CN102343251A - Spraytex desulfurization adsorbent, preparation method and application thereof - Google Patents
Spraytex desulfurization adsorbent, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a spraytex desulfurization adsorbent, a preparation method and application thereof. The adsorbent provided by the invention, based on a total weight of the adsorbent, comprises at least the following components: 1) SAPO molecular sieve with a content of 1-20wt%; 2) zirconium dioxide with a content of 3-35wt%; 3) pillared clay with a content of 5-40wt%; 4) zinc oxide with a content of 10-80wt%; 5) at least a metal promoter selected from cobalt, nickel, iron and manganese, with a content of 5-30wt%. The adsorbent of the invention has high desulfurization activity, high wear resistance and obvious advantage in increasing gasoline octane number, and is suitable for a desulphurization process of catalytic cracking gasoline or diesel engine fuel.
Description
Technical field
The present invention relates to adsorbent that from hydrocarbon ils, removes sulphur and its production and application.
Background technology
CN 1355727A provides a kind of novel absorbing composition that contains zinc oxide, silica, aluminium oxide and nickel or cobalt, and this preparation of adsorbent method is provided.This method is at first prepared the carrier that contains zinc oxide, silica, aluminium oxide, introduces nickel through dipping then.This adsorbent can be used for from cracking gasoline or diesel fuel, removing sulphur.
Adopt promoter metals such as cobalt and nickel dipping to comprise the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide among the CN 1208124C, reduction accelerator under suitable temperature prepares the adsorbent that is used for removing cracking gasoline sulfide then.
When above-mentioned adsorbent removes sulfur in gasoline under hydro condition, inevitably cause octane number to reduce owing to alkene is saturated.
CN 101433821A mentions a kind of adsorbent that reduces sulfur content in hydrocarbon oils, comprises rare earth faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; Above-mentioned rare earth faujasite and carrier mixture are configured as the porous heat-resistant solid particle in advance, on this solid particle, introduce metal active constituent again, prepare said adsorbent.
CN 101434854A mentions a kind of adsorbent that reduces sulfur content of light hydrocarbon oil, comprises phosphorus modified RE faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; Above-mentioned rare earth faujasite is configured as the porous heat-resistant solid particle with carrier mixture in advance after the phosphorus modification, on this solid particle, introduces metal active constituent again, prepare said adsorbent.
Though above-mentioned two methods add and select the type molecular sieve and help isomerization and increase octane number, owing to lack the promoter metals and the sulphur storage medium of appropriate level, it is enough desulphurizing activated to cause this adsorbent to lack.
Summary of the invention
The present invention provides a kind of adsorbent that can be used for from hydrocarbon ils, removing sulphur, and this preparation of adsorbent methods and applications method is provided.
Adsorbent provided by the invention is a benchmark with the adsorbent gross weight, comprises following composition at least:
1) SAPO molecular sieve, content are 1-20wt%
2) zirconium dioxide, content are 3-35wt%;
3) laminated clay column, content are 5-40wt%;
4) zinc oxide, content are 10-80wt%;
5) at least a metallic promoter agent that is selected from cobalt, nickel, iron and manganese, content is 5-30wt%.
Under the preferable case; The content of SAPO molecular sieve is 2-15wt%, and the content of zirconium dioxide is 5-25wt%, and the content of laminated clay column is 10-30wt%; The content of zinc oxide is 25-70wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 8-25wt%.
More preferably under the situation; The content of SAPO molecular sieve is 2-10wt%, and the content of zirconium dioxide is 8-15wt%, and the content of laminated clay column is 12-25wt%; The content of zinc oxide is 40-58wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 12-20wt%.
The SAPO molecular sieve is nearly body silicoaluminophosphate, silicon is introduced in the aluminum phosphate skeleton obtaining, and its skeleton is by PO
4 +, AlO
4 -And SiO
2Tetrahedron is formed.This molecular sieve analog comprises 13 kinds of three-dimensional microporous framework structures, and its hole size does
Pore volume is 0.18-0.48cm
3/ g, the hole size of SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieve is respectively
(12 yuan of rings),
(10 Yuans rings),
(10 Yuans rings),
(8 Yuans rings) and
(6 Yuans rings); Pore volume is respectively 0.31,0.18,0.42,0.42 and 0.40cm
3/ g.The preferred SAPO-11 of the application, SAPO-31 and SAPO-34.
Said laminated clay column is the interbed mineral crystal, is alternately to be rearranged by two kinds of individual layer mineral clay component rules, and its basal spacing is not less than 1.7nm, at 3.4 ° a stronger peak is arranged in its XRD figure spectrum.The instance of said laminated clay column includes but not limited to rectorite, Yun Mengshi, bentonite, imvite and smectite etc., preferred rectorite.
The invention provides the preparation method of hydrocarbon oil desulphurization adsorbing agent, comprising:
(1) makes the hydrolysis in acid solution of zirconium dioxide precursor, form colloidal sol;
(2) colloidal sol is contacted with laminated clay column, SAPO molecular sieve with zinc oxide, form carrier mixture, moulding, drying, roasting obtain carrier;
(3) compound of introducing containing metal promoter in carrier obtains the adsorbent precursor;
(4) dry, roasting adsorbent precursor;
(5) the adsorbent precursor after the roasting is reduced under hydrogen atmosphere, obtain adsorbent.
In the step (1); The compound that said zirconium dioxide precursor is can hydrolysis in step (1), exist with the zirconium dioxide form after the roasting in step (2), one or more in preferred zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO), the amorphous zirconium dioxide.The zirconium dioxide precursor contacts with excess acid solution, can hydrolysis and generate caking property colloidal solution.Said acid is selected from one or more in water-soluble inorganic acid and/or the organic acid, is preferably in hydrochloric acid, nitric acid, phosphoric acid and the acetic acid one or more, and wherein Suan consumption is to make the pH value of solution after the hydrolysis less than 6.0, preferably less than 4.0, to form colloidal sol.
In the step (2), said colloidal sol can adopt any way to contact mixing with laminated clay column, zinc oxide and SAPO molecular sieve.For example, can in colloidal sol, add laminated clay column earlier, add zinc oxide and SAPO molecular sieve more successively or simultaneously, also the three can be added simultaneously; Can directly in colloidal sol, add laminated clay column, zinc oxide and or the SAPO molecular sieve powder, also can add the slurries that prepare in advance.
In the step (2), resulting carrier mixture is shaped to extrudate, sheet, pill, ball or micro-spherical particle.For example; When said carrier mixture is dough or paste mixture, can make said mixture moulding (preferred extrusion molding) form particle, preferred diameter is at 1.0-8.0mm; Length makes the extrudate of gained carry out drying, roasting at the cylindrical extrudate of 2.0-5.0mm then.If the gained mixture is the wet mixture form, can make this mixture multiviscosisty, through the super-dry aftershaping.More preferably carrier mixture is the slurries form, and forming granularity through spray-drying is the microballoon of 20-200 micron, reaches the purpose of moulding.For the ease of spray-drying, the solid content of dry preceding slurries is 10-50wt%, is preferably 20-50wt%.
The drying means of carrier mixture and condition are conventionally known to one of skill in the art, for example Gan Zao method can be dry, oven dry, forced air drying.Dry temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.
The roasting condition of carrier mixture also is conventionally known to one of skill in the art, and in general, sintering temperature is 400-700 ℃, is preferably 450-650 ℃, and roasting time was at least 0.5 hour, was preferably 0.5-100 hour, more preferably 0.5-10 hour.
In the step (4), the said compound that contains the metallic promoter agent component is the material that can under roasting condition, be converted into metal oxide.The compound of said metallic promoter agent can be selected from acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metal, and two or more mixture etc. wherein.Preferably contain nickel in the said metallic promoter agent.Can adopt the method that well known to a person skilled in the art dipping or deposition on carrier, to introduce metallic promoter agent.Said dipping method is with the solution of the compound of containing metal promoter or the carrier of suspension impregnation after roasting; Said intermediate processing is that the solution of the compound of containing metal promoter or suspension are mixed with adsorbing agent carrier, adds ammoniacal liquor then, with the compound precipitation of metallic promoter agent on carrier.
In the step (4), the carrier of introducing the metallic promoter agent component carries out drying under about 50-300 ℃, and preferred baking temperature is 100-250 ℃, is about 0.5-8 hour drying time, more preferably from about 1-5 hour.After the drying; Under the condition that has oxygen or oxygen-containing gas to exist; About 300-800 ℃, more preferably carry out roasting under 450-750 ℃ the temperature; General about 0.5-4 hour of needed time of roasting; Preferred 1-3 hour; Be removed and the metallic promoter agent precursor is converted into metal oxide until volatile materials, obtain the adsorbent precursor.
In the step (5), the adsorbent precursor is reduced under 300-600 ℃ of hydrogeneous atmosphere, metallic promoter agent is existed to go back ortho states basically, obtain adsorbent of the present invention.Preferred reduction temperature is 400-500 ℃, and hydrogen content is 10-60vol%, recovery time 0.5-6 hour, and more preferably 1-3 hour.
The invention provides a kind of desulfurization of hydrocarbon oil method, comprising: hydrocarbon oil containing surphur is fully contacted under hydrogen atmosphere with adsorbent of the present invention, and the temperature and pressure condition is: 350-500 ℃, and 0.5-4MPa; Preferred 400-450 ℃, 1.0-2.0MPa.Sulphur in this process in the hydrocarbon ils is adsorbed on the adsorbent, thereby obtains the hydrocarbon ils of low sulfur content.
Can reuse behind the reacted adsorbent reactivation.Regenerative process is carried out under oxygen atmosphere, and regeneration condition is a normal pressure, and temperature is 400-700 ℃, preferred 500-600 ℃.
Regeneration back adsorbent also need reduce under hydrogen atmosphere before reusing, and the temperature and pressure scope of reduction is: 350-500 ℃, and 0.2-2MPa; Preferred 400-450 ℃, 0.2-1.5MPa.
Hydrocarbon ils according to the invention comprises cracking gasoline and diesel fuel, wherein " cracking gasoline " to mean boiling range be 40 to 210 ℃ hydrocarbon or its any cut, be from making bigger hydrocarbon molecule be cracked into the product of the heat or the catalytic process of less molecule.The thermal cracking process that is suitable for includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof.The example of the catalytic cracking process that is suitable for includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof.Therefore, the catalytically cracked gasoline of Shi Yonging includes but not limited to coker gasoline, pressure gasoline, visbreaking gasoline, fluid catalystic cracking gasoline and residual oil cracking gasoline and combination thereof.Can be during in some cases, in the methods of the invention as hydrocarbon-containifluids fluids with said cracking gasoline fractionation and/or hydrotreatment before desulfurization.It is 170 ℃ to 450 ℃ the hydrocarbon mixture or the liquid of its any fractional composition that institute's art " diesel fuel " means boiling range.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil and hydrotreatment diesel oil etc. and combination thereof.
The normal organosulfur compound that exists in term used herein " sulphur " any type of element sulphur of representative such as hydrocarbon-containifluids fluids such as cracking gasoline or the diesel fuel.The sulphur that exists in the hydrocarbon-containifluids fluids of the present invention includes but not limited to carbonyl sulfide (COS), carbon disulfide (CS
2), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, benzothiophene, alkylthrophene, alkylbenzene bithiophene and alkyl diphenyl bithiophene, and the normal bigger thiophenes of molecular weight that exists in the diesel fuel.
Adsorbent of the present invention has very high desulphurizing activated and abrasion resistance, also has the advantage of tangible increase octane number simultaneously, applicable to catalytically cracked gasoline or diesel fuel sweetening process.
The specific embodiment
Following instance will be done further explanation to the present invention, but therefore not limit the present invention.
Among the embodiment, adsorbent is formed employing XRD (X-ray diffraction) and is analyzed.
Embodiment 1
(Beijing Chemical Plant analyzes purely, 99wt.%) slowly joins in the salpeter solution of 2.7 kilograms of 5wt.%, and slowly stirs and avoid crystal of zirconium oxide to separate out, and obtains water white colloidal solution, is called zirconium colloidal sol with 1.90 kilograms of zirconium chlorides.Add 2.75 kilograms rectorite (catalyst branch company in Shandong contains 2.06 kilograms of butts) then in the above-mentioned titanium colloidal sol and mix.
With 4.43 kilograms of Zinc oxide powder (Headhorse companies; Purity 99.7wt.%); 1.00 kilogram SAPO-31 (catalyst branch company in Shandong contains 0.70 kilogram of butt) and 4.57 kilograms of deionized waters mix, and stir and obtain zinc oxide and SAPO-31 mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir the carrier pulp that obtains adsorbent after 1 hour.
Said carrier pulp adopts Niro Bowen Nozzle Tower
TMThe spray dryer of model carries out spray-drying, and spray-drying pressure is 8.5 to 9.5MPa, and inlet temperature is below 500 ℃, and outlet temperature is about 150 ℃.Microballoon by spray-drying obtains is first at 180 ℃ times dry 1 hour, obtains adsorbing agent carrier in 1 hour 635 ℃ of following roastings then.
With 3.2 kilograms adsorbing agent carriers with 3.51 kilograms of Nickelous nitrate hexahydrate (Beijing chemical reagents corporations; Purity is greater than 98.5%), 0.6 kilogram of deionized water solution dipping; The mixture that obtains after 4 hours, 1 hour can make adsorbent precursor in 635 ℃ of roastings of air atmosphere through 180 ℃ of dryings.
Adsorbent precursor reductase 12 in 425 ℃ hydrogen atmosphere hour can obtain adsorbent, and this adsorbent is designated as adsorbent A 1.The chemical composition of adsorbent A 1 is: zinc oxide content is 44.3wt.%, and rectorite content is 20.6wt.%, and SAPO-31 content is 7.0wt.%, and zirconium dioxide binding agent 10.0wt.%, metallic nickel content are 18.1wt.%.
Embodiment 2
With 1.71 kilograms of zirconium oxychloride (Aldrich companies; Analyze purely, 98.5wt.%) under condition of stirring, slowly join in the hydrochloric acid (chemical pure, Beijing Chemical Plant produce) of 3.2 kilograms of 15wt.% and stirred acidifying 1 hour; This moment, solution was water white colloidal solution, was called zirconium colloidal sol.The imvite (catalyst branch company in Shandong contains 1.50 kilograms of butts) that adds 2.21 kilograms in the above-mentioned zirconium colloidal sol under agitation mixes then.
5.52 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%), 0.43 kilogram of SAPO-31 (catalyst branch company in Shandong contains 0.30 kilogram of butt) and 5.0 kilograms of deionized waters mix stirring and obtain zinc oxide and SAPO-31 mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent A 2.The chemical composition of adsorbent A 2 is: zinc oxide content is 55.2wt.%, and the zirconium dioxide binder content is 11.7wt.%, and imvite content is 15.0wt.%, and SAPO-31 content is 3.0wt.%, and nickel content is 15.1wt.%.
Embodiment 3
(Aldrich company analyzes purely, 99wt.%) joins in the hydrochloric acid (chemical pure, Beijing Chemical Plant produce) of 3.1 kilograms of 30wt.% and stirs acidifying 1 hour, and obtain transparent colloidal solution this moment, is called zirconium colloidal sol with 1.76 kg of hydrogen zirconias.
With 4.93 kilograms of Zinc oxide powder (Headhorse companies; Purity 99.7%); 2.14 rectorite (the Shandong catalyst branch company of kilogram; Contain 1.60 kilograms of butts); 0.71 kilogram SAPO-34 (Shandong catalyst branch company; Contain 0.50 kilogram of butt) and 6.40 kilograms of deionized waters mixing, stir and obtain mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.
Carry out the spray drying forming of carrier and introduce active component nickel and cobalt with reference to the method for embodiment 1, obtain adsorbent A 3.The chemical composition of adsorbent A 3 is: zinc oxide content is 49.3wt.%, and the zirconium dioxide binding agent is 13.5wt.%, and rectorite is 16.0wt.%, and SAPO-34 content is 5.0wt.%, and nickel content is 8.1wt.%, and cobalt content is 8.1%.
Embodiment 4
(Aldrich company analyzes purely, 99wt.%) joins in the hydrochloric acid (chemical pure, Beijing Chemical Plant produce) of 3.1 kilograms of 30wt.% and stirs acidifying 1 hour, and obtain transparent colloidal solution this moment, is called zirconium colloidal sol with 1.76 kg of hydrogen zirconias.
With 4.93 kilograms of Zinc oxide powder (Headhorse companies; Purity 99.7%); 2.09 bentonite (the Shandong catalyst branch company of kilogram; Contain 1.60 kilograms of butts); 0.72 kilogram SAPO-11 (Shandong catalyst branch company; Contain 0.50 kilogram of butt) and 6.40 kilograms of deionized waters mixing, stir and obtain mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent A 4.The chemical composition of adsorbent A 4 is: zinc oxide content is 49.3wt.%, and the zirconium dioxide binding agent is 13.5wt.%, and bentonite is 16.0wt.%, and SAPO-11 content is 5.0wt.%, and nickel content is 16.2wt.%.
Comparative Examples 1
4.43 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%) and 4.57 kilograms of deionized waters are mixed, stir and obtain the zinc oxide slurries after 30 minutes.
(Shandong Aluminum Plant produces to get 1.87 kilograms in aluminium oxide; Contain 1.36 kilograms of butts) and 3.20 kilograms rectorite (containing 2.40 kilograms of butts) under agitation mix; Add then after 4.6 kilograms of deionized waters mix; Hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) the stirring acidifying that adds 360 milliliter 30% is warming up to 80 ℃ and wore out 2 hours after 1 hour.Add again to stir after the zinc oxide slurries mix and obtained carrier pulp in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent B 1.The chemical composition of adsorbent B 1 is that zinc oxide content is 44.3wt.%, and the alumina bound agent content is 13.6wt.%, and rectorite content is 24.0wt.%, and nickel content is 18.1wt.%.
Comparative Examples 2
(Shandong Aluminum Plant produces to get 1.61 kilograms of boehmites; Contain 1.17 kilograms of butts) and 2.65 kilograms imvite (containing 1.80 kilograms of butts) under agitation mix; Add then after 8.2 kilograms of deionized waters mix; Hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) the stirring acidifying that adds 260 milliliter 30% is warming up to 80 ℃ and wore out 2 hours after 1 hour.Treat to add 5.52 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%) again and stir after temperature reduces to obtain carrier pulp in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent B 2.The chemical composition of adsorbent B 2 is: zinc oxide content is 55.2wt.%, and the alumina bound agent content is 11.7wt.%, and imvite content is 18.0wt.%, and nickel content is 15.1wt.%.
Comparative Examples 3
4.93 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%) and 5.57 kilograms of deionized waters are mixed, stir and obtain the zinc oxide slurries after 30 minutes.
(Shandong Aluminum Plant produces to get 1.85 kilograms of boehmites; Contain 1.35 kilograms of butts) and 2.81 kilograms rectorite (Shandong catalyst branch company; Contain 2.10 kilograms of butts) under agitation mix; Add then after 4.6 kilograms of deionized waters mix; Hydrochloric acid (the chemical pure that adds 300 milliliter 30%; Beijing Chemical Plant's product) making slurry pH value is 2.5, and the stirring acidifying is warming up to 80 ℃ and wore out 2 hours after 1 hour.Add again to stir after the zinc oxide slurries mix and obtained carrier pulp in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel and cobalt with reference to the method for embodiment 1, obtain adsorbent B 3.The chemical composition of adsorbent B 3 is: zinc oxide content is 49.3wt.%, and alumina binder is 13.5wt.%, and rectorite is 21.0wt.%, and nickel content is 8.1wt.%, and cobalt content is 8.1%.
Comparative Examples 4
4.93 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%) and 5.57 kilograms of deionized waters are mixed, stir and obtain the zinc oxide slurries after 30 minutes.
(Shandong Aluminum Plant produces to get 1.86 kilograms of boehmites; Contain 1.35 kilograms of butts) and 2.74 kilograms bentonite (Shandong catalyst branch company; Contain 2.10 kilograms of butts) under agitation mix; Add then after 3.6 kilograms of deionized waters mix; Hydrochloric acid (the chemical pure that adds 300 milliliter 30%; Beijing Chemical Plant's product) making slurry pH value is 2.5, and the stirring acidifying is warming up to 80 ℃ and wore out 2 hours after 1 hour.Add again to stir after the zinc oxide slurries mix and obtained carrier pulp in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent B 4.The chemical composition of adsorbent B 4 is: zinc oxide content is 49.3wt.%, and alumina binder is 13.5wt.%, and bentonite is 21.0wt.%, and nickel content is 16.2wt.%.
Embodiment 5
Adsorbent to distinct methods is prepared is investigated abrasion strength resistance, desulfurization performance and three indexs of octane number.
The intensity of adsorbent adopts straight tube wearing and tearing method to estimate, and its evaluation method is with reference to the method for RIPP 29-90 in " petrochemical industry analytical method (RIPP) experimental technique ", and abrasion index is more little, shows that abrasion strength resistance is high more.Different adsorbent attrition evaluation results are as shown in table 1.
Desulfurization performance is weighed with The product sulfur content, and sulfur content adopts the off-line chromatography in the product, adopts the little anti-experimental provision of fixed bed to estimate, and it is the catalytically cracked gasoline of 1080ppm that the adsorption reaction raw material adopts sulphur concentration.The absorption test process adopts hydrogen atmosphere, and reaction temperature is 410 ℃, and the adsorption reaction weight space velocity is 4h
-1, in order accurately to characterize out adsorbent in the operating activity of industry practice, adsorbent carried out Regeneration Treatment after reaction was accomplished, and Regeneration Treatment is under 550 ℃ air atmosphere, to carry out.Its activity settled out basically after adsorbent carried out 6 circulations of reaction regeneration, and the sulfur content after stablizing with adsorbent in the product gasoline is represented the activity of adsorbent, and sulfur content is as shown in table 1 in the product gasoline of stable back.
Adopt GB/T 503-1995 and GB/T 5487-1995 to measure the motor octane number (MON) and the research octane number (RON) (RON) of reaction front and back gasoline respectively, the result sees table 1.Can find out through table 1, contain the sorbent reactions of SAPO molecular sieve after, the octane number of product gasoline all has increase in various degree.
The performance of the different adsorbents of table 1
| Adsorbent | A1 | A2 | A3 | A4 | B1 | B2 | B3 | B4 |
| Abrasion index | 4.8 | 6.8 | 5.9 | 6.0 | 4.9 | 6.8 | 6.0 | 6.0 |
| Sulfur content/ppm in the product gasoline | 9 | 6 | 11 | 16 | 20 | 13 | 23 | 38 |
| △MON | 0.55 | 0.10 | 0.35 | 0.20 | -0.55 | -0.45 | -0.35 | -0.40 |
| △RON | 0.55 | 0.20 | 0.35 | 0.20 | -0.45 | -0.35 | -0.45 | -0.40 |
| △(RON+MON)/2 | 0.55 | 0.15 | 0.35 | 0.20 | -0.50 | -0.40 | -0.40 | -0.40 |
Annotate:
1, the sulfur content of feed gasoline is 1080ppm, and RON is 93.1, and MON is 82.7.
2, △ MON representes the value added of product MON;
3, △ RON representes the value added of product RON;
4, △ (RON+MON)/2 is the poor of product anti-knock index and raw material anti-knock index.
Claims (18)
1. a hydrocarbon oil desulphurization adsorbing agent is a benchmark with the adsorbent gross weight, comprises following composition at least:
1) SAPO molecular sieve, content are 1-20wt%
2) zirconium dioxide, content are 3-35wt%;
3) laminated clay column, content are 5-40wt%;
4) zinc oxide, content are 10-80wt%;
5) at least a metallic promoter agent that is selected from cobalt, nickel, iron and manganese, content is 5-30wt%.
2. according to the described catalyst of claim 1; Wherein, The content of SAPO molecular sieve is 2-15wt%; The content of zirconium dioxide is 5-25wt%; The content of laminated clay column is 10-30wt%; The content of zinc oxide is 25-70wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 8-25wt%.
3. according to the described catalyst of claim 1; Wherein, The content of SAPO molecular sieve is 2-10wt%; The content of zirconium dioxide is 8-15wt%; The content of laminated clay column is 12-25wt%; The content of zinc oxide is 40-58wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 12-20wt%.
4. according to the described catalyst of one of claim 1～3, wherein, the SAPO molecular sieve is one or more among SAPO-11, SAPO-31 and the SAPO-34.
5. according to the described catalyst of claim 1, wherein, said laminated clay column is the interbed mineral crystal, is alternately to be rearranged by two kinds of individual layer mineral clay component rules, and its basal spacing is not less than 1.7nm, at 3.4 ° a stronger peak is arranged in its XRD figure spectrum.
6. according to the described catalyst of claim 1, wherein, said laminated clay column is selected from one or more in rectorite, Yun Mengshi, bentonite, imvite and the smectite.
7. the preparation method of the said hydrocarbon oil desulphurization adsorbing agent of one of claim 1～6 comprises:
(1) makes the hydrolysis in acid solution of zirconium dioxide precursor, form colloidal sol;
(2) colloidal sol is contacted with laminated clay column, SAPO molecular sieve with zinc oxide, form carrier mixture, moulding, drying, roasting obtain carrier;
(3) compound of introducing containing metal promoter in carrier obtains the adsorbent precursor;
(4) dry, roasting adsorbent precursor;
(5) the adsorbent precursor after the roasting is reduced under hydrogen atmosphere, obtain adsorbent.
8. according to the described preparation method of claim 7, the compound that in the step (1), said zirconium dioxide precursor is can hydrolysis in step (1), exist with the form of zirconium dioxide after the roasting in step (2).
9. according to the described preparation method of claim 7, in the step (1), said zirconium dioxide precursor is selected from one or more in zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO), the amorphous zirconium dioxide.
10. according to the described preparation method of claim 7, wherein, in the step (1), said acid is selected from one or more in water-soluble inorganic acid and/or the organic acid, and the consumption of acid is to make the pH value of solution after the hydrolysis less than 6.0.
11. according to the described preparation method of claim 7, wherein, in the step (1), said acid is selected from one or more in hydrochloric acid, nitric acid, phosphoric acid and the acetic acid, wherein Suan consumption is to make the pH value of solution after the hydrolysis less than 4.0.
12. according to the described preparation method of claim 7, in the step (2), in colloidal sol, add earlier laminated clay column, more simultaneously or add zinc oxide and SAPO molecular sieve successively, or the three added simultaneously.
13. according to the described preparation method of claim 7, in the step (2), the dry temperature of carrier mixture is a room temperature to 400 ℃, sintering temperature is 400-700 ℃, and roasting time was at least 0.5 hour.
14., in the step (3), adopt the method for dipping or deposition on carrier, to introduce the compound of containing metal promoter according to the described preparation method of claim 7.
15. according to the described preparation method of claim 7, the compound of said containing metal promoter is selected from the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide, and two or more mixture wherein.
16. according to the described preparation method of claim 7; In the step (4); The carrier of introducing promoter component is under about 50-300 ℃; Dry 0.5-8 hour; After the drying; Under the condition that has oxygen or oxygen-containing gas to exist,, be removed and metallic promoter agent is converted into metal oxide, obtain the adsorbent precursor until volatile materials about 300-800 ℃ of following roasting.
17. according to the described preparation method of claim 7, in the step (5), the adsorbent precursor is reduced under 300-600 ℃ of hydrogeneous atmosphere, metallic promoter agent is existed to go back ortho states basically.
18. desulfurization of hydrocarbon oil method; Comprise: the said adsorbent of hydrocarbon oil containing surphur and one of claim 1～6 is fully contacted under hydrogen atmosphere; The temperature and pressure condition is: 350-500 ℃; 0.5-4MPa; Sulphur in this process in the hydrocarbon ils is adsorbed on the adsorbent, thereby obtains the hydrocarbon ils of low sulfur content.
Priority Applications (1)
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Cited By (3)
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| CN105583001A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method |
| CN105582944A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method |
| CN116408104A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Adsorption desulfurization catalyst and preparation method and application thereof |
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| CN101481627A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbing agent and use method thereof |
| CN101618314A (en) * | 2008-05-20 | 2010-01-06 | 中国石油化工股份有限公司 | Desulfurizing adsorbent, preparation method and application thereof |
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| CN101481627A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbing agent and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105583001A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method |
| CN105582944A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method |
| CN105583001B (en) * | 2014-10-20 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN105582944B (en) * | 2014-10-20 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN116408104A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Adsorption desulfurization catalyst and preparation method and application thereof |
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