invention, under preferable case, the SiO of described ZSM-5 molecular sieve 2: Al 2o 3mol ratio be 10-70:1; Preferably, the SiO of described ZSM-5 molecular sieve 2: Al 2o 3mol ratio be 15-60:1; More preferably, the SiO of described ZSM-5 molecular sieve 2: Al 2o 3mol ratio be 20-40:1.The ZSM-5 molecular sieve with above-mentioned molar ratio range is more conducive to desulfurization of hydrocarbon oil and produces high-octane gasoline products.
Described in preparation method's step (2) of desulfurization of hydrocarbon oil catalyst provided by the invention, the process of mixing can to the opportunity that adds of silica source, there is no particular limitation, and a kind of detailed description of the invention is: the process of step (2) described mixing comprises: the contact of alumina binder, silica source, water and acidic liquid is formed slurries by (a): the P-Fe-ZSM-5 molecular sieve that described slurries and zinc oxide and step (1) obtain is mixed to get carrier pulp by (b).Another kind of detailed description of the invention is: the process of step (2) described mixing comprises: alumina binder, water and acidic liquid contact and form slurries by (i): the P-Fe-ZSM-5 molecular sieve that described slurries and zinc oxide, silica source and step (1) obtain is mixed to get carrier pulp by (ii-1); Or (ii-2) zinc oxide, silica source and water are mixed into mixed serum, then the ZSM-5 molecular sieve adding above-mentioned slurries and P and Fe modification is mixed to get carrier pulp.
According to the present invention, described alumina binder for aluminium oxide or can change γ-Al under the condition of described first roasting 2o 3material.Under preferable case, described alumina binder can be selected from least one in SB powder, hydrated alumina, Alumina gel, boehmite (boehmite), false boehmite (boehmite), hibbsite and amorphous hydroted alumina; Preferably, described alumina binder is at least one in SB powder, boehmite and Alumina gel.
According to the present invention, described silica source can for providing cementation between each component in described desulfurization of hydrocarbon oil catalyst.Under preferable case, the natural crystal that described silica source can be greater than 45 % by weight for silica or silica content.Preferably, described silica source can be at least one in diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
It should be noted that, although may contain aluminium oxide in above-mentioned silica source, in the present invention, the content of aluminium oxide does not comprise the amount of aluminium oxide contained in above-mentioned silica source, and the content of aluminium oxide only comprises the amount of the aluminium oxide formed by alumina source.The amount of aluminium oxide contained in silica source still can be regarded as the amount of silica source.Namely in the desulphurization catalyst obtained by method provided by the invention, the content of each component calculates according to inventory.
According to the present invention, described acidic liquid can be acid or aqueous acid, and described acid can be selected from water-soluble inorganic acid and/or organic acid, and preferably described acid can be at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
According to the present invention, in the process of step (2) described mixing, under preferable case, the consumption of described acidic liquid makes the pH value of described slurries be 1-5, and preferable ph is 1.5-4.
In the present invention, the amount adding water in step (a) and (i) can not limit, especially as long as can obtain described slurries.The weight ratio such as adding the amount of water and alumina binder or add the amount of water and the weight summation of alumina binder and silica source is 5-10:1.
In preparation method's step (2) of desulfurization of hydrocarbon oil catalyst provided by the invention, zinc oxide for add with the powder type of zinc oxide, also can add water after being mixed into slurries and add in form of slurry by adding of zinc oxide.After Zinc oxide powder and silica source can also being mixed into mixed serum, then add.
In the present invention, the carrier pulp that step (2) obtains can be the form such as pastel or slurries.Can by dry reshaping after this carrier pulp multiviscosisty.More preferably this carrier pulp is slurry form, can form the microballoon that granularity is 20-200 micron, reach shaping object by spraying dry.For the ease of spraying dry, before dry, the solid content of described carrier pulp can be 10-50 % by weight, is preferably 20-50 % by weight.Can obtain also comprising in the process of described carrier pulp adding water in step (b), (ii-1) and (ii-2), there is no particular limitation for the addition of water, as long as the carrier pulp obtained meets above-mentioned solid content.
In the present invention, the first drying means of carrier pulp and condition are conventionally known to one of skill in the art in step (2), such as dry method can be dry, dry, forced air drying.Under preferable case, the temperature of described first drying can be room temperature to 400 DEG C, is preferably 100-350 DEG C; The time of described first drying is more than 0.5h, is preferably 0.5-100h, more preferably 2-20h.
In the present invention, in step (2), the first roasting condition of carrier pulp is also conventionally known to one of skill in the art, and under preferable case, the temperature of described first roasting is 400-700 DEG C, is preferably 450-650 DEG C; The time of described first roasting is at least 0.5h, is preferably 0.5-100h, is more preferably 0.5-10h.
According to the present invention, step (3) is for adding active component.The described compound containing active component is the material that can change the oxide of active component under the second roasting condition into; The described compound containing active component is selected from least one in the acetate of active component, carbonate, nitrate, sulfate, rhodanate and oxide.
In the present invention, described active component comprises nickel and/or cobalt; The compound containing active component is preferably selected from least one in the acetate of nickel and/or cobalt, carbonate, nitrate, sulfate, rhodanate and oxide.
According to the present invention, under preferable case, method carrier introduced containing the compound of active component is dipping or precipitation.Described dipping can for using solution or the suspension impregnation carrier of the compound containing active component; Described precipitation can be the solution of the compound containing active component or suspension are mixed with carrier, then adds ammoniacal liquor and will contain the compound precipitation of active component on carrier.
According to the present invention, under preferable case, the temperature of described second drying is 50-300 DEG C, and the time of described second drying is 0.5-8h; Preferably, the temperature of described second drying is 100-250 DEG C, and the time of described second drying is 1-5h; The temperature of described second roasting is 300-800 DEG C, and the time of described second roasting is more than 0.5h; Preferably, the temperature of described second roasting is 450-750 DEG C, and the time of described second roasting is 1-3h.Described second roasting can be carried out under having oxygen or oxygen-containing gas to exist, until volatile materials is removed and is converted into the oxide form of active component containing the compound of active component, obtains catalyst precarsor.
According to the present invention, in step (4), change the oxide of the active component in described catalyst precarsor into active component simple substance, described catalyst precarsor can be reduced under hydrogen atmosphere, active component is existed with reduction-state substantially, obtains catalyst of the present invention.The condition of described reduction only changes the oxide of the active component in described catalyst precarsor into active component simple substance, and other the various metal oxides in described carrier can not change.Under preferable case, the temperature of described reduction is 300-600 DEG C, and the time of described reduction is 0.5-6h, and in described hydrogen atmosphere, the content of hydrogen is 10-60 volume %; The temperature of preferred described reduction is 400 DEG C-500 DEG C, and the time of preferred described reduction is 1-3h.
In the present invention, catalyst precarsor reduction can be carried out immediately by step (4) after obtained catalyst precarsor, also can before use (namely for desulfurization absorption before) carry out.Because active component is easily oxidized, and the active component in catalyst precarsor exists in the form of an oxide, and therefore for ease of transport, catalyst precarsor reduction is carried out by preferred steps (4) before carrying out desulfurization absorption.Described being reduced to makes the active component in the oxide of active component substantially exist with reduction-state, obtains desulfurization of hydrocarbon oil catalyst of the present invention.
According to the present invention, under preferable case, described alumina binder, described silica source, zinc oxide, described P-Fe-ZSM-5 molecular sieve and the described addition containing the compound of active component make in the desulfurization of hydrocarbon oil catalyst obtained, with the gross weight of this catalyst for benchmark, zinc oxide content is 10-80 % by weight, alumina content is 3-35 % by weight, described silica source content is 5-40 % by weight, described active component content is 5-30 % by weight and described P-Fe-ZSM-5 molecular sieve content is 1-30 % by weight; Preferably, with the gross weight of this catalyst for benchmark, zinc oxide content is 25-70 % by weight, alumina content is 6-25 % by weight, described silica source content is 10-30 % by weight, described active component content is 8-25 % by weight and described P-Fe-ZSM-5 molecular sieve content is 6-30 % by weight; More preferably, with the gross weight of this catalyst for benchmark, zinc oxide content is 40-60 % by weight, alumina content is 8-15 % by weight, described silica source content is 12-25 % by weight, described active component content is 12-20 % by weight and described P-Fe-ZSM-5 molecular sieve content is 8-25 % by weight.
The present invention also provides the desulfurization of hydrocarbon oil prepared by method of the present invention catalyst.
Present invention also offers a kind of method of desulfurization of hydrocarbon oil, the method comprises: under the condition of facing H-H reaction, by hydrocarbon oil containing surphur and desulfurization of hydrocarbon oil catalyst exposure provided by the invention.
According to the present invention, under preferable case, described in face H-H reaction discharge amounts of hydrogen Q2 be greater than described in face H-H reaction add amounts of hydrogen Q1.Sulphur in this process in hydrocarbon ils is adsorbed on catalyst, obtains the hydrocarbon ils of low sulfur content, increases amounts of hydrogen simultaneously.
Preferably, relative to the hydrocarbon oil containing surphur of 1000g, meet between Q2 and Q1: Q2-Q1 >=0.5g; More preferably, Q2-Q1=0.5-5g; Further preferably, Q2-Q1=1-4.5g; Particularly preferably, Q2-Q1=2-4.5g.
Facing H-H reaction described in the present invention can be preferably tandem reaction sequence.In the present invention, Q2 and Q1 can determine by the following method: face H-H reaction described in carrying out, and hydrocarbon oil containing surphur is added reaction unit with the feed rate of 100g/h, is that the hydrogen of 99.9 volume % adds reaction unit with the feed rate of 6.3L/h by purity simultaneously.The flow velocity of the emission gases of assaying reaction device outlet is 7.8L/h (analyzing wherein density of hydrogen with the heat-conducted hydrogen analyzer of QRD-1102A is 87 volume %), by standard state (1atm, 25 DEG C) calculate device add amounts of hydrogen (Q1) and discharge amounts of hydrogen (Q2) difference be Q2-Q1=0.4g.This numerical value faces the increase of H-H reaction acquisition amounts of hydrogen described in carrying out on the occasion of explanation.In same mensuration prior art, this difference is negative value, faces H-H reaction and consumes hydrogen, do not have amounts of hydrogen to increase described in explanation.
According to the present invention, under preferable case, described in face H-H reaction temperature be 350-500 DEG C, described in face H-H reaction pressure be 0.5-4MPa; The described hydrogen partial pressure facing H-H reaction is 0.12-2MPa.
In the preferred detailed description of the invention of one of the present invention, use catalyst provided by the invention, above-mentioned face hydroformylation reaction condition under, not only can remove the sulfide in hydrocarbon ils efficiently, simultaneously can voluminous hydrogen, reduce the hydrogen-consuming volume of desulfurization of hydrocarbon oil process, reduce the operating cost of sweetening process.
In the present invention, reacted catalyst can be reused after regeneration.Described regeneration is carried out under oxygen atmosphere, and the condition of regeneration comprises: the pressure of regeneration is normal pressure, and the temperature of regeneration is 400-700 DEG C, is preferably 500-600 DEG C.
In the present invention, the catalyst after regeneration is before re-starting desulfurization of hydrocarbon oil, and also need to reduce under hydrogen atmosphere, the reducing condition of the catalyst after regeneration comprises: temperature is 350-500 DEG C, is preferably 400-450 DEG C; Pressure is 0.2-2MPa, is preferably 0.2-1.5MPa.
In the present invention, described hydrocarbon ils comprises cracking gasoline and diesel fuel, and wherein " cracking gasoline " means hydrocarbon or its any cut that boiling range is 40 DEG C to 210 DEG C, is the product from making larger crack hydrocarbon molecules become more micromolecular heat or catalytic process.The thermal cracking process be suitable for includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof.The example of the catalytic cracking process be suitable for includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof.Therefore, the catalytically cracked gasoline be suitable for includes but not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and heavy oil cracked gasoline and combination thereof.In some cases, be in the methods of the invention used as hydrocarbon-containifluids fluids time can by described cracking gasoline fractionation and/or hydrotreatment before desulfurization.Described " diesel fuel " means boiling range is the hydrocarbon mixture of 170 DEG C to 450 DEG C or the liquid of its any fractional composition.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil and hydroprocessed diesel etc. and combination thereof.
Term used herein " sulphur " represents any type of element sulphur if hydrocarbon-containifluids fluids is as the organosulfur compound existed normal in cracking gasoline or diesel fuel.The sulphur existed in hydrocarbon-containifluids fluids of the present invention includes but not limited to carbonyl sulfide (COS), carbon disulfide (CS2), mercaptan or other thiophenes etc. and combination thereof, especially thiophene, benzothiophene, alkylthrophene, alkyl benzothiophenes and methyldibenzothiophene is comprised, and the thiophenes that in diesel fuel, the normal molecular weight existed is larger.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples, the composition of desulfurization of hydrocarbon oil catalyst calculates according to feeding intake; The anhydrous chemical expression of the ZSM-5 molecular sieve of P and Fe modification is by using x-ray fluorescence method (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the Yang Cui volume such as surely, Science Press, nineteen ninety publishes) measure the content of each metal oxide in the ZSM-5 molecular sieve of P and Fe modification to determine.
The B acid of catalyst and concrete assay method infrared acidity assay method (90-92 page) disclosed in " catalyst analysis " (publishing house of Northeastern University published in July, 2000) of L acid measure, specific as follows: the preparation of (I) sample: to get levigate rear sample (granularity is less than 200 orders) 10mg, being pressed into diameter is that 13mm thin slice is placed in cell for infrared absorption, that gets that 100mg sample (sheet) loads quartz spring lower end again hangs in cup, system pump down to 1 × 10 -2pa, is heated to 500 DEG C of constant temperature 1 hour, purification sample, removes the adsorbate and water that cover on specimen surface; (II) drop to room temperature in the above-mentioned condition of finding time, Adsorption of Pyridine 5min, be then warmed up to 160 DEG C, balance 1h, the pyridine of desorption physical absorption, records the infrared spectrogram of gained under above-mentioned condition, the bands of a spectrum 1545cm that wherein B acid is corresponding -1, the bands of a spectrum 1455cm that L acid is corresponding -1, thus, the acid molar ratio of B acid/L acid when obtaining 160 DEG C.
Density of hydrogen is obtained by heat-conducted hydrogen analyzer (Beijing North divides Rayleigh analytical instrument (group) company QRD-1102A) analysis.
Below will be described the present invention by embodiment.
Embodiment 1
The present embodiment is for illustration of the method preparing desulfurization of hydrocarbon oil catalyst of the present invention.
(1) under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 100g 2: Al 2o 3mol ratio be 20:1) with 10 % by weight of 70g ammonium phosphate solution stir at 85 DEG C and dry at 120 DEG C, and roasting 2h obtains P-ZSM-5 molecular sieve at 500 DEG C;
The iron nitrate solution of the P-ZSM-5 molecular sieve of 80g and 5 % by weight of 20g is stirred and filters at 85 DEG C, repeat this to stir and filter 23, dry at 120 DEG C, and roasting 2h obtains P-Fe-ZSM-5 molecular sieve at 500 DEG C, its anhydrous chemical expression is counted with the weight of oxide: 0.04Na 2o3.71Al 2o 32.81P 2o 51.56Fe 2o 374.15SiO 2; P content is with P 2o 5count 3.42 % by weight, Fe content with Fe 2o 3count 1.90 % by weight, P 2o 5/ Fe 2o 3mass ratio be 1.8:1;
(2) carrier is prepared.The deionized water of the Zinc oxide powder (Headhorse company, purity 99.7 % by weight) of 4.13kg and 6.57kg is mixed, stirs and obtain zinc oxide slurries after 30 minutes;
Get boehmite 1.14kg (catalyst Nanjing branch company, containing butt 0.86kg) and expanded perlite (the catalyst Nanjing branch company of 0.95kg, containing butt 0.8kg) be uniformly mixed, then adding deionized water 4.6kg mixes as after slurries, add the hydrochloric acid (Beijing Chemical Plant of 30 % by weight of 360ml again, chemical pure) stir make slurries pH=2.1, be warming up to 80 DEG C of aging 2h after acidifying 1h, then add and stir 1h after P-Fe-ZSM-5 molecular sieve 2.4kg that zinc oxide slurries and (1) obtains mixes and obtain carrier pulp;
Described carrier pulp is adopted NiroBowenNozzleTower tMthe spray dryer of model carries out spraying dry, and spraying dry pressure is 8.5 to 9.5MPa, and inlet temperature less than 500 DEG C, outlet temperature is about 150 DEG C.The microballoon obtained by spraying dry is dry 1h at 180 DEG C first, and then at 635 DEG C, roasting 1h obtains carrier;
(3) controlling catalyst precursor.By Nickelous nitrate hexahydrate (Beijing chemical reagents corporation of the carrier 3.51kg of 3.2kg, purity > 98.5 % by weight) and 0.6kg deionized water solution dipping, the macerate obtained is after 180 DEG C of dry 4h, at air atmosphere 635 DEG C of roasting 1h, obtained catalyst precarsor;
(4) reduce.By catalyst precarsor reductase 12 h at 425 DEG C in hydrogen atmosphere, obtain desulfurization of hydrocarbon oil catalyst A 1.
The chemical composition of A1 is: zinc oxide content is 41.3 % by weight, and expanded perlite content is 8.0 % by weight, and alumina content is 8.6 % by weight, and nickel content is 18.1 % by weight, P-Fe-ZSM-5 molecular sieve content is 24.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying A1 is 0.6:1.
Embodiment 2
The present embodiment is for illustration of the method preparing desulfurization of hydrocarbon oil catalyst of the present invention.
(1) under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 100g 2: Al 2o 3mol ratio be 40:1) with 10 % by weight of 70g ammonium phosphate solution stir at 85 DEG C and dry at 120 DEG C, and roasting 2h obtains P-ZSM-5 molecular sieve at 500 DEG C;
The iron nitrate solution of the P-ZSM-5 molecular sieve of 80g and 5 % by weight of 20g is stirred and filters at 85 DEG C, repeat this to stir and filter 23, dry at 120 DEG C, and roasting 2h obtains P-Fe-ZSM-5 molecular sieve at 500 DEG C, its anhydrous chemical expression is counted with the weight of oxide: A2:0.04Na 2o2.0Al 2o 33.28P 2o 51.10Fe 2o 377.8SiO 2; P content is with P 2o 5count 3.89 % by weight, Fe content with Fe 2o 3count 1.31 % by weight, P 2o 5/ Fe 2o 3mass ratio be 3:1;
(2) carrier, catalyst precarsor and reduction is prepared.By boehmite 1.56kg (catalyst Nanjing branch company, containing butt 1.17kg) and diatomite (the catalyst Nanjing branch company of 1.63kg, containing butt 1.60kg) be uniformly mixed, then adding deionized water 8.2kg mixes as after slurries, the hydrochloric acid adding 30 % by weight of 260ml again makes slurries pH=1.9, be warming up to 80 DEG C of aging 2h after stirring acidifying 1h, after temperature reduces, add P-Fe-ZSM-5 molecular sieve that the Zinc oxide powder of 4.92kg and (1) obtains again and stir 1h and obtain carrier pulp.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulfurization of hydrocarbon oil catalyst A 2 after reduction.
The chemical composition of A2 is: zinc oxide content is 49.2 % by weight, and diatomite content is 16.0 % by weight, and alumina content is 11.7 % by weight, and nickel content is 15.1 % by weight, P-Fe-ZSM-5 molecular sieve content is 8.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying A2 is 0.35:1.
Embodiment 3
The present embodiment is for illustration of the method preparing desulfurization of hydrocarbon oil catalyst of the present invention.
(1) under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 100g 2: Al 2o 3mol ratio be 30:1) with 10 % by weight of 70g ammonium phosphate solution stir at 85 DEG C and dry at 120 DEG C, and roasting 2h obtains P-ZSM-5 molecular sieve at 500 DEG C;
The iron nitrate solution of the P-ZSM-5 molecular sieve of 80g and 5 % by weight of 20g is stirred and filters at 85 DEG C, repeat this to stir and filter 23, dry at 120 DEG C, and roasting 2h obtains P-Fe-ZSM-5 molecular sieve at 500 DEG C, its anhydrous chemical expression is counted with the weight of oxide: 0.04Na 2o2.51Al 2o 33.08P 2o 51.28Fe 2o 375.3SiO 2; P content is with P 2o 5count 3.75 % by weight, Fe content with Fe 2o 3count 1.56 % by weight, P 2o 5/ Fe 2o 3mass ratio be 2.4:1;
(2) carrier is prepared.The deionized water of the diatomite (catalyst Nanjing branch company, containing butt 1.4kg) of the Zinc oxide powder of 4.23kg, 1.43kg and 8.8kg is mixed, stirs and obtain zinc oxide and diatomaceous mixed serum after 30 minutes;
Get boehmite 1.54kg (Shandong Aluminum Plant, containing butt 1.16kg) and deionized water 4.6kg to mix as after slurries, the hydrochloric acid adding 30 % by weight of 300ml stirs and makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after acidifying 1h; Stir 1h after adding the P-Fe-ZSM-5 molecular sieve mixing that zinc oxide and diatomaceous mixed serum and (1) obtains again and obtain carrier pulp.
The spray drying forming that method with reference to embodiment 1 carries out carrier pulp obtains carrier.
(3) catalyst precarsor and reduction.With reference to method Kaolinite Preparation of Catalyst precursor and the catalyst of embodiment 1, unlike, substitute Nickelous nitrate hexahydrate impregnated carrier with the solution of nickel nitrate and cobalt nitrate, introduce active component nickel and cobalt, after reduction, obtain desulfurization of hydrocarbon oil catalyst A 3.
The chemical composition of A3 is: zinc oxide content is 42.3 % by weight, and diatomite content is 14.0 % by weight, and alumina content is 11.5 % by weight, and nickel content is 8.1 % by weight, and cobalt content is 8.1 % by weight, P-Fe-ZSM-5 molecular sieve content is 16.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying A3 is 0.5:1.
Embodiment 4
The present embodiment is for illustration of the method preparing desulfurization of hydrocarbon oil catalyst of the present invention.
(1) under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 100g 2: Al 2o 3mol ratio be 15:1) with 10 % by weight of 70g ammonium phosphate solution stir at 85 DEG C and dry at 120 DEG C, and roasting 2h obtains P-ZSM-5 molecular sieve at 500 DEG C;
The iron nitrate solution of the P-ZSM-5 molecular sieve of 80g and 5 % by weight of 20g is stirred and filters at 85 DEG C, repeat this to stir and filter 23, dry at 120 DEG C, and roasting 2h obtains P-Fe-ZSM-5 molecular sieve at 500 DEG C, its anhydrous chemical expression is counted with the weight of oxide: 0.04Na 2o2.51Al 2o 33.08P 2o 51.28Fe 2o 375.3SiO 2; P content is with P 2o 5count 3.75 % by weight, Fe content with Fe 2o 3count 1.56 % by weight, P 2o 5/ Fe 2o 3mass ratio be 2.4:1;
(2) carrier, catalyst precarsor and reduction is prepared.The deionized water of the Zinc oxide powder of 4.73kg, 2.57kg kaolin (Kaolin of Suzhou factory, containing butt 1.90kg) and 8.8kg is mixed, stirs and obtain zinc oxide and kaolinic mixed serum after 30 minutes;
Get boehmite 1.80kg (Shandong Aluminum Plant, containing butt 1.36kg) and deionized water 4.6kg mix as after slurries, the hydrochloric acid adding 30 % by weight of 300ml stirs and makes slurries pH=2.5, be warming up to 80 DEG C of aging 2h after acidifying 1h, then stir 1h after adding P-Fe-ZSM-5 molecular sieve mixing that zinc oxide and kaolinic mixed serum and (1) obtains and obtain carrier pulp.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulfurization of hydrocarbon oil catalyst A 4 after reduction.
The chemical composition of A4 is: zinc oxide content is 48.3 % by weight, and kaolin content is 19.0 % by weight, and alumina content is 13.5 % by weight, and nickel content is 15.2 % by weight, P-Fe-ZSM-5 molecular sieve content is 4.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying A4 is 0.3:1.
Comparative example 1
The deionized water of the Zinc oxide powder of 4.13kg and 6.57kg is mixed, stirs and obtain zinc oxide slurries after 30 minutes;
Get boehmite 2.48kg (catalyst Nanjing branch company, containing butt 1.86kg) and expanded perlite (the catalyst Nanjing branch company of 2.25kg, containing butt 2.20kg) be uniformly mixed, then add deionized water 4.6kg to mix, be warming up to 80 DEG C of aging 2h after adding the hydrochloric acid stirring acidifying 1h of 30 % by weight of 360ml again, then after adding the mixing of zinc oxide slurries, stirring 1h obtains carrier pulp.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulfurization of hydrocarbon oil catalyst B 1 after reduction.
The chemical composition of B1 is: zinc oxide content is 41.3 % by weight, and expanded perlite content is 22.0 % by weight, and alumina content is 18.6 % by weight, and nickel content is 18.1 % by weight.
The acid molar ratio of the B acid/L acid of infrared acidity assaying B1 is 0.
Comparative example 2
Get boehmite 1.14kg (catalyst Nanjing branch company, containing butt 0.86kg) and expanded perlite (the catalyst Nanjing branch company of 0.95kg, containing butt 0.80kg) be uniformly mixed, then add deionized water 4.6kg to mix, the hydrochloric acid adding 30 % by weight of 360ml again stirs the pH=2.1 making slurries, is warming up to 80 DEG C of aging 2h after acidifying 1h.The Zinc oxide powder of 4.13kg and the ZSM-5 molecular sieve (SiO of 2.4kg is added again after temperature reduces 2: Al 2o 3mol ratio be 20:1) and stir 1h and obtain carrier pulp.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulfurization of hydrocarbon oil catalyst B 2 after reduction.
The chemical composition of B2 is: zinc oxide content is 41.3 % by weight, and expanded perlite content is 8.0 % by weight, and alumina content is 8.6 % by weight, and nickel content is 18.1 % by weight, and ZSM-5 molecular sieve content is 24.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying B2 is 0.1:1.
Comparative example 3
Under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 100g 2: Al 2o 3mol ratio be 30:1) with 10 % by weight of 70g ammonium phosphate solution stir at 85 DEG C and dry at 120 DEG C, and roasting 2h obtains P-ZSM-5 molecular sieve at 500 DEG C; Its anhydrous chemical expression is counted with the weight of oxide: 0.04Na 2o2.51Al 2o 34.38P 2o 575.3SiO 2; P content is with P 2o 5count 5.20 % by weight;
The deionized water of the diatomite (catalyst Nanjing branch company, containing butt 1.4kg) of the Zinc oxide powder of 4.23kg, 1.43kg and 8.8kg is mixed, stirs and obtain zinc oxide and diatomaceous mixed serum after 30 minutes;
Get boehmite 1.54kg (Shandong Aluminum Plant, containing butt 1.15kg) and deionized water 4.6kg to mix, then add 300ml 30 % by weight hydrochloric acid stir make slurries pH=2.5, be warming up to 80 DEG C of aging 2h after acidifying 1h.Add zinc oxide and diatomaceous mixed serum again, and after the mixing of P-ZSM-5 molecular sieve, stirring 1h obtains carrier pulp.
Method with reference to embodiment 3 is carried out the spray drying forming of carrier pulp and is obtained desulfurization of hydrocarbon oil catalyst B 3 after introducing active component nickel reduction.
The chemical composition of B3 is: zinc oxide content is 42.3 % by weight, and diatomite content is 14.0 % by weight, and alumina content is 11.5 % by weight, and nickel content is 8.1 % by weight, and cobalt content is 8.1 % by weight, P-ZSM-5 molecular sieve content is 16.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying B3 is 0.15:1.
Comparative example 4
Under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 80g 2: Al 2o 3mol ratio be 40:1) with 10 % by weight of 20g iron nitrate solution stir at 85 DEG C and filter, repeat this to stir and filter 23, dry at 120 DEG C, and roasting 2h obtains Fe-ZSM-5 molecular sieve at 500 DEG C, its anhydrous chemical expression is counted with the weight of oxide: 0.04Na 2o2.0Al 2o 34.38Fe 2o 377.8SiO 2; Fe content is with Fe 2o 3count 5.20 % by weight;
Get boehmite 1.56kg (Shandong Aluminum Plant, containing butt 1.17kg) and diatomite (the catalyst Nanjing branch company of 1.63kg, containing butt 1.60kg) be uniformly mixed, then adding deionized water 8.2kg mixes as after slurries, the hydrochloric acid adding 30 % by weight of 260ml again makes slurries pH=1.9, be warming up to 80 DEG C of aging 2h after stirring acidifying 1h, after temperature reduces, add P-Fe-ZSM-5 molecular sieve that the Zinc oxide powder of 4.92kg and (1) obtains again and stir 1h and obtain carrier pulp.
Method with reference to embodiment 2 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulfurization of hydrocarbon oil catalyst B 4 after reduction.
The chemical composition of B4 is: zinc oxide content is 49.2 % by weight, and kaolin content is 16.0 % by weight, and alumina content is 11.7 % by weight, and nickel content is 15.1 % by weight, Fe-ZSM-5 molecular sieve content is 8.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying B4 is 0.7:1.
Comparative example 5
Under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 100g 2: Al 2o 3mol ratio be 20:1) with 10 % by weight of 70g lanthanum nitrate hexahydrate stir at 85 DEG C and dry at 120 DEG C, and roasting 2h obtains La-ZSM-5 molecular sieve at 500 DEG C, and wherein, La is with La 2o 3the content of meter is 5.20 % by weight;
The deionized water of the Zinc oxide powder of 4.13kg and 6.57kg is mixed, stirs and obtain zinc oxide slurries after 30 minutes;
Get boehmite 1.14kg (catalyst Nanjing branch company, containing butt 0.86kg) and expanded perlite (the catalyst Nanjing branch company of 0.95kg, containing butt 0.8kg) be uniformly mixed, then add deionized water 4.6kg to mix, the hydrochloric acid adding 30 % by weight of 360ml again stirs and makes slurries pH=2.1, be warming up to 80 DEG C of aging 2h after acidifying 1h, then after adding zinc oxide slurries and La-ZSM-5 molecular sieve 2.4kg mixing, stirring 1h obtains carrier pulp.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulfurization of hydrocarbon oil catalyst B 5 after reduction.
The chemical composition of B5 is: zinc oxide content is 41.3 % by weight, and expanded perlite content is 8.0 % by weight, and alumina content is 8.6 % by weight, and nickel content is 18.1 % by weight, La-ZSM-5 molecular sieve content is 24.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying B5 is 0.1:1.
Comparative example 6
According to the method for embodiment 1, unlike, step (1) is:
Under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 100g 2: Al 2o 3mol ratio be 20:1) with 5 % by weight of 70g ammonium phosphate solution stir at 85 DEG C and dry at 120 DEG C, and roasting 2h obtains P-ZSM-5 molecular sieve at 500 DEG C;
The iron nitrate solution of the P-ZSM-5 molecular sieve of 80g and 5 % by weight of 20g is stirred and filters at 85 DEG C, repeat this stir and filter 5 times, dry at 120 DEG C, and roasting 2h obtains P-Fe-ZSM-5 molecular sieve at 500 DEG C, its anhydrous chemical expression is: 0.04Na 2o3.71Al 2o 31.46P 2o 52.91Fe 2o 374.15SiO 2; P content is with P 2o 5count 1.46 % by weight, Fe content with Fe 2o 3count 2.91 % by weight, P 2o 5/ Fe 2o 3mass ratio be 0.5:1.
Obtain desulfurization of hydrocarbon oil catalyst B 6.
The chemical composition of B6 is: zinc oxide content is 41.3 % by weight, and expanded perlite content is 8.0 % by weight, and alumina content is 8.6 % by weight, and nickel content is 18.1 % by weight, P-Fe-ZSM-5 molecular sieve content is 24.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying B6 is 0.65:1.
Comparative example 7
According to the method for embodiment 1, unlike, step (1) is:
Under the condition of exchange reaction, by ZSM-5 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, the SiO of 100g 2: Al 2o 3mol ratio be 20:1) with 12 % by weight of 70g ammonium phosphate solution stir at 85 DEG C and dry at 120 DEG C, and roasting 2h obtains P-ZSM-5 molecular sieve at 500 DEG C;
The iron nitrate solution of the P-ZSM-5 molecular sieve of 80g and 5 % by weight of 15g is stirred and filters at 85 DEG C, repeat this to stir and filter 23, dry at 120 DEG C, and roasting 2h obtains P-Fe-ZSM-5 molecular sieve at 500 DEG C, its anhydrous chemical expression is: 0.04Na 2o3.71Al 2o 33.58P 2o 50.80Fe 2o 374.15SiO 2; P content is with P 2o 5count 4.35 % by weight, Fe content with Fe 2o 3count 0.97 % by weight, P 2o 5/ Fe 2o 3mass ratio be 4.5:1.
Obtain desulfurization of hydrocarbon oil catalyst B 7.
The chemical composition of B7 is: zinc oxide content is 41.3 % by weight, and expanded perlite content is 8.0 % by weight, and alumina content is 8.6 % by weight, and nickel content is 18.1 % by weight, P-Fe-ZSM-5 molecular sieve content is 24.0 % by weight;
The acid molar ratio of the B acid/L acid of infrared acidity assaying B7 is 2.0:1.
Comparative example 8
According to the method for embodiment 1, unlike, in step (3), substitute the Nickelous nitrate hexahydrate of 3.51kg with the Nickelous nitrate hexahydrate of 6.32kg.
Obtain desulfurization of hydrocarbon oil catalyst B 8,
The chemical composition of B8 is: zinc oxide content is 41.3 % by weight, and expanded perlite content is 8.0 % by weight, and alumina content is 8.6 % by weight, and nickel content is 32.6 % by weight, P-Fe-ZSM-5 molecular sieve content is 9.3 % by weight; Wherein the mass ratio of Ni/P-Fe-ZSM-5 molecular sieve is 3.5:1.
The acid molar ratio of the B acid/L acid of infrared acidity assaying B8 is 0.6:1.
Embodiment 5
(1) abrasion strength resistance evaluation.Abrasion strength resistance test is carried out to desulfurization of hydrocarbon oil catalyst A 1-A4 and B1-B8.Adopt straight tube wearing and tearing method, method, with reference to RIPP29-90 in " Petrochemical Engineering Analysis method (RIPP) experimental technique ", the results are shown in Table 1.Test the numerical value obtained less, show that abrasion strength resistance is higher.What in table 1, abrasion index was corresponding is fine powder generates when wearing and tearing under certain condition percentage.
(2) desulfurization performance evaluation.Adopting the micro-anti-experimental provision of fixed bed to carry out HDS evaluation experiment to desulfurization of hydrocarbon oil catalyst A 1-A4 and B1-B8, is 30mm, long in the fixed bed reactors of 1m by the desulfurization of hydrocarbon oil Catalyst packing of 16g at internal diameter.Raw material hydrocarbon ils is simulation hydrocarbon ils, and composition is in table 2 (containing 1000ppm thiophene), and composition analysis adopts the ThermoQuestTrace2000 gas chromatograph-mass spectrometer (GC-MS) (FID detection) of Finnigan company of the U.S. to carry out.Reaction pressure is 2MPa, and adding hydrogen flowing quantity is 6.3L/h, and raw material hydrocarbon ils flow is 100g/h, and reaction temperature is 410 DEG C, and the weight space velocity of simulation hydrocarbon ils is 4h -1, carry out the desulphurization reaction of hydrocarbon oil containing surphur.
Weigh desulphurizing activated with sulfur content in product gasoline.In product gasoline, sulfur content is by off-line chromatogram analysis method, adopts the GC6890-SCD instrument of An Jielun company to measure.In order to accurate characterization goes out the activity of desulfurization of hydrocarbon oil catalyst in industrial actual motion, HDS evaluation tested after catalyst carry out under the air atmosphere of 550 DEG C regeneration process.Desulfurization of hydrocarbon oil catalyst is carried out HDS evaluation experiment, and after regenerating 6 circulations, its activity settles out substantially, represents the activity of catalyst with the sulfur content in the product gasoline after catalyst the 6th stable circulation, and after stable, in product gasoline, sulfur content is as shown in table 1.Composition in product gasoline after analysis of catalyst the 6th stable circulation, analytical method, with the analytical method of raw material hydrocarbon ils, the results are shown in Table 2.
Employing GB/T503-1995 and GB/T5487-1995 simulates motor octane number (MON) and the research octane number (RON) (RON) of hydrocarbon ils after measuring and reacting front and the 6th stable circulation respectively, the results are shown in Table 1.
The emission gases flow velocity facing H-H reaction is carried out after measuring catalyst the 6th circulation, and analyze wherein density of hydrogen with the heat-conducted hydrogen analyzer of QRD-1102A, calculate and discharge amounts of hydrogen (Q2), add amounts of hydrogen (Q1) and obtain amounts of hydrogen difference, the results are shown in Table 1.
Table 1
Note:
1, the sulfur content of simulation hydrocarbon ils is 1000ppm, RON is 74.
2, △ MON represents the value added of product MON;
3, △ RON represents the value added of product RON;
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index;
5, amounts of hydrogen difference is the simulation hydrocarbon ils relative to 1000g, adds the difference of amounts of hydrogen (Q1) and discharge amounts of hydrogen (Q2); "+" represents that hydrogen produces, and "-" represents hydrogen consumption.
Table 2
Note: n-hexane, hexene, hexahydrotoluene, dimethyl pentane, toluene (AcrosOrganics, 99.9%) are detailed hydrocarbon model compound.
Desulfurization of hydrocarbon oil catalyst provided by the invention contains specific composition, in the ZSM-5 molecular sieve of P and Fe modification wherein, have extra fine quality ratio between P and Fe, and between this molecular sieve and active component, quality bit is fixed, this catalyst has the acid molar ratio of the B acid/L acid at specific 160 DEG C in addition.Using this catalyst for simulating the desulfurization of hydrocarbon ils, effectively can remove the sulfide in hydrocarbon ils, promote the dehydrogenation reaction of hydrocarbon ils in sweetening process simultaneously, volume increase hydrogen.As can be seen from the result data of table 2, in the product gasoline that embodiment 1-4 uses desulfurization of hydrocarbon oil catalyst provided by the invention to obtain, cycloalkane and normal paraffin content reduce, and aromatisation and cyclization product such as the content of Benzene and Toluene increase; And the catalyst in comparative example 1-8 does not have above-mentioned effect, also can there is olefin saturated simultaneously, consume hydrogen, and product octane number decrease.Illustrate that desulfurization of hydrocarbon oil catalyst provided by the invention is while carrying out desulfurization of hydrocarbon oil, also enhances the dehydrogenation reaction of hydrocarbon ils.Thus can find out at the result data of table 1, the amounts of hydrogen in H-H reaction result of facing of embodiment 1-4 is increase, and in comparative example 1-8, amounts of hydrogen reduces for consuming.Can finding out, when adopting desulfurization of hydrocarbon oil catalyst provided by the invention, greatly can reduce the hydrogen consumption of catalytic hydrogenation adsorption desulfurize technology, save the cost of desulfurization of hydrocarbon oil operation.And this desulfurization of hydrocarbon oil catalyst has better desulphurizing activated and activity stability.Desulphurization catalyst has better abrasion strength resistance, thus makes desulphurization catalyst have longer service life.
As can be seen from table 1 and 2 result, in comparative example 1-5, there is no the ZSM-5 of modification containing molecular sieve or use in catalyst or only with the ZSM-5 of P or Fe modification or use rare earth modified ZSM-5 all can not bring the effect of volume increase hydrogen.Comparative example 1 can find out with the result of comparative example 6 and 7, in the ZSM-5 molecular sieve of P and Fe modification, between P and Fe content be extra fine quality than time, catalyst can have the acid molar ratio of suitable B acid/L acid, can volume increase hydrogen while desulfurized effect better.And the result of comparative example 8 can be found out, time between the ZSM-5 molecular sieve of active component and P and Fe modification in specific weight ratio, catalyst can volume increase hydrogen while desulfurized effect better.
According to the data result of embodiment, reach 3,540 ten thousand tons/year (referring to the processing capacity of hydrocarbon oil containing surphur) with the total working ability of 2014 China S-Zorb in the end of the year, volume increase hydrogen 1.77-14.16 ten thousand tons/year while using the present invention to realize deep desulfuration can be calculated.To significantly reduce the running cost of S-Zorb process technology.

Claims (17)

1. a desulfurization of hydrocarbon oil catalyst, this catalyst comprises carrier and active component, and described carrier comprises the ZSM-5 molecular sieve of aluminium oxide, silica source, zinc oxide and P and Fe modification, and described active component comprises nickel and/or cobalt; Wherein, in the ZSM-5 molecular sieve of described P and Fe modification, P 2o 5/ Fe 2o 3mass ratio be 1-4:1, the mass ratio of the ZSM-5 molecular sieve of described active component and described P and Fe modification is 0.5-4:1, and the acid molar ratio of the B acid/L acid of described catalyst is 0.3-0.8:1.
2. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein, with the gross weight of this catalyst for benchmark, the ZSM-5 molecular sieve content that zinc oxide content is 10-80 % by weight, alumina content is 3-35 % by weight, described silica source content is 5-40 % by weight, described active component content is 5-30 % by weight and described P and Fe modification is 4-35 % by weight; With the gross weight of the ZSM-5 molecular sieve of described P and Fe modification for benchmark, with P in the ZSM-5 molecular sieve of described P and Fe modification 2o 5the P content of meter is 1-8 % by weight, with Fe 2o 3the Fe content of meter is 0.3-5 % by weight.
3. desulfurization of hydrocarbon oil catalyst according to claim 1 and 2, wherein, the SiO of described ZSM-5 molecular sieve 2: Al 2o 3mol ratio be 10-70:1.
4. desulfurization of hydrocarbon oil catalyst according to claim 1 and 2, wherein, described silica source is the natural crystal that silica or silica content are greater than 45 % by weight.
5. the preparation method of the desulfurization of hydrocarbon oil catalyst in claim 1-4 described in any one, the method comprises:
(1) under the condition of exchange reaction, ZSM-5 molecular sieve and the solution of phosphorus-containing compound, the solution of iron containing compounds are carried out exchange reaction, obtains the ZSM-5 molecular sieve of P and Fe modification;
(2) ZSM-5 molecular sieve of P and Fe modification alumina binder, silica source, zinc oxide, step (1) obtained, water and acidic liquid are mixed to get carrier pulp, described carrier pulp is carried out shaping, first dry and the first roasting, obtain carrier;
(3) introduce the compound containing active component on the carrier and carry out second dry and the second roasting, obtaining catalyst precarsor;
(4) described catalyst precarsor is reduced in a hydrogen atmosphere, obtain desulfurization of hydrocarbon oil catalyst.
6. preparation method according to claim 5, wherein, the process of step (1) described exchange reaction comprises:
(A) under the condition of the first exchange reaction, the solution of ZSM-5 molecular sieve and phosphorus-containing compound is reacted, obtains the ZSM-5 molecular sieve of P modification;
(B) under the condition of the second exchange reaction, the ZSM-5 molecular sieve of described P modification and the solution of iron containing compounds are carried out the reaction of more than 2 times, obtain the ZSM-5 molecular sieve of P and Fe modification.
7. the preparation method according to claim 5 or 6, wherein, described alumina binder is selected from least one in SB powder, hydrated alumina, Alumina gel, boehmite, false boehmite, hibbsite and amorphous hydroted alumina.
8. preparation method according to claim 5, wherein, the described compound containing active component is selected from least one in the acetate of active component, carbonate, nitrate, sulfate, rhodanate and oxide.
9. preparation method according to claim 5, wherein, method carrier introduced containing the compound of active component is dipping or precipitation.
10. preparation method according to claim 5, wherein, the temperature of described first drying is room temperature-400 DEG C, and the time of described first drying is 0.5-8h; The temperature of described first roasting is 400-700 DEG C, and the time of described first roasting is more than 0.5h.
11. preparation methods according to claim 5, wherein, the temperature of described second drying is 50-300 DEG C, and the time of described second drying is 0.5-8h; The temperature of described second roasting is 300-800 DEG C, and the time of described second roasting is 0.5-4h.
12. preparation methods according to claim 5, wherein, the temperature of described reduction is 300-600 DEG C, and the time of described reduction is 0.5-6h, and in described hydrogen atmosphere, hydrogen content is 10-60 volume %.
Desulfurization of hydrocarbon oil catalyst prepared by the method in 13. claim 5-12 described in any one.
The method of 14. 1 kinds of desulfurization of hydrocarbon oil, the method comprises: under the condition of facing H-H reaction, by the desulfurization of hydrocarbon oil catalyst exposure in hydrocarbon oil containing surphur and claim 1-4 and 13 described in any one.
15. methods according to claim 14, wherein, described in face H-H reaction discharge amounts of hydrogen Q2 be greater than described in face H-H reaction add amounts of hydrogen Q1.
16. methods according to claim 15, wherein, relative to the hydrocarbon oil containing surphur of 1000g, meet between Q2 and Q1: Q2-Q1 >=0.5g.
17. according to the method in claim 14-16 described in any one, wherein, described in face H-H reaction temperature be 350-500 DEG C, described in face H-H reaction pressure be 0.5-4MPa; The described hydrogen partial pressure facing H-H reaction is 0.12-2MPa.
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CN111013642A (en) * 2018-10-10 2020-04-17 中国石油化工股份有限公司 Anti-carbon deposition catalyst for preparing propylene by propane dehydrogenation and preparation method thereof
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