CN101434855B - Sorbent for reducing sulfide in light hydrocarbon oil - Google Patents
Sorbent for reducing sulfide in light hydrocarbon oil Download PDFInfo
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Abstract
The invention provides a sorbent used for reducing the content of sulfide in light hydrocarbon oil. According to weight percentage, the sorbent comprises 1-30% of phosphorus-modified rare earth shape-selective zeolite, 5-40% of active metal oxide and 30-94% of carrier; wherein, the carrier comprises alumina and zinc oxide; the rare earth shape-selective zeolite is modified by phosphorus and is pre-formed into porous heat-resistance solid grains together with carrier mixture; subsequently, the active metal oxide is led into the solid grains, thus preparing the sorbent; the light hydrocarbon oil raw material containing the sulfur and hydrogen donor enter a reactor filled with the sorbent; the materials are separated after reaction; the reaction products are sent to a subsequent separation system so that the product is separated; the sorbent to be regenerated after reaction is stripped, burned and regenerated; and the regenerated sorbent is reduced by the hydrogen donor and subsequently returns to the reactor so as to be circularly used. The sorbent realizes that the sulfide of light hydrocarbon oil is deeply removed, and meanwhile, the octane number of the outcome gasoline is higher, while the benzene content is lower and the strength is higher.
Description
Technical field
The invention belongs to a kind of reduce light petroleum hydrocarbon in the adsorbent of sulfur content and preparation thereof, application.
Background technology
Along with the pay attention to day by day of people to environmental protection, more and more stricter to the restriction of the sulfur content in the light hydrocarbon oil that acts as a fuel.Take gasoline as example, EPA (EPA) regulation sulphur limit value is 30 μ g/g (TierII); Europe requires content of sulfur in gasoline lower than 50 μ g/g (Europe IV discharge standard); China also will be progressively in line with international standards 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 hydrogen addition technology, and it is also a very attracting technology in recent years that absorption method removes sulfur-containing compound in fuel oil.as US6350422, US6955752, US6482314, US6428685, US6346190 is described, adopt adsorbent to face H-H reaction absorption to light oil, the hydrogen consumption is lower, desulfuration efficiency is high, can the production sulfur content at the 30 following gasoline of μ g/g or diesel oil, its adsorbent is by the reduction-state cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, one or both in vanadium metal are stated from carrier and consist of, described carrier adopts the zinc oxide oxide, the mixture of silica and aluminium oxide, in carrier, zinc oxide accounts for 10～90 heavy %, 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 sulphur in catching gasoline under the operating condition of hydrogen, generate metal sulfide or utilize sulfide polarity to remove sulphur, the sulfur-bearing catalyst cyclic regeneration.Although 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, consume without hydrogen, without loss of octane number, but, the same with the mink cell focus catalytic cracking and desulfurizing, its desulfurization degree is affected 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 for the production of 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 light-weight fuel oil is provided on the basis of existing technology.
Two of purpose of the present invention is to provide the preparation method of described adsorbent.
Three of purpose of the present invention is to provide a kind of method that described adsorbent reduces the petroleum hydrocarbon sulfur content of using.
In reduction hydrocarbon ils provided by the invention, the adsorbent of sulfur content comprises: the phosphorus modified RE of the heavy % of 1-30 is selected the shape zeolite, and the carrier of the reactive metal oxides of 5～40 heavy % and 30～94 heavy % is all take the adsorbent gross weight as calculating benchmark.
Described phosphorus modified RE is selected the heavy % of 1-30 that the shape zeolite accounts for the adsorbent gross weight, preferred 3～20 heavy %.Select the weight of shape zeolite take the phosphorus modified RE as calculating benchmark, the phosphorus modified RE is selected the composed as follows of shape zeolite: 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 for selecting the shape zeolite.
Wherein the predecessor of phosphorus can adopt any form phosphorus-containing compound, 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), ammonium phosphite, more preferably phosphoric acid ammonium, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP).
Described rare earth all is selected from one or more elements in La, Ce, Pr, Nd, Sm.
In the Beta zeolite 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, 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, ZSM-57 zeolite; The Beta zeolite comprises one or more in Na β type, H β type, US zeolite beta.The rare earth shape-selective zeolite preferably contains the ZSM-5 zeolite of rare earth or/and contain the ZRP zeolite of rare earth.
Described reactive metal oxides accounts for 5～40 heavy % of adsorbent 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.
The heavy % of described carrier argillaceous 5～85, preferred 35～80 heavy %.Take the weight of carrier as calculating benchmark, carrier composed as follows: the heavy % of aluminium oxide 5～30, preferred 5～15 heavy %; The heavy % of zinc oxide 10～65, preferred 15～50 heavy %; Surplus is 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, tires out one or more mixtures in inorganic oxides such as taking off soil, preferential oxidation silicon, kaolin, the tired mixture that takes off in soil two or more, wherein the weight ratio between any two kinds of clay compositions is 0.1～100: 1, preferred 0.5～50: 1.
Absorbent preparation method provided by the invention is that above-mentioned rare earth shape-selective zeolite is the porous heat-resistant solid particle with carrier mixture is preshaped after the phosphorus modification, then introduces the method for metal active constituent on this solid particle.
The phosphorus modifying method of zeolite provided by the invention can adopt the method for existing various load nonmetal oxides, as the method for dipping, namely 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, grind or the method for not grinding; Perhaps colloidal sol facture etc.
Phosphorus modified RE zeolite and carrier mixture can mix formation mixture uniformly basically by any suitable mode, then dry forming, roasting.The preferred preparation method of phosphorus modified RE zeolite and carrier mixture is sol-gel process.
The present invention introduces the method for metal active constituent on solid particle, can adopt existing various metal oxide-loaded method, as the method for dipping, namely adopts the in type carrier of above-mentioned one or more metal salt solution dippings; Perhaps the method for precipitation, namely adopt 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, grind or the method for not grinding; Perhaps colloidal sol facture, gelling process and hydro-thermal method etc.Described slaine is mainly 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 the method moulding such as granulation, extrusion or spray-drying; Drying, roasting etc. after moulding.Its baking temperature can be 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, preferred preparation method is as follows for adsorbent:
(1) the phosphorus modified RE is selected the preparation of shape zeolite sol
With commercially available rare earth shape-selective zeolite or the rare earth shape-selective zeolite by rare earth exchanged according to zeolite: ammonium salt: the weight ratio of deionized water=1: 0～1: 3～40 (preferred 1: 1: 20) was 50～100 ℃ of lower ion-exchanges 0.1～5 hour, after filtering, washing, repeated exchanged once obtains ammonium type rare earth shape-selective zeolite, its Na
2O content is not more than 0.15 heavy %, and ammonium type rare earth shape-selective zeolite mixes with the weight ratio 1: 0.3～1 of deionized water according to water and solid with phosphorous water soluble compound, and at room temperature stirring was flooded 0.3～5 hour, made phosphorous rare earth shape-selective 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 % by weight, the aqueous solution that under agitation adds hydrochloric acid or nitric acid, make slurries pH=2～4, stir, made carrier colloidal sol at least in standing aging 0.5 hour under 30～100 ℃;
(3) solid particle preparation
With step (1) and step (2) make aging after carrier colloidal sol mix, and add appropriate aluminium colloidal sol, adsorbent solid content and aluminium colloidal sol solid content (take aluminium oxide) weight ratio are 10～50, continue to stir until form uniform colloidal sol; Be 250～300 ℃ with this colloidal sol controlling exhaust temperature, 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
+, in oven dry under 100～200 ℃ after at least 2 hours, then roasting at least 2 hours under 500～800 ℃ of conditions, obtain the particle of microspheroidal rare earth shape-selective zeolite 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 microspheroidal rare earth shape-selective zeolite that step (3) makes and the particle of carrier mixture according to the ratio of metal oxide and carrier, adding while stirring concentration is the ammoniacal liquor of 0.5～5mol/L, keeping pH is 7～10, constantly be stirred to precipitation fully after, be warming up to 60～100 ℃ and placed aging at least 0.5 hour, filter, washing leaching cake is to make the mixture of metal hydroxides rare earth shape-selective zeolite and carrier material without acid ion, after drying at least 2 hours under 100～200 ℃, roasting at least 2 hours under 500～800 ℃ of conditions again, pulverize, sieve and obtain 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), ammonium phosphite, one or more in preferably phosphoric acid ammonium, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP).
The above-mentioned oxidation state reactive metal adsorbent that makes adopts specific method activation process 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 the temperature of 200～400 ℃, under hydrogen partial pressure 0.5-2.5MPa condition, reduction is at least 30 minutes, 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 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 after separating reaction, product is sent into subsequent separation system and is carried out separation of products, reacted adsorbent to be generated coke burning regeneration after 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, 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 more than 100 μ g/g, more than being preferably in 500 μ g/g.
Described hydrogen donor is selected from one or more the mixture in hydrogen, hydrogen-containing gas, 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, thermal cracking dry gas, more than hydrogeneous best 30 volume %, hydrogen supply agent is selected from one or more the mixture in naphthane, decahydronaphthalene, indane.
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 one or more in fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed, dense-phase fluidized bed.
The present invention compared with prior art has following unforeseeable technique effect:
1, adsorbent provided by the invention is selected the inorganic oxides such as shape rare earth zeolite, zinc oxide and silica, aluminium oxide, kaolin and is formed by the metals such as reduction-state cobalt, nickel, phosphorus modification, the employing sol-gel process makes, the 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 reduction-state of one or both metals in nickel is active component, preferential oxidation silicon, aluminium oxide, the above mixture of in kaolin two or three is carrier, add a certain amount of rare earth shape-selective zeolite, by the cooperative effect between these components, when making this adsorbent realize the deep removal sulfide in light hydrocarbon oil, 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, adsorbent provided by the invention is suitable for production super-low sulfur clean gasoline.
When 3, adopting method provided by the present invention to process gasoline stocks, can even realize deep desulfuration under the condition without the hydrogen consumption in the low hydrogen consumption, more than the removal efficiency of sulphur can reach 97 heavy %, can for the production of sulfur content lower than 10 μ g/g's and improved octane number when having reduced gasoline olefin, the yield of gasoline is more than 97 heavy %, the product benzene content in gasoline is low, can be for the production of the clean gasoline with high octane of sulfur content lower than 10 μ g/g.
When 4, adopting method provided by the present invention to process diesel raw material, facing under the condition of hydrogen, diesel raw material has desulfurized effect preferably, more than desulfurization degree reaches 99 heavy %.The aromatic content of diesel oil Cetane number of producing slightly is improved.
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 further described, but does not therefore make the present invention be subject 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 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 with the dense fluidized bed bioreactor, and reaction oil gas is sent into follow-up product separation 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 after 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 nitrogen stripping, after cooling, with hydrogen reducing, desulfurizing agent after reduction returns to carrier pipe 2 bottom cycle by regenerator sloped tube 17 and uses, loosening wind nitrogen enters regenerative agent reductor 16 through pipeline 18.
The following examples will be further described method provided by the invention, but therefore not make the present invention be subject to any restriction.
The feedstock property that uses in embodiment is listed in table 1.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 Engineering Analysis 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 liter/mins of flows are measured adsorbent hourly average abrasion index.
The present embodiment adopts being prepared as follows of adsorbent solids particle:
The primary raw material of carrier that the present embodiment adopts is as follows:
1
#Carrier: (solid content is 64 heavy % to 10 kilograms of boehmites, Shandong Zibo aluminium manufacturer industrial products, lower same)+(solid content is 25 % by weight to 1.0 kilograms of Ludox, produce in vertical sail chemical plant, Qingdao, lower with)+13.1 kilograms of zinc oxide (purity 99.7%, Cangzhou outstanding waffle work Co., Ltd product);
2
#Carrier: 4 kilograms of boehmite+1.0 kilogram Ludox+6 kilograms of kaolin (solid content is 73 % by 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);
3
#Carrier: 5 kilograms of boehmite+4 kilogram kaolin+2 kilograms is tired takes off soil (solid content is 68 % by weight, and From Zhongxiang Hubei is produced)+3.5 kilo sulfuric acid zinc (purity 98%, sea, Jinan chemical industry Co., Ltd product);
The above-mentioned support material that will mix is respectively mixed making beating with deionized water, obtain the slurries that solid content is 15 % by weight, under agitation add the aqueous hydrochloric acid solution (volumetric concentration 30%) of 1.6 kilograms, continue to stir, until form uniform colloidal sol, make respectively 1
#, 2
#, 3
#Carrier colloidal sol, stand-by.
The present embodiment adopts being prepared as follows of phosphorus modified RE zeolite sol:
The present embodiment adopts the raw material of phosphorus modified RE zeolite as follows:
1
#Phosphorus modified RE zeolite: 7.92 kilograms of ZSM-5 zeolites (silica alumina ratio 25, the Qilu Petrochemical Company catalyst plant is produced)+(Inner Mongol Baotou rare earth factory produces 0.356 kilogram of rare earth chloride, and dry basis 48 weighs %, and 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%, lower same)+0.14 kilogram of commercially available phosphoric acid (purity 85%, Hubei auspicious cloud chemical industry Co., Ltd produces);
2
#Phosphorus modified RE zeolite: 2.85 kilograms of ZRP zeolites (silica alumina ratio 50, the Qilu Petrochemical Company catalyst plant is produced)+2.19 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);
3
#Phosphorus modified RE zeolite: 5.4 kilograms of Na β zeolites (silica alumina ratio 50, the Qilu Petrochemical Company catalyst plant is produced)+7.16 kilograms of rare earth chloride+1.21 kilogram diammonium hydrogen phosphates (contain P
2O
564%, Yuntianhua international corporation produces);
Respectively with above-mentioned metering ZSM-5 zeolite, ZRP zeolite, Na β zeolite according to zeolite: ammonium nitrate: the weight ratio of deionized water=1: 1: 20 is filtered 90 ℃ of lower ion-exchanges 2 hours, repeated exchanged once obtains the ammonium type and selects the shape zeolite, its Na after washing
2O content is not more than 0.15 heavy %.At room temperature above-mentioned ammonium type zeolite was stirred dipping 2 hours with the aqueous solution of metering rare earth chloride preparation respectively, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours make RE-ZSM5, RE-ZRP, RE-β rare earth shape-selective zeolite.The rare earth shape-selective zeolite that makes and phosphorous water soluble compound and deionized water are mixed according to water-solid ratio at 2: 1, at room temperature stirred dipping 2 hours, making beating, stirring makes the phosphorus modified RE and selects the shape zeolite sol.
The above-mentioned P-RE-ZSM5 that makes, P-RE-ZRP, P-RE-β phosphorus modified RE are selected the shape zeolite sol respectively with above-mentioned 1
#, 2
#, 3
#Carrier colloidal sol mixes, and adds appropriate aluminium colloidal sol, and adsorbent solid content and aluminium colloidal sol solid content (take aluminium oxide) weight ratio are 15, continues to stir until form uniform colloidal sol; Be 250～300 ℃ with this colloidal sol controlling exhaust temperature, atomisation pressure is 50～60 atmospheric pressure, and spray drying forming makes the solid particle of the microspheric P-RE-ZSM5 of containing, P-RE-ZRP, P-RE-β.Free Na is removed in the microspheroidal solid particle washing that obtains
+, in oven dry under 100～200 ℃ after at least 2 hours, then roasting at least 2 hours under 500～800 ℃ of conditions, microspheroidal P-RE-ZSM5/1 obtained
#, P-RE-ZRP/2
#, P-RE-β/3
#Solid particle.
Embodiment 1-3
The adsorbent that the phosphorous modified RE of embodiment 1-3 explanation is selected the shape zeolite forms, 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, stand-by.
At room temperature with nickel chloride aqueous solution and P-RE-ZSM5/1
#Carrier mixes, adding while stirring concentration is the ammoniacal liquor of 3mol/L, keeping pH is 7～10, constantly be stirred to precipitation fully after, be warming up to 90 ℃ and placed aging at least 0.5 hour, filter, washing leaching cake is washed to without chlorion to make the mixture of nickel hydroxide and P-RE-ZSM5 and alumina supporting material without acid ion.In oven dry under 100～200 ℃ after at least 2 hours, then roasting at least 2 hours under 500～800 ℃ of conditions, pulverize, sieving obtains microspheroidal adsorbent Ni-Zn/P-RE-ZSM5/1
#, called after PZS-1.
At room temperature the aqueous solution saturation with cobalt nitrate and nickel nitrate floods P-RE-ZRP/2
#Carrier constantly stirred dipping after at least 4 hours, and oven dry is at least 2 hours under 100～200 ℃, then roasting at least 2 hours under 500～800 ℃ of conditions, pulverized, sieving obtains microspheroidal adsorbent Co-Ni-Zn/P-RE-ZRP/2
#, called after PZS-2.
With 7.3 kilograms of cobalt oxides (Zhangjagang City China adopted chemical industry Co., Ltd product) and P-RE-β/3
#Rare earth shape-selective zeolite/carrier granular adds 60 kg of water making beating; Perhaps with cobalt oxide separately after making beating directly with P-RE-β zeolite sol and 3
#Carrier colloidal sol mixes, and after stirring, adds appropriate aluminium colloidal sol, and adsorbent solid content and aluminium colloidal sol solid content (take aluminium oxide) weight ratio are 15, continues to stir until form uniform colloidal sol; Be 250～300 ℃ with this colloidal sol controlling exhaust temperature, atomisation pressure is 50～60 atmospheric pressure, and spray drying forming makes the microspheric solid particle that contains cobalt oxide and RE-β.Wash its solid particle and remove free Na
+After, oven dry is at least 2 hours under 100～200 ℃, then roasting at least 2 hours under 500～800 ℃ of conditions, obtains microspheroidal adsorbent Co-Zn/P-RE-β/3
#, called after PZS-3.
The composition of adsorbent PZS-1, PZS-2, PZS-3 (each component is all take the gross weight of adsorbent as calculating benchmark) and polishing machine see Table 2.
Comparative Examples 1-3
Form with the adsorbent of embodiment 1-3 and compare, the not phosphorous modified RE of this Comparative Examples explanation is selected the composition of the bimetallic oxide adsorbent of shape zeolite, conventional preparation method and performance.
According to 1
#, 2
#, 3
#Carrier forms wet mixing, grinds, and dry forming, roasting (drying, method of roasting are with embodiment 1-3), then the impregnating metal ion concentration is the nickel sulfate solution of 1～10mol/L respectively, cobalt nitrate-nickel nitrate mixed aqueous solution and the cobalt acetate aqueous solution.Oven dry, roasting, pulverize, sieving obtains not containing the microspheroidal adsorbent Ni-Zn/1 of rare earth shape-selective zeolite again
#, Co-Ni-Zn/2
#, Co-Zn/3
#, difference called after S-4, S-5, S-6.It forms and polishing machine is listed in table 2.
As can be seen from Table 2, adsorbent PZS-1, PZS-2, PZS-3 intensity are all better, and its wear rate is all less than 1.0%h
-1Above, all greater than adsorbent S-4, the S-5, the S-6 that do not contain the rare earth shape-selective zeolite that adopt the conventional method preparation.
Embodiment 4-5
Embodiment 4-5 explanation phosphorus modified RE is selected the adsorbent of shape zeolite and is used aspect gasoline desulfur.
Feed gasoline A, B in the table 1 be as raw material, investigates the feed gasoline raw material and fully contact with adsorbent PZS-1, PZS-2 respectively in the small-sized fluidized bed reactor and adsorb and the catalyzed conversion situation.Adsorbent loadings 500 grams adopt hydrogen the temperature of 360 ℃ before use, and under the condition that hydrogen flowing quantity is 1.5 l/hs, reduction is 60 minutes.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 adsorbent mixtures to be generated by the water vapour stripping.Adsorbent after stripping contacts with the air that heated regenerates, and the catalyst mixture after regeneration recycles after 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 bimetallic oxide adsorbent S-4, the S-5 of rare earth shape-selective zeolite for the situation of gasoline desulfur.
Feed gasoline A, B contact with adsorbent S-4, S-5 after 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, and do not add the gasoline desulfur product oil phase contrast of selecting the shape zeolite adsorbents, add phosphorous gasoline desulfur rate of selecting the shape zeolite adsorbents high, all more than 96.78 heavy %; Octane number is higher, all higher than feedstock oil; And its benzene content is lower, all lower than feedstock oil.
Embodiment 6-7
Embodiment 6-7 explanation phosphorus modified RE is selected the bimetallic oxide adsorbent of shape zeolite for the situation of diesel fuel desulfurization.
Raw material diesel oil C, D in the table 1 be as raw material, investigates diesel raw material and fully contact with adsorbent PZS-2, PZS-3 respectively in the small-sized fluidized bed reactor and adsorbs and the catalyzed conversion situation.Adsorbent loadings 500 grams adopt hydrogen the temperature of 360 ℃ before use, and under the condition that hydrogen flowing quantity is 1.5 l/hs, reduction is 60 minutes.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 adsorbent mixtures to be generated by the water vapour stripping.Adsorbent after stripping contacts with the air that heated regenerates, and the catalyst mixture after regeneration recycles after 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 bimetallic oxide adsorbent S-5, the S-6 of rare earth shape-selective zeolite for the situation of diesel fuel desulfurization.
Raw material diesel oil C, D contact with adsorbent S-5, S-6 after 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, and do not add the diesel fuel desulfurization product oil phase contrast of selecting the shape zeolite adsorbents, add the diesel fuel desulfurization rate of the phosphorous adsorbent of selecting the shape zeolite higher, all more than 99.17 heavy %; Diesel cetane-number is higher, all 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 ℃), kg/m 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 | PZS-1 | S-4 | PZS-2 | S-5 | PZS-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 | - | 0.8 | - | 2.6 | - |
| Rare earth, heavy % | 0.05 | - | 2.2 | - | 5.4 | - |
| Zeolite, heavy % | ZSM-5 /4.50 | - | ZRP /12.1 | - | β/18.0 | - |
| Wear rate, %h -1 | 0.7 | 1.4 | 0.8 | 1.6 | 1.0 | 2.1 |
Table 3
| |
Comparative Examples 4 | |
Comparative Examples 5 | |
| Adsorbent | PZS-1 | S-4 | PZS-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 | 2.01 | 0.56 | 2.12 | 0.49 |
| Gasoline | 97.70 | 99.14 | 97.53 | 99.1 |
| Diesel oil | 0.13 | 0.15 | 0.13 | 0.15 |
| Coke | 0.15 | 0.14 | 0.21 | 0.24 |
| Loss | 0.01 | 0.01 | 0.01 | 0.02 |
| The gasoline main character | ||||
| RON | 95.9 | 88.3 | 91.8 | 83.4 |
| MON | 82.6 | 74.1 | 81.2 | 72.8 |
| Sulphur, μ g/g | 4.0 | 36.2 | 7.8 | 23.1 |
| Alkali nitrogen, μ g/g | 8.6 | 9.8 | 8.9 | 10.2 |
| Benzene, heavy % | 0.6 | 2.4 | 0.3 | 3.5 |
| Alkene, heavy % | 18.2 | 26.5 | 11.5 | 20.34 |
| Desulfurization degree, heavy % | 96.78 | 70.95 | 99.54 | 98.64 |
Table 4
| Embodiment 6 | Comparative Examples 6 | |
Comparative Examples 7 | |
| Adsorbent | PZS-2 | S-5 | PZS-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 | 0.21 | 0.34 | 0.23 | 0.28 |
| Liquefied gas | 1.33 | 0.32 | 1.82 | 0.87 |
| Gasoline | 1.62 | 1.24 | 1.81 | 1.15 |
| Diesel oil | 96.43 | 97.52 | 95.62 | 97.04 |
| Coke | 0.40 | 0.56 | 0.51 | 0.64 |
| Loss | 0.01 | 0.02 | 0.01 | 0.02 |
| The diesel oil main character | ||||
| Sulphur, μ g/g | 7.2 | 17.3 | 85.4 | 165.0 |
| Desulfurization degree, heavy % | 99.32 | 98.37 | 99.17 | 98.39 |
| Density (20 ℃), kg/m 3 | 874.2 | 878.2 | 884.5 | 893.2 |
| Cetane number | 34.5 | 28.0 | 28.6 | 21.2 |
Claims (14)
1. adsorbent that reduces sulfide in light hydrocarbon oil, it is characterized in that, take the adsorbent gross weight as calculating benchmark, this adsorbent comprises: the phosphorus modified RE of the heavy % of 1-30 is selected the shape zeolite, the carrier of the reactive metal oxides of 5～40 heavy % and 30～94 heavy %, wherein carrier is by aluminium oxide, zinc oxide and Clay composition; Select the weight of shape zeolite take the phosphorus modified RE as calculating benchmark, the phosphorus modified RE is selected the composed as follows of shape zeolite: 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 for selecting the shape zeolite; Described reactive metal is selected from one or more metals in cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, vanadium.
2. according to the adsorbent of claim 1, 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.
3. according to the adsorbent of claim 2, 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, ZSM-57 zeolite; The Beta zeolite is selected from one or more in Na β type, H β type, US zeolite beta.
4. according to the adsorbent of claim 1, it is characterized in that described rare earth shape-selective zeolite is to contain the ZSM-5 zeolite of rare earth or/and contain the ZRP zeolite of rare earth.
5. according to the adsorbent of claim 1, it is characterized in that described reactive metal is that cobalt is or/and nickel.
6. according to the adsorbent of claim 1, it is characterized in that, take the weight of carrier as calculating benchmark, described carrier comprises the aluminium oxide of 5～30 heavy %, the zinc oxide of 10～65 heavy %, the clay of surplus.
7. according to the adsorbent of claim 6, it is characterized in that described clay is selected from silica, amorphous aluminum silicide, kaolin, imvite, bentonite, diatomite, sepiolite, tired one or more mixtures that take off in soil.
8. according to the adsorbent of claim 7, it is characterized in that described kaolin is halloysite.
9. a method for preparing the described adsorbent of claim 1, is characterized in that the method comprises the following steps:
(1) the phosphorus modified RE is selected the preparation of shape zeolite sol
With commercially available rare earth shape-selective zeolite or the rare earth shape-selective zeolite by rare earth exchanged according to zeolite: ammonium salt: the weight ratio of deionized water=1: 0～1: 3～40 was 50～100 ℃ of lower ion-exchanges 0.1～5 hour, after filtering, washing, repeated exchanged once obtains ammonium type rare earth shape-selective zeolite, its Na
2O content is not more than 0.15 heavy %, and ammonium type rare earth shape-selective zeolite mixes with the weight ratio 1: 0.3～1 of deionized water according to water and solid with phosphorous water soluble compound, and at room temperature stirring was flooded 0.3～5 hour, made phosphorous rare earth shape-selective zeolite sol;
(2) carrier colloidal sol preparation
The powder carrier material of scheduled volume or the solid sediment of carrier are mixed making beating with deionized water, obtain the slurries that solid content is 5～30 % by weight, the aqueous solution that under agitation adds hydrochloric acid or nitric acid, make slurries pH=2～4, stir, made carrier colloidal sol at least in standing aging 0.5 hour under 30～100 ℃;
(3) solid particle preparation
With step (1) and step (2) make aging after carrier colloidal sol mix, and add appropriate aluminium colloidal sol, adsorbent solid content and aluminium colloidal sol solid content weight ratio are 10～50, continue to stir until form uniform colloidal sol; Be 250～300 ℃ with this colloidal sol controlling exhaust temperature, 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
+, in oven dry under 100～200 ℃ after at least 2 hours, then roasting at least 2 hours under 500～800 ℃ of conditions, obtain the particle of microspheroidal rare earth shape-selective zeolite and carrier mixture;
(4) the metal oxide active component is introduced
one or more slaine of the containing metal active component of scheduled volume is made into the aqueous solution that concentration of metal ions is 1～10mol/L, at room temperature add microspheroidal rare earth shape-selective zeolite that step (3) makes and the particle of carrier mixture according to the ratio of metal oxide and carrier, adding while stirring concentration is the ammoniacal liquor of 0.5～5mol/L, keeping pH is 7～10, constantly be stirred to precipitation fully after, be warming up to 60～100 ℃ and placed aging at least 0.5 hour, filter, washing leaching cake is to make the mixture of metal hydroxides rare earth shape-selective zeolite and carrier material without acid ion, after drying at least 2 hours under 100～200 ℃, roasting at least 2 hours under 500～800 ℃ of conditions again, pulverize, sieve and obtain the microspheroidal absorbent particles.
10. according to the method for claim 9, it is characterized in that described 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), ammonium phosphite.
11. an 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 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 after separating reaction, product is sent into subsequent separation system and is carried out separation of products, reacted adsorbent to be generated coke burning regeneration after stripping, the adsorbent after regeneration Returning reactor after the hydrogen donor reduction recycles.
12. according to the method for claim 11, 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, gas oil fraction.
13. the method according to claim 11, it is characterized in that described hydrogen donor is selected from more than one in hydrogen, hydrogen-containing gas, 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, thermal cracking dry gas, and hydrogen supply agent is selected from more than one in naphthane, decahydronaphthalene, indane.
14. according to the method for claim 11, 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.
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