CN101433819B - Desulphurization sorbent composition - Google Patents
Desulphurization sorbent composition Download PDFInfo
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- CN101433819B CN101433819B CN200710177409A CN200710177409A CN101433819B CN 101433819 B CN101433819 B CN 101433819B CN 200710177409 A CN200710177409 A CN 200710177409A CN 200710177409 A CN200710177409 A CN 200710177409A CN 101433819 B CN101433819 B CN 101433819B
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Abstract
The invention discloses a desulfurization adsorbent composition, which comprises 1 to 30 weight percent of phosphorus-modified rare earth-zeolite mixture, 5 to 40 weight percent of active metal oxide and 30 to 94 weight percent of carrier, wherein the carrier comprises alumina and zinc oxide; a rare earth-zeolite mixture is modified by phosphorus and then is preformed with a carrier mixture into porous heat-resistant solid particles, and then active metal components are introduced on the solid particles to obtain an adsorbent; and a light hydrocarbon oil raw material containing sulfur and a hydrogen donor enter a reactor filled with the adsorbent, materials remained after the reaction are separated, a reaction product is sent into a subsequent separation system for product separation, a spent adsorbent after the reaction is steam-stripped and then is subject to coke-burning regeneration, and the regenerated adsorbent is reduced by the hydrogen donor and is returned to the reactor for cyclic use. The adsorbent realizes the deep removal of sulfide in light hydrocarbon oil, and the produced gasoline has higher octane number, lower benzene content, and higher strength at the same time.
Description
Technical field
The invention belongs in a kind of adsorbent that reduces sulfur content in the light petroleum hydrocarbon and preparation thereof, application.
Background technology
Along with people's is to the pay attention to day by day of environmental protection, and is more and more stricter to the restriction of the sulfur content in the light hydrocarbon oil that acts as a fuel.With gasoline is example, and EPA (EPA) regulation sulphur limit value is 30 μ g/g (TierII); Europe requires content of sulfur in gasoline to be lower than 50 μ g/g (Europe IV discharge standard); China will be progressively in line with international standards also to the restriction of content of sulfur in gasoline.Thereby, the hydrocarbon ils deep desulfuration just can be meeted the requirements.
At present, the process for deep desulphurization of oil product is except that hydrogen addition technology, and the sulfur-containing compound that absorption method removes in the fuel oil also is a very attracting in recent years technology.Of US6350422, US6955752, US6482314, US6428685, US6346190; Adopt adsorbent that light oil is faced H-H reaction absorption; The hydrogen consumption is lower; Desulfuration efficiency is high, can the production sulfur content at following gasoline of 30 μ g/g or diesel oil, its adsorbent is stated from the carrier and constitutes by going back in ortho states cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, the vanadium metal one or both; Said carrier adopts the mixture of zinc oxide oxide, silica and aluminium oxide, and zinc oxide accounts for that 10～90 heavy %, silica account for 5～85 heavy %, aluminium oxide accounts for 5～30 heavy % in the carrier.Carrier component and metal component through mix, granulating, drying, calcining process bimetallic junction configuration desulfuration adsorbent; 0.7～2.1MPa, 343～413 ℃ with face under the operating condition of hydrogen and catch the sulphur in the gasoline; Generate metal sulfide or utilize sulfide polarity to remove sulphur, the regeneration of sulfur-bearing catalyst circulation.Though above-mentioned patent has realized the deep desulfuration of hydrocarbon ils under the low hydrogen consumption, however the still slightly loss of its gasoline product octane number.
CN1261218C, CN1583973A, CN1583972A all adopt the zeolite desulfurizing agent to light-end products cracking desulfurization under conditions of non-hydrogen, and selective cracking sulfide converts it into hydrocarbon and inorganic sulphide, no hydrogen consumption; No loss of octane number; But the same with the mink cell focus catalytic cracking and desulfurizing, its desulfurization degree is influenced by feed sulphur content, catalyst property and conversion level etc.; Be not enough to realize deep desulfuration; Desulfurization degree can only be used to produce the low-sulfur product oil generally at 50-80%, and loss of octane number is low.
Summary of the invention
One of the object of the invention is that a kind of adsorbent composition that reduces sulfur content in the light-weight fuel oil is provided on the basis of existing technology.
Two of the object of the invention provides the preparation method of said adsorbent composition.
Three of the object of the invention provides a kind of method that said adsorbent composition reduces the petroleum hydrocarbon sulfur content of using.
Desulphurization sorbent composition provided by the invention comprises: the phosphorus modified RE zeolite mixture of the heavy % of 1-30, the reactive metal oxides of 5～40 heavy % and 30～94 heavy % contain zinc sial medium carrier, serve as to calculate benchmark with the adsorbent gross weight all.
Said phosphorus modified RE zeolite mixture accounts for the heavy % of 1-30 of adsorbent composition gross weight, preferred 5～25 heavy %.Weight with phosphorus modified RE zeolite mixture serves as to calculate benchmark, and the composition of phosphorus modified RE zeolite mixture is following: phosphorus is with P
2O
5Meter accounts for the heavy % of 1-10; Rare earth is with RE
2O
3Meter accounts for the heavy % of 1-35; Surplus is a zeolite mixture.
Wherein the predecessor of phosphorus can adopt any form phosphorus-containing compound, like one or more mixtures in phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate.The mixture of one or more in preferred phosphorous water soluble compound such as orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), the ammonium phosphite, more preferably phosphoric acid ammonium, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP).
Said rare earth all is selected from one or more elements among La, Ce, Pr, Nd, the Sm.
Said phosphorus modified RE zeolite mixture refers to that the phosphorus modified RE selects shape zeolite and phosphorus modified RE faujasite according to 10: 1 to 1: 10 preferred mixtures that mixed in 1: 1.1 to 1: 5 of part by weight.
In the Beta zeolite that wherein said rare earth shape-selective is selected from the five-membered ring silica-rich zeolite that contains rare earth, the ZRP zeolite that contains rare earth, contain rare earth one or more, its silica alumina ratio is 20-500.Wherein said five-membered ring silica-rich zeolite is selected from one or more in ZSM-5 zeolite, ZSM-8 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-48 zeolite, the ZSM-57 zeolite; The Beta zeolite comprises one or more in Na β type, H β type, the US zeolite beta.
Said faujasite is that X type series zeolite is or/and Y type series zeolite.The preferred Y-type rare earth series zeolite of rare earth faujasite comprises one or more the mixture in REY type, REHY type, the REUSY type zeolite.
Said reactive metal oxides accounts for 5～40 heavy % of adsorbent composition total amount, the heavy % of preferred 15-30.Said reactive metal is selected from one or more metals in the transition metal such as cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, vanadium, and preferred cobalt is or/and nickel.
Said zinc sial medium carrier argillaceous 5～85 heavy %, preferred 35～80 heavy % of containing.Weight with carrier serves as to calculate benchmark, and the composition of carrier is following: aluminium oxide 5～30 heavy %, preferred 5～15 heavy %; Zinc oxide 10～65 heavy %, preferred 15～50 heavy %; Surplus is a clay.Said zinc oxide can adopt zinc oxide, also can adopt its presoma, comprises zinc hydroxide and zinc-containing metal salt such as zinc sulfate, zinc nitrate, zinc acetate, zinc halide and contains the zinc ammonium salt, contains zinc sodium salt etc.Said clay is selected from silica, amorphous aluminum silicide, natural porous carrier materials such as kaolin, halloysite, imvite, bentonite, diatomite, sepiolite, tires out one or more mixtures in the inorganic oxides such as taking off soil; Preferred silica, kaolin, the tired mixture that takes off in the soil two or more; Weight ratio between wherein any two kinds of clay compositions is 0.1～100: 1, preferred 0.5～50: 1.
Adsorbent preparation method provided by the invention is; Will through the mixture of the above-mentioned rare earth shape-selective zeolite of phosphorus modification and rare earth faujasite after the phosphorus modification with contain zinc sial medium carrier mixture and be configured as the porous heat-resistant solid particle in advance, on this solid particle, introduce the method for metal active constituent again.
The phosphorus modifying method of zeolite provided by the invention can adopt the method for existing various load nonmetal oxides, like the method for dipping, promptly adopts the aqueous solution dipping rare earth zeolite of the predecessor of above-mentioned one or more phosphorus; Perhaps soild oxide and/or its precursor-slaine or its ammonium salt and zeolite mechanical mixture are ground or abrasive method not; Perhaps colloidal sol facture etc.
Phosphorus modified RE zeolite can mix formation mixture, dry forming, roasting more uniformly basically through any suitable mode with carrier mixture.Phosphorus modified RE zeolite and carrier mixture preferred manufacturing procedure are sol-gel processes.
The present invention introduces the method for metal active constituent on solid particle, can adopt existing various metal oxide-loaded method, and the method like dipping promptly adopts above-mentioned one or more metal salt solutions to flood in type carrier; Perhaps the method for deposition promptly adopts above-mentioned one or more metal salt solutions or its oxide, hydroxide to deposit on the porous heat-resistant carrier; Perhaps soild oxide and/or its precursor-slaine or its hydroxide and carrier mechanical mixture are ground or abrasive method not; Perhaps colloidal sol facture, gelling process and hydro-thermal method etc.Said slaine mainly is sulfate, nitrate, acetate, halide and metal ammonium salt, metal sodium salt of above-mentioned metal etc.The metal active constituent of adsorbent according to the invention adopts the form of slaine in the preparation process, thereby the method for optimizing of introducing metal active constituent is the method for deposition or the method for dipping.
Metal active constituent and carrier mixture thereof can adopt method moulding such as granulation, extrusion or spray-drying; Drying, roasting etc. after the moulding.Its baking temperature can be a room temperature to 400 ℃, is preferably 100～200 ℃, also can adopt microwave drying.Sintering temperature can be 400～1200 ℃, is preferably 500～800 ℃; Roasting time 0.5～100 hour is preferably 1～10 hour.
According to method provided by the present invention, the adsorbent preferred manufacturing procedure is following:
(1) phosphorus modified RE zeolite mixture colloidal sol preparation
With commercially available rare earth shape-selective zeolite and rare earth faujasite according to a certain percentage mechanical mixture evenly be mixed with zeolite mixture; According to zeolite mixture: ammonium salt: the weight ratio of deionized water=1: 0～1: 3～40 (preferred 1: 1: 20) was 50～100 ℃ of following ion-exchanges 0.1～5 hour; Filter, wash the back repeated exchanged and once obtain ammonium type rare earth zeolite mixture, its Na
2O content is not more than 0.15 heavy %; Ammonium type rare earth zeolite mixture and phosphorous water soluble compound and deionized water mix according to the weight ratio (hereinafter to be referred as water-solid ratio) 1: 0.3～1 of water and solid; At room temperature stir dipping 0.3～5 hour, make phosphorous rare earth zeolite mixture colloidal sol;
(2) carrier colloidal sol preparation
The powder carrier material of reservation amount or the solid sediment of carrier are mixed making beating with deionized water; Obtain the slurries that solid content is 5～30 weight %; The aqueous solution that under agitation adds hydrochloric acid or nitric acid; Make slurries pH=2～4, stir, under 30～100 ℃, leave standstill and made carrier colloidal sol at least in aging 0.5 hour;
(3) solid particle preparation
With step (1) and step (2) make aging after carrier colloidal sol mixes, and add an amount of aluminium colloidal sol, adsorbent solid content and aluminium colloidal sol solid content (in aluminium oxide) weight ratio are 10～50, continue stirring up to the formation uniform sol; Is 250～300 ℃ with this colloidal sol at the control exhaust temperature, and atomisation pressure is 50～60 atmospheric pressure, and spray drying forming makes microspheric solid carrier particle.Free Na is removed in the microspheroidal solid particle washing that obtains
+, 100～200 ℃ of down oven dry after at least 2 hours, roasting at least 2 hours under 500～800 ℃ of conditions again obtains the particle of microspheroidal rare earth zeolite mixture and carrier mixture;
(4) the metal oxide active component is introduced
One or more slaine of the containing metal active component of reservation amount is made into the aqueous solution that concentration of metal ions is 1～10mol/L; At room temperature add the microspheroidal rare earth zeolite mixture that step (3) makes and the particle of carrier mixture according to the ratio of metal oxide and carrier; Add the ammoniacal liquor that concentration is 0.5～5mol/L while stirring, keeping pH is 7～10, constantly be stirred to deposition fully after; Being warming up to 60～100 ℃ also placed aging 0.5 hour at least; Filter, washing leaching cake is to there not being the mixture that acid ion makes metal hydroxides rare earth zeolite mixture and carrier material, after drying at least 2 hours under 100～200 ℃; Roasting at least 2 hours under 500～800 ℃ of conditions is again pulverized, sieving obtains the microspheroidal absorbent particles.
Wherein said phosphorus-containing compound is phosphorous water soluble compound; Be selected from one or more the mixture in orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), the ammonium phosphite, one or more in preferably phosphoric acid ammonium, diammonium hydrogen phosphate, the ammonium dihydrogen phosphate (ADP).
The above-mentioned oxidation state reactive metal adsorbent that makes adopts the specific method activation processing before use, makes the oxidation state reactive metal be converted into the zero-valent state reactive metal.Processing method provided by the invention is that the reducing agent that adopt to be fit to such as hydrogen etc. make above-mentioned adsorbent activity metal precursor 200～400 ℃ temperature; Reduction is at least 30 minutes under the hydrogen partial pressure 0.5-2.5MPa condition, contains the adsorbent composition of zero-valent state reactive metal basically thereby produce.
Adsorbent used in the present invention is preferably microspheroidal for ease of fluidisation, and its average grain diameter is at 40-200 μ m, and its abrasion index is preferably less than 2.5%h
-1
The method of reduction sulfur content of light hydrocarbon oil provided by the invention is:
Sulfur-bearing light hydrocarbon oil raw material and hydrogen donor after the preheating get into and are equipped with in the reactor of adsorbent, at temperature 350-450 ℃, and pressure 0.5-2.5MPa, feedstock oil weight (hourly) space velocity (WHSV) 0.5-10h
-1, preferred 4-8h
-1The weight ratio 1-20 of adsorbent total amount and hydrocarbon oil crude material; React under the condition of preferred 5-15; Material behind the separating reaction; Product is sent into subsequent separation system and is carried out the product separation, and reacted adsorbent to be generated coke burning regeneration behind stripping, the adsorbent after regeneration Returning reactor after the hydrogen donor reduction recycles.
The hydrocarbon oil crude material of said sulfur-bearing is selected from one or more the mixture in gasoline, kerosene, diesel oil, the gas oil fraction, and preferred gasoline is or/and diesel oil.Above-mentioned gasoline, kerosene, diesel oil, gas oil fraction are that its full cut is or/and its part narrow fraction.The hydrocarbon oil crude material sulfur content of said sulfur-bearing is preferably in more than the 500 μ g/g more than 100 μ g/g.
Said hydrogen donor is selected from one or more the mixture in hydrogen, hydrogen-containing gas, the hydrogen supply agent; Wherein hydrogen is the hydrogen of various purity; The mixture of one or more in hydrogen-containing gas dry gas that preferred this method is produced, catalytic cracking (FCC) dry gas, coking dry gas, the thermal cracking dry gas; More than the hydrogeneous best 30 volume %, hydrogen supply agent is selected from one or more the mixture in naphthane, decahydronaphthalene, the dihydro indenes.
Said reactor can adopt the reactor of fluidized-bed reactor, fixed bed reactors, moving-burden bed reactor or other type and compound; The preferred streams fluidized bed reactor comprises in fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, Transport Bed, the dense-phase fluidized bed one or more.
The present invention compared with prior art has following unforeseeable technique effect:
1, adsorbent provided by the invention by go back metals such as ortho states cobalt, nickel, the phosphorus modification is selected inorganic oxides such as shape rare earth zeolite, zinc oxide and silica, aluminium oxide, kaolin and is formed; The adsorbent that adopts sol-gel process to make; It is desulphurizing activated good to have; Characteristics such as adsorbent is evenly distributed, and intensity is good;
2, the ortho states of going back of one or both metals in the preferred cobalt of adsorbent provided by the invention, the nickel is an active component, and the mixture more than two or three in preferred silica, aluminium oxide, the kaolin is a carrier, adds a certain amount of rare earth zeolite mixture; Through the cooperative effect between these components; Make when this adsorbent is realized in deep removal light hydrocarbon oil sulfide, kept higher liquid to receive, during in particular for gasoline desulfur; Compared with prior art; The product octane number is higher, and its benzene content is lower, and adsorbent provided by the invention is suitable for production super-low sulfur clean gasoline.
When 3, adopting method provided by the present invention to handle gasoline stocks; Can even not have under the condition of hydrogen consumption and realize deep desulfuration in low hydrogen consumption; The removal efficiency of sulphur can reach more than the 97 heavy %, can be used for the production sulfur content be lower than 10 μ g/g's and improved octane number when having reduced gasoline olefin, the yield of gasoline is more than the 98 heavy %; The product benzene content in gasoline is low, can be used for the high-octane rating clean gasoline that the production sulfur content is lower than 10 μ g/g.
When 4, adopting method provided by the present invention to handle diesel raw material, facing under the condition of hydrogen, diesel raw material has desulfurized effect preferably, and desulfurization degree reaches more than the 99 heavy %.The aromatic content of diesel oil Cetane number of producing slightly improves.
Description of drawings
Accompanying drawing is that hydrocarbon ils provided by the invention faces the method flow sketch map that the hydrogen adsoption catalysis transforms desulfurization in fluidized-bed reactor.
The specific embodiment
Below in conjunction with accompanying drawing method provided by the invention is further explained, but therefore do not made the present invention receive any restriction.
Accompanying drawing is that hydrocarbon ils provided by the invention faces the method flow sketch map that the hydrogen adsoption catalysis transforms desulfurization in fluidized-bed reactor.Accompanying drawing adopts a fluidized-bed reactor, a regenerator and a regenerative agent reductor.Said regenerator, regenerative agent reductor are fluid bed.
Gasoline fraction raw material after the preheating and hydrogen donor get into carrier pipe 2 bottoms through pipeline 1, and contact from the adsorbent after the regeneration of regenerator sloped tube 17, and at temperature 350-450 ℃, pressure 0.5-2.5MPa, feedstock oil weight (hourly) space velocity (WHSV) 0.5-10h
-1, preferred 4-8h
-1The weight ratio 1-20 of adsorbent total amount and hydrocarbon oil crude material reacts under the condition of preferred 3-15, and reactant flows into the settler 7 that has the dense, fluidized bed bioreactor, and reaction oil gas is sent into follow-up product piece-rate system through pipeline 8.Adsorbent to be generated gets into stripper 3, and by from the entrained reaction oil gas of the steam stripped of pipeline 4 adsorbent to be generated, the spent agent behind the stripping gets into regenerators 13 through inclined tube 5 to be generated; Oxygen-containing gas is introduced regenerator 13 through pipeline 14; Desulfurizing agent to be generated is coke burning regeneration under the effect of oxygen-containing gas, and regenerated flue gas is drawn regenerator through pipeline 12, and the reproducing adsorbent of high temperature gets into regenerative agent reductor 16 through pipeline 15; After adopting nitrogen stripping, cooling; With hydrogen reducing, the desulfurizing agent after the reduction returns carrier pipe 2 bottom cycle by regenerator sloped tube 17 and uses, and loosening wind nitrogen gets into regenerative agent reductor 16 through pipeline 18.
Following embodiment will further explain method provided by the invention, but therefore not make the present invention receive any restriction.
Employed feedstock property is listed in table 1 among the embodiment.Zeolite and carrier mixture solid particle adopt sol-gel process to produce.
The composition of adsorbent adopts x ray fluorescence spectrometry (RIPP 134-90 sees Science Press's " petrochemical industry analytical method (RIPP test method) ").Wherein the mensuration of adsorbent attrition rate adopts RIPP 29-90 method, with compressed air as fluidizing agent, pressure 0.6MPa, 20 liters/minute of flows are measured adsorbent hourly average abrasion index.
Present embodiment adopts the preparation of adsorbent solids particle following:
The primary raw material of carrier that present embodiment adopts is following:
C1
#Carrier: (solid content is 64 heavy % to 10 kilograms of boehmites; Shandong Zibo aluminium manufacturer industrial products, down together)+(solid content is 25 weight % to 1.0 kilograms of Ludox, produces in upright sail chemical plant, Qingdao; Down together)+13.1 kilograms of zinc oxide (purity 99.7%, Cangzhou outstanding one-tenth chemical industry Co., Ltd product);
C2
#Carrier: 4 kilograms of boehmite+1.0 kilogram Ludox+6 kilograms of kaolin (solid content is 73 weight %, and the industry of Suzhou china clay company is produced)+10 kg of hydrogen zinc oxide (zinc oxide content 71.5%, Pei County zinc oxide factory product);
C3
#Carrier: 5 kilograms of boehmite+4 kilogram kaolin+2 kilograms of tired soil (solid content is 68 weight %, and Zhongxiang City, Hubei produces)+3.5 kilo sulfuric acid zinc (purity 98%, sea, Jinan chemical industry Co., Ltd product) that take off;
The above-mentioned support material that will mix is respectively mixed making beating with deionized water, obtain the slurries that solid content is 15 weight %, under agitation adds 1.6 kilograms aqueous hydrochloric acid solution (volumetric concentration 30%); Continue to stir; Up to forming uniform sol, make 1#, 2#, 3# carrier colloidal sol respectively, for use.
Present embodiment adopts the preparation of phosphorus modified RE zeolite sol following:
Present embodiment adopts the raw material of phosphorus modified RE zeolite following:
PS1
#Phosphorus modified RE zeolite: 7.13 kilograms of ZSM-5 zeolite (silica alumina ratios 25; Qilu Petrochemical company catalyst plant is produced)+0.79 kilogram of NaY zeolite (silica alumina ratio 3.5; Qilu Petrochemical company catalyst plant is produced)+(Baotou rare earth factory in the Inner Mongol produces 0.36 kilogram of rare earth chloride; Dry basis 48 heavy %, wherein the contents on dry basis of each component is La
2O
325.0%, Ce
2O
36.0%, Pr
2O
35.0%, Nd
2O
310.0%, down together)+0.14 kilogram of commercially available phosphoric acid (purity 85%, Hubei auspicious cloud chemical industry Co., Ltd produces);
PS2
#Phosphorus modified RE zeolite: 0.48 kilogram of ZRP zeolite (silica alumina ratio 50, Qilu Petrochemical company catalyst plant is produced)+2.38 kilograms of HY zeolites (silica alumina ratio 3.8, Qilu Petrochemical company catalyst plant is produced)+2.31 kilograms of rare earth chloride+0.29 kilogram ammonium dihydrogen phosphate (ADP)s (contain P
2O
561%, Hubei auspicious cloud chemical industry Co., Ltd produces);
PS3
#Phosphorus modified RE zeolite: 0.45 kilogram of Na β zeolite (silica alumina ratio 50, Qilu Petrochemical company catalyst plant is produced)+4.95 kilograms of 13X zeolites (silica alumina ratio 2.3, Qilu Petrochemical company catalyst plant is produced)+7.95 kilograms of rare earth chloride+1.21 kilogram diammonium hydrogen phosphates (contain P
2O
564%, skies international corporation produces);
Respectively with above-mentioned phosphorus-modified zeolite mixture according to zeolite mixture: ammonium nitrate: the weight ratio of deionized water=1: 1: 20 is filtered 90 ℃ of following ion-exchanges 2 hours, washing back repeated exchanged once obtains the ammonium type and selects the shape zeolite, its Na
2O content is not more than 0.15 heavy %.At room temperature above-mentioned ammonium type zeolite is mixed with the aqueous solution with rare earth chloride according to proportioning metering respectively, stirred dipping 2 hours, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours make PS1
#, PS2
#, PS3
#The rare earth shape-selective zeolite.The rare earth zeolite that makes was mixed according to the solid-liquid weight ratio with decationized Y sieve water in 1: 1～1: 10, making beating, stirring makes the rare earth zeolite sol.
The above-mentioned PS1 that makes
#, PS2
#, PS3
#The rare earth zeolite sol is mixed with above-mentioned C1#, C2#, C3# carrier colloidal sol respectively, and adds an amount of aluminium colloidal sol, and adsorbent solid content and aluminium colloidal sol solid content (in aluminium oxide) weight ratio are 15, continues to stir up to forming uniform sol; Is 250～300 ℃ with this colloidal sol at the control exhaust temperature, and atomisation pressure is 50～60 atmospheric pressure, and spray drying forming makes the microspheroidal solid particle.Free Na is removed in the microspheroidal solid particle washing that obtains
+, 100～200 ℃ of down oven dry after at least 2 hours, roasting at least 2 hours under 500～800 ℃ of conditions again obtains microspheroidal PS1
#-C1
#, PS2
#-C2
#, PS3
#-C3
#The rare earth solid particle.
Embodiment 1-3
Embodiment 1-3 explains that the adsorbent of phosphorous modified RE zeolite mixture is formed, the preparation method.
Respectively Zhangjagang City China adopted chemical industry Co., Ltd is produced 7.5 kilograms of nickel chlorides, reach each metal salt mixture of 8.5 kilograms of cobalt nitrate and nickel nitrate and be made into the aqueous solution that concentration of metal ions is 1～10mol/L, for use.
At room temperature with nickel chloride aqueous solution and PS1
#-C1
#Solid particle mixes; Add the ammoniacal liquor that concentration is 3mol/L while stirring, keeping pH is 7～10, constantly be stirred to deposition fully after; Being warming up to 90 ℃ also placed aging 0.5 hour at least; Filter, washing leaching cake is not to there being the mixture that acid ion makes nickel hydroxide and P-RE-ZSM5, P-REY and alumina supporting material, and washing is to there not being chlorion.100～200 ℃ of down oven dry after at least 2 hours, roasting at least 2 hours under 500～800 ℃ of conditions is again pulverized, sieving obtains microspheroidal adsorbent Ni-Zn/PS1
#-C1
#, called after PZYS-1.
At room temperature the aqueous solution saturation with cobalt nitrate and nickel nitrate floods PS2
#-C2
#Carrier constantly stirred dipping after at least 4 hours, and 100～200 ℃ of oven dry at least 2 hours down, roasting at least 2 hours under 500～800 ℃ of conditions is again pulverized, sieving obtains microspheroidal adsorbent Co-Ni-Zn/PS2
#-C2
#, called after PZYS-2.
With 7.3 kilograms of cobalt oxides (Zhangjagang City China adopted chemical industry Co., Ltd product) and PS3
#-C3
#Solid particle adds the making beating of 60 kg of water; Direct and and PS3 after perhaps cobalt oxide being pulled an oar separately
#Zeolite sol and C3
#Carrier colloidal sol mixes, and after stirring, adds an amount of aluminium colloidal sol, and adsorbent solid content and aluminium colloidal sol solid content (in aluminium oxide) weight ratio are 15, continues to stir up to forming uniform sol; Is 250～300 ℃ with this colloidal sol at the control exhaust temperature, and atomisation pressure is 50～60 atmospheric pressure, and spray drying forming makes microspheric solid particle.Wash its solid particle and remove free Na
+After, 100～200 ℃ of down oven dry at least 2 hours, roasting at least 2 hours under 500～800 ℃ of conditions again obtains microspheroidal adsorbent Co-Zn/PS3
#-C3
#, called after PZYS-3.
The composition of adsorbent PZYS-1, PZYS-2, PZYS-3 (each component serves as to calculate benchmark with the gross weight of adsorbent all) and polishing machine are seen table 2.
Comparative Examples 1-3
Compare composition, conventional preparation method and the performance of the bimetallic oxide adsorbent of the not phosphorous modified RE zeolite mixture of this Comparative Examples explanation with the adsorbent composition of embodiment 1-3.
According to C1
#, C2
#, C3
#Carrier is formed wet mixing, grinds, and dry forming, roasting (drying, method of roasting are with embodiment 1-3), the impregnating metal ion concentration is the nickel sulfate solution of 1～10mol/L respectively again, the cobalt nitrate-nickel nitrate mixed aqueous solution and the cobalt acetate aqueous solution.Oven dry, roasting once more, the microspheroidal adsorbent Ni-Zn/C1 that pulverizes, sieves and do not contained the rare earth zeolite mixture
#, Co-Ni-Zn/C2
#, Co-Zn/C3
#, difference called after S-4, S-5, S-6.It is formed and polishing machine is listed in table 2.
Can find out that from table 2 adsorbent PZYS-1, PZYS-2, PZYS-3 intensity are all better, its wear rate is all less than 1.0%h
-1More than, all greater than the adsorbent S-4, S-5, the S-6 that do not contain the rare earth zeolite mixture that adopt the conventional method preparation.
Embodiment 4-5
The adsorbent of embodiment 4-5 explanation phosphorus modified RE zeolite mixture is used aspect gasoline desulfur.
With the feed gasoline A in the table 1, B is raw material, and investigation feed gasoline raw material fully contacts with adsorbent PZYS-1, PZYS-2 respectively in the small-sized fluidized bed reactor and adsorbs and the catalyzed conversion situation.Adsorbent loadings 500 gram adopts hydrogen 360 ℃ temperature before use, and reduction is 60 minutes under the condition that hydrogen flowing quantity is 1.5 liters/hour.Product, steam and adsorbent mixtures to be generated separate in settler, and reaction product isolated obtains gaseous product and product liquid, and adsorbent to be generated is gone out the hydrocarbon product that adsorbs on the adsorbent mixtures to be generated by the water vapour stripping.Adsorbent behind the stripping contacts with the air that heated regenerates, and the catalyst mixture after the regeneration recycles behind cooling, hydrogen reducing.Experimental condition, result of the test and product gasoline property and sulfur content thereof are all listed in table 3.
Comparative Examples 4-5
Compare with the adsorbent application test of embodiment 4-5, the explanation of this Comparative Examples does not contain the bimetallic oxide adsorbent S-4 of rare earth zeolite mixture, the situation that S-5 is used for gasoline desulfur.
Feed gasoline A, B in the small-sized fluidized bed reactor respectively with hydrogen reducing after adsorbent S-4, S-5 contact and react.Other test technology conditions and test method are with embodiment 4～5.Experimental condition, result of the test and product gasoline property and sulfur content thereof are all listed in table 3.
Can find out that from table 3 with the gasoline desulfur product oil phase contrast that does not add the zeolite mixture adsorbent, the gasoline desulfur rate that adds P-contained zeolite mixture adsorbent is high, all more than 97.27 heavy %; Octane number is higher, all is higher than feedstock oil; And its benzene content is lower, all is lower than feedstock oil.
Embodiment 6-7
The bimetallic oxide adsorbent of embodiment 6-7 explanation phosphorus modified RE zeolite mixture is used for the situation of diesel fuel desulfurization.
Raw material diesel oil C, D with in the table 1 are raw material, and the investigation diesel raw material fully contacts with adsorbent PZYS-2, PZYS-3 respectively in the small-sized fluidized bed reactor adsorbs and the catalyzed conversion situation.Adsorbent loadings 500 gram adopts hydrogen 360 ℃ temperature before use, and reduction is 60 minutes under the condition that hydrogen flowing quantity is 1.5 liters/hour.Product, steam and adsorbent mixtures to be generated separate in settler, and reaction product isolated obtains gaseous product and product liquid, and adsorbent to be generated is gone out the hydrocarbon product that adsorbs on the adsorbent mixtures to be generated by the water vapour stripping.Adsorbent behind the stripping contacts with the air that heated regenerates, and the catalyst mixture after the regeneration recycles behind cooling, hydrogen reducing.Experimental condition, result of the test and product diesel oil character and sulfur content thereof are all listed in table 4.
Comparative Examples 6-7
Compare with the adsorbent application test of embodiment 6-7, the explanation of this Comparative Examples does not contain the bimetallic oxide adsorbent S-5 of rare earth zeolite mixture, the situation that S-6 is used for diesel fuel desulfurization.
Raw material diesel oil C, D in the small-sized fluidized bed reactor respectively with hydrogen reducing after adsorbent S-5, S-6 contact and react.Other test technology conditions and test method are with embodiment 4～5.Experimental condition, result of the test and product diesel oil character and sulfur content thereof are all listed in table 4.
Can find out that from table 4 with the diesel fuel desulfurization product oil phase contrast that does not add the zeolite mixture adsorbent, the diesel fuel desulfurization rate of the adsorbent of adding P-contained zeolite mixture is higher, all more than 99.17 heavy %; Diesel cetane-number is higher, all is higher than feedstock oil.
Table 1
| The raw material numbering | A | B | C | D |
| Type of feed | Gasoline | Gasoline | Diesel oil | Diesel oil |
| Density (20 ℃), kilogram/rice 3 | 787.5 | 708.3 | 886.8 | 911.6 |
| Octane number | ||||
| RON | 89.8 | 93.6 | - | - |
| MON | 78.8 | 79.4 | - | - |
| Cetane number | - | - | 29.5 | 22.0 |
| Sulphur, μ g/g | 1696.5 | 124.6 | 1060 | 10267.6 |
| Alkali nitrogen, μ g/g | 92.4 | 73.6 | 682 | 878.7 |
| Carbon, heavy % | 86.28 | 86.46 | 88.24 | 87.68 |
| Hydrogen, heavy % | 12.98 | 13.15 | 11.48 | 10.80 |
| Alkene, heavy % | 24.8 | 32.5 | 2.1 | 1.9 |
| Aromatic hydrocarbons, heavy % | 19.4 | 17.1 | 22.5 | 24.6 |
| Benzene, heavy % | 3.6 | 2.5 | - | - |
| Boiling range, ℃ | ||||
| Initial boiling point | 90 | 62 | 191 | 195 |
| 10％ | 92 | 75 | 208 | 234 |
| 30％ | 121 | 89 | 226 | 267 |
| 50％ | 154 | 112 | 247 | 298 |
| 70％ | 175 | 141 | 277 | 328 |
| 90％ | 189 | 173 | 324 | 358 |
| The end point of distillation | 203 | 202 | 361 | 374 |
Table 2
| Embodiment 1 | Comparative Examples 1 | Embodiment 2 | Comparative Examples 2 | |
Comparative Examples 3 | |
| The adsorbent numbering | PZYS-1 | S-4 | PZYS-2 | S-5 | PZYS-3 | S-6 |
| ?SiO 2, heavy % | 1.1 | 1.18 | 18.0 | 22.19 | 14.8 | 25.59 |
| ?Al 2O 3, heavy % | 29.0 | 29.43 | 14.4 | 17.75 | 19.5 | 31.29 |
| ZnO, heavy % | 55.3 | 59.39 | 32.5 | 40.06 | 4.7 | 8.13 |
| Reactive metal oxides, heavy % | NiO/10 | NiO/10 | CoO/10 NiO/10 | CoO/10 NiO/10 | CoO/35 | CoO/35 |
| ?P 2O 5, heavy % | 0.05 | - | 0.73 | - | 2.6 | - |
| Rare earth, heavy % | 0.05 | - | 2.19 | - | 5.4 | - |
| Select the shape zeolite, heavy % | ZSM-5/ 4.10 | - | ZRP/ 2.02 | - | β/ 1.62 | - |
| Faujasite, heavy % | Y/ 0.40 | - | HY/ 10.16 | - | 13X/ 16.38 | - |
| Wear rate, %h -1 | 0.7 ? | 1.4 | 0.75 | 1.6 | 0.9 | 2.1 |
Table 3
| Embodiment 4 | Comparative Examples 4 | |
Comparative Examples 5 | |
| Adsorbent | PZYS-1 | S-4 | PZYS-2 | S-5 |
| Feedstock oil | B | B | A | A |
| Medium | Dry gas | Dry gas | H 2 | H 2 |
| Reaction condition | ||||
| Temperature, ℃ | 370 | 370 | 425 | 425 |
| Pressure, MPa | 2.0 | 2.0 | 1.0 | 1.0 |
| The gasoline weight (hourly) space velocity (WHSV), hour -1 | 4 | 4 | 8 | 8 |
| |
5 | 5 | 10 | 10 |
| Hydrogen and gasoline volume ratio | 300 | 300 | 500 | 500 |
| Product distributes, heavy % | ||||
| Gas | 1.46 | 0.56 | 1.28 | 0.49 |
| Gasoline | 98.25 | 99.14 | 98.33 | 99.1 |
| Diesel oil | 0.16 | 0.15 | 0.2 | 0.15 |
| Coke | 0.12 | 0.14 | 0.18 | 0.24 |
| Loss | 0.01 | 0.01 | 0.01 | 0.02 |
| The gasoline main character | ||||
| RON | 95.9 | 88.3 | 91.6 | 83.4 |
| MON | 81.8 | 74.1 | 80.5 | 72.8 |
| Sulphur, μ g/g | 3.4 | 36.2 | 6.7 | 23.1 |
| Alkali nitrogen, μ g/g | 7.8 | 9.8 | 6.5 | 10.2 |
| Benzene, heavy % | 0.8 | 2.4 | 0.4 | 3.5 |
| Alkene, heavy % | 20.6 | 26.5 | 12.8 | 20.34 |
| Desulfurization degree, heavy % | 97.27 | 70.95 | 99.61 | 98.64 |
Table 4
| Embodiment 6 | Comparative Examples 6 | |
Comparative Examples 7 | |
| Adsorbent | PZYS-2 | ?S-5 | PZYS-3 | ?S-6 |
| Feedstock oil | C | ?C | D | ?D |
| Reaction condition | ||||
| Temperature, ℃ | 400 | 400 | 450 | ?450 |
| Pressure, MPa | 0.5 | 0.5 | 2.5 | ?2.5 |
| The diesel oil weight (hourly) space velocity (WHSV), hour -1 | 10 | 3.0 | 0.5 | ?50 |
| Oil ratio | 20 | 15 | 1 | ?8 |
| The volume ratio of hydrogen donor and diesel raw material | Naphthane/0.1 | Naphthane/0.1 | Coking dry gas/500 | Coking dry gas/500 |
| Product distributes, heavy % | ||||
| Dry gas | 0.16 | 0.34 | 0.18 | ?0.28 |
| Liquefied gas | 1.29 | 0.32 | 1.75 | ?0.87 |
| Gasoline | 1.65 | 1.24 | 1.92 | ?1.15 |
| Diesel oil | 96.53 | 97.52 | 95.83 | ?97.04 |
| Coke | 0.35 | 0.56 | 0.31 | ?0.64 |
| Loss | 0.02 | 0.02 | 0.01 | ?0.02 |
| The diesel oil main character | ||||
| Sulphur, μ g/g | 6.5 | 17.3 | 85.6 | ?165.0 |
| Desulfurization degree, heavy % | 99.39 | 98.37 | 99.17 | ?98.39 |
| Density (20 ℃), kilogram/rice 3 | 875.2 | 878.2 | 885.8 | ?893.2 |
| Cetane number | 33.0 | 28.0 | 27.1 | ?21.2 |
Claims (17)
1. desulphurization sorbent composition; It is characterized in that; With the adsorbent gross weight serves as to calculate benchmark; This adsorbent comprises: the phosphorus modified RE zeolite mixture of the heavy % of 1-30, and the carrier of the reactive metal oxides of 5～40 heavy % and 30～94 heavy %, wherein carrier comprises aluminium oxide and zinc oxide; Said rare earth zeolite mixture refers to that the phosphorus modified RE selects the mixture that shape zeolite and phosphorus modified RE faujasite mixed according to part by weight in 10: 1 to 1: 10, and said reactive metal is selected from more than one metals in cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, the vanadium.
2. according to the adsorbent composition of claim 1, it is characterized in that, serves as to calculate benchmark with the weight of phosphorus modified RE zeolite mixture, and the composition of phosphorus modified RE zeolite mixture is following: phosphorus is with P
2O
5Meter accounts for the heavy % of 1-10; Rare earth is with RE
2O
3Meter accounts for the heavy % of 1-35; Surplus is a zeolite mixture.
3. according to the adsorbent composition of claim 1, it is characterized in that said rare earth zeolite mixture refers to that the phosphorus modified RE selects the mixture that shape zeolite and phosphorus modified RE faujasite mixed according to part by weight in 1: 1.1 to 1: 5.
4. according to the adsorbent composition of claim 1 or 3, it is characterized in that said rare earth shape-selective zeolite is selected from the five-membered ring silica-rich zeolite that contains rare earth, the ZRP zeolite that contains rare earth, in the Beta zeolite that contains rare earth one or more, its silica alumina ratio is 20-500.
5. according to the adsorbent composition of claim 4, it is characterized in that said five-membered ring silica-rich zeolite is selected from one or more in ZSM-5 zeolite, ZSM-8 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-48 zeolite, the ZSM-57 zeolite; The Beta zeolite is selected from one or more in Na β type, H β type, the US zeolite beta.
6. according to the adsorbent composition of claim 1 or 3, it is characterized in that said rare earth faujasite is that X type series zeolite is or/and Y type series zeolite.
7. according to the adsorbent composition of claim 6, it is characterized in that said rare earth Y type zeolite is selected from one or more in REY type, REHY type, the REUSY type zeolite.
8. according to the adsorbent composition of claim 1, it is characterized in that said reactive metal is that cobalt is or/and nickel.
9. according to the adsorbent composition of claim 1, it is characterized in that, serves as to calculate benchmark with the weight of carrier, and said carrier comprises the aluminium oxide of 5～30 heavy %, the zinc oxide of 10～65 heavy %, the clay of surplus.
10. according to the adsorbent composition of claim 9, it is characterized in that said clay is selected from silica, amorphous aluminum silicide, kaolin, imvite, bentonite, diatomite, sepiolite, tiredly takes off in the soil more than one.
11., it is characterized in that said kaolin is halloysite according to the adsorbent composition of claim 10.
12. a method for preparing the said adsorbent composition of claim 1 is characterized in that this method comprises the following steps:
(1) phosphorus modified RE zeolite mixture colloidal sol preparation
With commercially available rare earth shape-selective zeolite and rare earth faujasite according to a certain percentage mechanical mixture evenly be mixed with zeolite mixture; According to zeolite mixture: ammonium salt: the weight ratio of deionized water=1: 0～1: 3～40 was 50～100 ℃ of following ion-exchanges 0.1～5 hour; Filter, wash the back repeated exchanged and once obtain ammonium type rare earth zeolite mixture, its Na
2O content is not more than 0.15 heavy %; Ammonium type rare earth zeolite mixture and phosphorous water soluble compound and deionized water mix according to the weight ratio 1: 0.3～1 of water and solid; At room temperature stir dipping 0.3～5 hour, make phosphorous rare earth zeolite mixture colloidal sol;
(2) carrier colloidal sol preparation
The powder carrier material of reservation amount or the solid sediment of carrier are mixed making beating with deionized water; Obtain the slurries that solid content is 5～30 weight %; The aqueous solution that under agitation adds hydrochloric acid or nitric acid; Make slurries pH=2～4, stir, under 30～100 ℃, leave standstill and made carrier colloidal sol at least in aging 0.5 hour;
(3) solid particle preparation
With step (1) and step (2) make aging after carrier colloidal sol mixes, and add an amount of aluminium colloidal sol, adsorbent solid content and aluminium colloidal sol solid content weight ratio are 10～50, continue stirring up to the formation uniform sol; Is 250～300 ℃ with this colloidal sol at the control exhaust temperature, and atomisation pressure is 50～60 atmospheric pressure, and spray drying forming makes microspheric solid carrier particle, and free Na is removed in the microspheroidal solid particle washing that obtains
+, 100～200 ℃ of down oven dry after at least 2 hours, roasting at least 2 hours under 500～800 ℃ of conditions again obtains the particle of microspheroidal rare earth zeolite mixture and carrier mixture;
(4) the metal oxide active component is introduced
One or more slaine of the containing metal active component of reservation amount is made into the aqueous solution that concentration of metal ions is 1～10mol/L; At room temperature add the microspheroidal rare earth zeolite mixture that step (3) makes and the particle of carrier mixture according to the ratio of metal oxide and carrier; Add the ammoniacal liquor that concentration is 0.5～5mol/L while stirring, keeping pH is 7～10, constantly be stirred to deposition fully after; Being warming up to 60～100 ℃ also placed aging 0.5 hour at least; Filter, washing leaching cake is to there not being the mixture that acid ion makes metal hydroxides rare earth zeolite mixture and carrier material, after drying at least 2 hours under 100～200 ℃; Roasting at least 2 hours under 500～800 ℃ of conditions is again pulverized, sieving obtains the microspheroidal absorbent particles.
13., it is characterized in that said phosphorous water soluble compound is selected from more than one in orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), the ammonium phosphite according to the method for claim 12.
14. an application rights requires 1 said adsorbent composition to reduce the method for sulfur content of light hydrocarbon oil; It is characterized in that sulfur-bearing light hydrocarbon oil raw material and hydrogen donor after the preheating; Entering is equipped with in the reactor of adsorbent; At temperature 350-450 ℃, pressure 0.5-2.5MPa, feedstock oil weight (hourly) space velocity (WHSV) 0.5-10h
-1React under the condition of the weight ratio 1-20 of adsorbent total amount and hydrocarbon oil crude material; Material behind the separating reaction; Product is sent into subsequent separation system and is carried out the product separation, and reacted adsorbent to be generated coke burning regeneration behind stripping, the adsorbent after regeneration Returning reactor after the hydrogen donor reduction recycles.
15. according to the method for claim 14, the hydrocarbon oil crude material that it is characterized in that said sulfur-bearing is selected from more than one in gasoline, kerosene, diesel oil, the gas oil fraction.
16. method according to claim 14; It is characterized in that said hydrogen donor is selected from more than one in hydrogen, hydrogen-containing gas, the hydrogen supply agent; Wherein hydrogen is the hydrogen of various purity; Hydrogen-containing gas is more than one in catalytic cracked dry gas, coking dry gas, the thermal cracking dry gas, and hydrogen supply agent is selected from more than one in naphthane, decahydronaphthalene, the dihydro indenes.
17., it is characterized in that said reactor is selected from the reactor of fluidized-bed reactor, fixed bed reactors, moving-burden bed reactor or other type and compound according to the method for claim 14.
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| CN102839011B (en) * | 2011-06-23 | 2015-03-18 | 中国石油化工股份有限公司 | Adsorption desulfurization method |
| CN103212389B (en) * | 2012-01-18 | 2015-05-13 | 中国石油天然气股份有限公司 | Method for preparing gas organic sulfur refining removal adsorbent through using petroleum coke |
| CN103773431B (en) * | 2012-10-24 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of gasoline desulfating method |
| CN103773432B (en) * | 2012-10-24 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of gasoline desulfating method |
| CN103433056B (en) * | 2013-09-11 | 2016-08-10 | 广东中烟工业有限责任公司 | A kind of based on heterogeneous Fenton catalyst that meerschaum is carrier and preparation method thereof |
| CN104549139B (en) * | 2013-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Cu-containing molecular sieve adsorbent and preparation method thereof |
| CN105642225B (en) * | 2014-11-10 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of preparation method of adsorbent for unsaturated acid ester depickling |
| CN105854917B (en) * | 2015-01-22 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN105771892A (en) * | 2016-03-24 | 2016-07-20 | 山东成泰化工有限公司 | Oil product desulfurizing agent and desulfurizing method thereof |
| RU2648985C1 (en) * | 2017-08-14 | 2018-03-29 | Дмитрий Александрович Усанов | Method for increasing octane number |
| CN110586028B (en) * | 2019-10-08 | 2021-11-19 | 中国石油化工股份有限公司 | Desulfurizing agent and preparation method and application thereof |
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| US6350422B1 (en) * | 1998-09-21 | 2002-02-26 | Phillips Petroleum Company | Sorbent compositions |
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