CN101433817A - Desulphurization sorbent - Google Patents
Desulphurization sorbent Download PDFInfo
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- CN101433817A CN101433817A CNA2007101774156A CN200710177415A CN101433817A CN 101433817 A CN101433817 A CN 101433817A CN A2007101774156 A CNA2007101774156 A CN A2007101774156A CN 200710177415 A CN200710177415 A CN 200710177415A CN 101433817 A CN101433817 A CN 101433817A
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Abstract
The invention discloses a desulfurization adsorbent, which comprises 1 to 30 weight percent of 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; the rare earth-zeolite mixture and a carrier mixture are preformed into porous heat-resistant solid particles, and then active metal ingredients are introduced on the solid particles to obtain the 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 the pay attention to day by day of people, more and more stricter to the restriction of the sulfur content in the light hydrocarbon oil that acts as a fuel to environmental protection.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.As US6350422, US6955752, US6482314, US6428685, US6346190 is described, adopt adsorbent that light oil is faced H-H reaction absorption, the hydrogen consumption is lower, the desulfuration efficiency height, can the production sulfur content at following gasoline of 30 μ g/g or diesel oil, its adsorbent is by going back the ortho states cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, in the vanadium metal one or both are stated from the carrier and constitute, described carrier adopts the zinc oxide oxide, the mixture of silica and aluminium oxide, zinc oxide accounts for 10～90 heavy % in the carrier, silica accounts for 5～85 heavy %, aluminium oxide accounts for 5～30 heavy %.Carrier component and metal component through mix, granulating, drying, calcining make bimetallic junction configuration desulfuration adsorbent, 0.7～2.1MPa, 343～413 ℃ with face the sulphur of catching under the operating condition of hydrogen 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, 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 is generally at 50-80%, can only be used to produce the low-sulfur product oil, loss of octane number is low.
Summary of the invention
One of purpose of the present invention is that a kind of adsorbent that reduces sulfur content in the light-weight fuel oil is provided on the basis of existing technology.
Two of purpose of the present invention provides described preparation of adsorbent method.
Three of purpose of the present invention provides a kind of method that described adsorbent reduces the petroleum hydrocarbon sulfur content of using.
Desulfuration adsorbent provided by the invention comprises: the rare earth 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.
Described rare earth zeolite mixture accounts for the heavy % of 1-30 of adsorbent composition gross weight, preferred 5～25 heavy %.With the weight of rare earth zeolite mixture serves as to calculate benchmark, rare earth zeolite mixture composed as follows: rare earth accounts for the heavy % of 1-35 in RE2O3; Zeolite mixture accounts for the heavy % of 65-99.
Described rare earth all is selected from one or more elements among La, Ce, Pr, Nd, the Sm.
Described rare earth zeolite mixture refers to the mixture that rare earth shape-selective zeolite and rare earth faujasite are mixed according to the preferred 1:1.1 to 1:5 of part by weight 10:1 to 1:10.
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.
Described 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.
Described reactive metal oxides accounts for 5～40 heavy % of adsorbent composition total amount, the heavy % of preferred 15-30.Described 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.
Described zinc sial medium carrier argillaceous 5～85 heavy %, preferred 35～80 heavy % of containing.With the weight of carrier serves as to calculate benchmark, carrier composed as follows: aluminium oxide 5～30 heavy %, preferred 5～15 heavy %; Zinc oxide 10～65 heavy %, preferred 15～50 heavy %; Surplus is a clay.Described 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.Described 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, with the mixture of above-mentioned rare earth shape-selective zeolite and rare earth faujasite 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 rare earth zeolite can mix formation mixture, dry forming, roasting more uniformly basically by any suitable mode with carrier mixture.Rare earth 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 as dipping promptly adopts above-mentioned one or more metal salt solutions to flood in type carrier; Perhaps Chen Dian method 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.Described 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 of the present invention adopts the form of slaine in preparation process, thereby the method for optimizing of introducing metal active constituent is the method for precipitation 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 as follows:
(1) rare earth 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: the weight ratio of ammonium salt: 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 zeolite, its Na
2O content is not more than 0.15 heavy %.At room temperature the aqueous solution with above-mentioned ammonium type zeolite and metering rare earth chloride stirred dipping 2 hours, 120～200 ℃ of oven dry, and 450～850 ℃ of roastings 0.5～4 hour obtain with RE
2O
3The content of rare earth of meter is the zeolite mixture of the heavy % of 1.0-35.The rare earth zeolite mixture that makes is mixed according to solid-liquid weight ratio 1:1～1:10 with decationized Y sieve water, making beating, stirring makes the rare earth zeolite 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 precipitation 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, sieve and obtain the microspheroidal absorbent particles.
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 enter in the reactor that adsorbent is housed, 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, 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 described 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 described sulfur-bearing is preferably in more than the 500 μ g/g more than 100 μ g/g.
Described 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.
Described 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, conveying 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 is made up of inorganic oxides such as going back metals such as ortho states cobalt, nickel, rare earth zeolite mixture, zinc oxide and silica, aluminium oxide, kaolin, the employing sol-gel process makes, characteristics such as it is desulphurizing activated good to have, and adsorbent is evenly distributed, and intensity is good;
2, the preferred cobalt of adsorbent provided by the invention, the ortho states of going back of one or both metals in the nickel is an active component, preferred silica, aluminium oxide, the above mixture of in the kaolin two or three is a carrier, add a certain amount of rare earth zeolite mixture, by 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 %, 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 schematic diagram 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 given further instruction, but therefore do not make the present invention be subjected to any restriction.
Accompanying drawing is that hydrocarbon ils provided by the invention faces the method flow schematic diagram 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.Described regenerator, regenerative agent reductor are fluid bed.
Gasoline fraction raw material after the preheating and hydrogen donor enter 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 to 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 enters stripper 3, by from the entrained reaction oil gas of the steam stripping of pipeline 4 adsorbent to be generated, spent agent behind the stripping enters regenerator 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, regenerated flue gas is drawn regenerator through pipeline 12, the reproducing adsorbent of high temperature enters regenerative agent reductor 16 through pipeline 15, adopt the nitrogen stripping, after the cooling, with hydrogen reducing, desulfurizing agent after the reduction returns carrier pipe 2 bottom cycle by regenerator sloped tube 17 and uses, and loosening wind nitrogen enters regenerative agent reductor 16 through pipeline 18.
The following examples will give further instruction to method provided by the invention, but therefore not make the present invention be subjected to 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 being prepared as follows of adsorbent solids particle:
The primary raw material of carrier that present embodiment adopts is as follows:
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%, the outstanding waffle worker in Cangzhou 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 %, Hubei Mingliu Leituoshi Stone Science ﹠ Technology Co. Ltd.'s product)+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%), continues to stir, and up to forming uniform sol, makes 1 respectively
#, 2
#, 3
#Carrier colloidal sol, stand-by.
Present embodiment adopts being prepared as follows of rare earth zeolite sol:
Present embodiment adopts the raw material of rare earth zeolite as follows:
S1
#Rare earth zeolite mixture: 7.2 kilograms of ZSM-5 zeolite (silica alumina ratios 25, Qilu Petrochemical company catalyst plant is produced)+0.8 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);
S2
#Rare earth zeolite mixture: 0.5 kilogram of ZRP zeolite (silica alumina ratio 50, Qilu Petrochemical company catalyst plant is produced)+2.5 kilograms of HY zeolites (silica alumina ratio 3.8, Qilu Petrochemical company catalyst plant is produced)+2.31 kilograms of rare earth chlorides;
S3
#Rare earth zeolite mixture: 0.5 kilogram of Na β zeolite (silica alumina ratio 50, Qilu Petrochemical company catalyst plant is produced)+5.5 kilograms of 13X zeolites (silica alumina ratio 2.3, Qilu Petrochemical company catalyst plant is produced)+7.95 kilograms of rare earth chlorides;
Respectively with above-mentioned zeolite mixture according to zeolite mixture: the weight ratio of ammonium nitrate: deionized water=1:1:20 is 90 ℃ of following ion-exchanges 2 hours, filters, washing back repeated exchanged once obtains the ammonium type and select 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 S1
#, S2
#, S3
#The rare earth shape-selective zeolite.The rare earth zeolite that makes is mixed according to solid-liquid weight ratio 1:1～1:10 with decationized Y sieve water, making beating, stirring makes the rare earth zeolite sol.
The above-mentioned S1 that makes
#, S2
#, S3
#The rare earth zeolite sol respectively with above-mentioned C1
#, C2
#, C3
#Carrier colloidal sol mixes, 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 S1
#-C1
#, S2
#-C2
#, S3
#-C3
#The rare earth solid particle.
Embodiment 1-3
Embodiment 1-3 explanation contains adsorbent composition, the preparation method of rare earth zeolite mixture.
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, stand-by.
At room temperature with nickel chloride aqueous solution and S1
#-C1
#Solid particle mixes; add the ammoniacal liquor that concentration is 3mol/L while stirring; keeping pH is 7～10; constantly be stirred to precipitation fully after; being warming up to 90 ℃ also placed aging 0.5 hour at least; filter, washing leaching cake is washed to no chlorion to there not being the mixture that acid ion makes nickel hydroxide and P-RE-ZSM5, P-REY and alumina supporting material.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/S1
#-C1
#, called after ZYS-1.
At room temperature the aqueous solution saturation with cobalt nitrate and nickel nitrate floods S2
#-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/S2
#-C2
#, called after ZYS-2.
With 7.3 kilograms of cobalt oxides (Zhangjagang City China adopted chemical industry Co., Ltd product) and S3
#-C3
#Solid particle adds the making beating of 60 kg of water; Direct and and the S3 in back perhaps pulls an oar cobalt oxide 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/S3
#-C3
#, called after ZYS-3.
The composition of adsorbent ZYS-1, ZYS-2, ZYS-3 (each component serves as to calculate benchmark with the gross weight of adsorbent all) and polishing machine see Table 2.
Comparative Examples 1-3
Compare with the adsorbent composition of embodiment 1-3, the explanation of this Comparative Examples does not contain composition, conventional preparation method and the performance of the bimetallic oxide adsorbent of rare earth zeolite mixture.
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.
As can be seen from Table 2, adsorbent ZYS-1, ZYS-2, ZYS-3 intensity are all better, and its wear rate is all less than 1.0%h
-1More than, all greater than adsorbent S-4, the 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 rare earth 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 ZYS-1, ZYS-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 contact with adsorbent S-4, S-5 behind the hydrogen reducing respectively in the small-sized fluidized bed reactor 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.
As can be seen from Table 3, with the gasoline desulfur product oil phase contrast that does not add the zeolite mixture adsorbent, add the gasoline desulfur rate height of P-contained zeolite mixture adsorbent, all more than 97.19 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 rare earth zeolite mixture is used for the situation of diesel fuel desulfurization.
With raw material diesel oil C, D in the table 1 is raw material, and the investigation diesel raw material fully contacts with adsorbent ZYS-2, ZYS-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 contact with adsorbent S-5, S-6 behind the hydrogen reducing respectively in the small-sized fluidized bed reactor 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.
As can be seen 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 99.04 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 | |
Comparative Examples 2 | |
Comparative Examples 3 | |
| The adsorbent numbering | ZYS-1 | S-4 | ZYS-2 | S-5 | ZYS-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 |
| Rare earth, heavy % | 0.05 | - | 2.3 | - | 6.0 | - |
| Select the shape zeolite, heavy % | ZSM-5/ 4.14 | - | ZRP/ 2.13 | - | β/ 1.8 | - |
| Faujasite, heavy % | Y/ 0.41 | - | HY/ 10.67 | - | 13X/ 18.2 | - |
| Wear rate, %h -1 | 0.8 | 1.4 | 0.85 | 1.6 | 1.1 | 2.1 |
Table 3
| |
Comparative Examples 4 | |
Comparative Examples 5 | |
| Adsorbent | ZYS-1 | S-4 | ZYS-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), |
4 | 4 | 8 | 8 |
| |
5 | 5 | 10 | 10 |
| Hydrogen and gasoline volume ratio | 300 | 300 | 500 | 500 |
| Product distributes, heavy % | ||||
| Gas | 1.5 | 0.56 | 1.35 | 0.49 |
| Gasoline | 98.15 | 99.14 | 98.2 | 99.1 |
| Diesel oil | 0.16 | 0.15 | 0.18 | 0.15 |
| Coke | 0.18 | 0.14 | 0.26 | 0.24 |
| Loss | 0.01 | 0.01 | 0.01 | 0.02 |
| The gasoline main character | ||||
| RON | 95.1 | 88.3 | 91.0 | 83.4 |
| MON | 81.5 | 74.1 | 80.2 | 72.8 |
| Sulphur, μ g/g | 3.5 | 36.2 | 8.5 | 23.1 |
| Alkali nitrogen, μ g/g | 8.5 | 9.8 | 7.3 | 10.2 |
| Benzene, heavy % | 0.9 | 2.4 | 0.5 | 3.5 |
| Alkene, heavy % | 22.5 | 26.5 | 14.6 | 20.34 |
| Desulfurization degree, heavy % | 97.19 | 70.95 | 99.50 | 98.64 |
Table 4
| Embodiment 6 | Comparative Examples 6 | Embodiment 7 | Comparative Examples 7 | |
| Adsorbent | ZYS-2 | S-5 | ZYS-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 | 0.20 | 0.34 | 0.20 | 0.28 |
| Liquefied gas | 1.30 | 0.32 | 1.80 | 0.87 |
| Gasoline | 1.58 | 1.24 | 1.80 | 1.15 |
| Diesel oil | 96.43 | 97.52 | 95.63 | 97.04 |
| Coke | 0.47 | 0.56 | 0.56 | 0.64 |
| Loss | 0.02 | 0.02 | 0.01 | 0.02 |
| The diesel oil main character | ||||
| Sulphur, μ g/g | 8.8 | 17.3 | 98.9 | 165.0 |
| Desulfurization degree, heavy % | 99.17 | 98.37 | 99.04 | 98.39 |
| Density (20 ℃), kilogram/rice 3 | 876.5 | 878.2 | 888.8 | 893.2 |
| Cetane number | 32.5 | 28.0 | 26.8 | 21.2 |
Claims (16)
1, a kind of desulfuration adsorbent, it is characterized in that, serve as to calculate benchmark with the adsorbent gross weight, and this adsorbent comprises: the rare earth zeolite mixture of the heavy % of 1-30, the carrier of the reactive metal oxides of 5～40 heavy % and 30～94 heavy %, wherein carrier comprises aluminium oxide and zinc oxide.
2, according to the adsorbent of claim 1, it is characterized in that, serves as to calculate benchmark with the weight of rare earth zeolite mixture, rare earth zeolite mixture composed as follows: rare earth is with RE
2O
3Meter accounts for the heavy % of 1-35; Zeolite mixture accounts for the heavy % of 65-99.
3,, it is characterized in that described rare earth zeolite mixture refers to the mixture that rare earth shape-selective zeolite and rare earth faujasite are mixed according to the preferred 1:1.1 to 1:5 of part by weight 10:1 to 1:10 according to the adsorbent of claim 1 or 2.
4, according to the adsorbent of claim 3, it is characterized in that described 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,, it is characterized in that described 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 according to the adsorbent composition of claim 4; The Beta zeolite is selected from one or more in Na β type, H β type, the US zeolite beta.
6,, it is characterized in that described rare earth faujasite is that X type series zeolite is or/and Y type series zeolite according to the adsorbent of claim 3.
7,, it is characterized in that described rare earth Y type zeolite is selected from one or more in REY type, REHY type, the REUSY type zeolite according to the adsorbent of claim 6.
8,, it is characterized in that described reactive metal is selected from one or more metals in cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, the vanadium according to the adsorbent of claim 1.
9,, it is characterized in that described reactive metal is that cobalt is or/and nickel according to the adsorbent of claim 1.
10, according to the adsorbent of claim 1, it is characterized in that, serves as to calculate benchmark with the weight of carrier, and described carrier comprises the aluminium oxide of 5～30 heavy %, the zinc oxide of 10～65 heavy %, the clay of surplus.
11,, it is characterized in that described clay is selected from silica, amorphous aluminum silicide, kaolin, halloysite, imvite, bentonite, diatomite, sepiolite, tired one or more mixtures that take off in the soil according to the adsorbent of claim 1.
12, a kind of method for preparing the described adsorbent of claim 1 is characterized in that this method comprises the following steps:
(1) rare earth 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: the weight ratio of ammonium salt: 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 zeolite, its Na
2O content is not more than 0.15 heavy %.At room temperature the aqueous solution with above-mentioned ammonium type zeolite and metering rare earth chloride stirred dipping 2 hours, 120～200 ℃ of oven dry, and 450～850 ℃ of roastings 0.5～4 hour obtain with RE
2O
3The content of rare earth of meter is the zeolite mixture of the heavy % of 1.0-35.The rare earth zeolite mixture that makes is mixed according to solid-liquid weight ratio 1:1～1:10 with decationized Y sieve water, making beating, stirring makes the rare earth zeolite 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.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 precipitation 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, sieve and obtain the microspheroidal absorbent particles.
13, a kind of application rights requires 1 described adsorbent 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, enter in the reactor that adsorbent is housed, 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, reacted adsorbent to be generated coke burning regeneration behind stripping, the adsorbent after regeneration Returning reactor after the hydrogen donor reduction recycles.
14, according to the method for claim 13, the hydrocarbon oil crude material that it is characterized in that described sulfur-bearing is selected from one or more the mixture in gasoline, kerosene, diesel oil, the gas oil fraction.
15, according to the method for claim 13, it is characterized in that described 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, hydrogen-containing gas is one or more the mixture in dry gas that this method is produced, catalytic cracked dry gas, coking dry gas, the thermal cracking dry gas, and hydrogen supply agent is selected from one or more the mixture in naphthane, decahydronaphthalene, the dihydro indenes.
16,, it is characterized in that described 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 13.
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