CN1485132A - Sulfur transfer catalyst and and the preparation thereof - Google Patents
Sulfur transfer catalyst and and the preparation thereof Download PDFInfo
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Abstract
A sulfur-transferring catalyst comprises a cerium oxide of 2-30% by weight as the active component and a spinel compound of 70-98% by weight containing magnetium and aluminum as the carrier. The spinel compound containing magnetium and aluminum comprises MgO of 5-70%, Al2O3 of 30-95%, an oxide of a rare earth element of 0-15 % except cerium, V2O5 of 0-10%,relative to the total weight of the compound. Moreover, the invention provides a method of producing the catalyst. The sulfur-transferring catalyst has a high efficiency of absorbing and desorbing SO x.
Description
Technical field
The present invention relates to a kind of sulfur transfer catalyst and preparation thereof, more particularly, is a kind of sulfur transfer catalyst that contains the magnesium aluminate spinel composition and preparation method thereof.
Background technology
Fluid catalytic cracking (FCC) is to obtain gasoline, the topmost method of the contour use value light-end products of diesel oil by heavy raw oil.FCC apparatus all is made up of a riser reactor and a regenerator usually.In the FCC operating process, Cracking catalyst microballoon and heavier feedstocks oil with cracking activity carry out the pyrolytic cracking reaction in riser reactor, generate light oil and gas products, and meanwhile, Cracking catalyst also loses cracking activity because of coking.The Cracking catalyst of inactivation need be regenerated.In regenerator, the Cracking catalyst of inactivation is high temperature regeneration in the presence of air.Because of containing a large amount of sulphur compounds in the catalyst surface coke, therefore, in combustion process, can produce a large amount of sulfur oxide SO
x(SO
2And SO
3).SO
xCan corrode regenerator device on the one hand; On the other hand, SO
xAlso serious air pollution can be caused after entering in the atmosphere with regenerator flue gas, therefore, otherwise effective technique control SO must be taked
xDischarging.
At present, control SO
xA kind of effective method of discharging is to add a small amount of fluidizing performance SO close with Cracking catalyst in catalytic cracking catalyst
xSorbing material (also claiming sulfur transfer catalyst).This sorbing material can promote SO in FCC coke burning regeneration process
2Be oxidized to SO
3, and with SO
3Be adsorbed on the surface and form metal sulfate, be adsorbed with SO
3Sorbing material with regeneration after catalyst enter riser reactor, under the reducing condition in reactor, the metal sulfate that is adsorbed on the sorbing material is reduced into H
2S, H
2S enters the FCC gaseous product, reclaims by sulfur recovery facility, thereby, make the SO that enters in the atmosphere
xReduce, metal sulfate is reduced into H
2In the time of S, described sorbing material is also regenerated, and is circulated to regenerator again with the catalyst of inactivation, performance absorption SO
xEffect.
In addition, other industrial process is as SO in the Industrial Boiler
xSO is also adopted in emission control usually
xSorbing material.
U.S.P.4,472,532 disclose the preparation method of the spinel composition of a kind of alkaline-earth metal and aluminium, comprise that (1) mix a kind of acidic aqueous solution of at least a alkaline earth metal component and aluminium wherein of containing with the alkaline solution that contains at least a al composition that anionic form exists, form a kind of mixture that contains liquid phase and alkaline including earth metal and aluminum precipitation, wherein, the pH value of liquid phase remains on the scope of 7.0-8.5 in mixed process, (2) precipitation of roasting gained obtains the spinel composition of alkaline including earth metal and aluminium.This method can also comprise the process that at least a additional metal component is added above-mentioned precipitation or dipping above-mentioned composition.Described additional metal component is selected from IB in the periodic table of elements, IIB, IVB, VIA, VIB, VIIA and VIII family metal, rare earth metal, vanadium, tin, antimony and their mixture.
U.S.P.4,476,245 disclose the preparation method of the spinel composition of a kind of alkaline-earth metal and aluminium, this method comprises that (1) mix a kind of acid solution and a kind of wherein aluminium with the alkaline solution that contains at least a al composition that anionic form exists, (2) with the mixture and the aqueous solution that contains at least a alkaline earth metal component, the precipitation that (3) roasting obtains that obtain.Can also further gained precipitation or spinel composition be contacted with at least a additional metal component in this method, in said composition in the load effective dose can under oxidizing condition, promote SO
2Be oxidized to SO
3The carried metal component.Described additional metal component is selected from IB in the periodic table of elements, IIB, IVB, VIA, VIB, VIIA and VIII family metal, rare earth metal, vanadium, tin, antimony and their mixture.
U.S.P.4,492,677 disclose the preparation method of the spinel composition of a kind of alkaline-earth metal and aluminium, this method comprise (1) with a kind of acid medium that contains at least a alkaline earth metal component, at least aly have the organic compound of intrinsic alkalescence and aluminium wherein mixes with the aluminium alkaline solution that contains that anionic form exists, obtain a kind of mixture that contains liquid phase and alkaline-earth metal and aluminum precipitation, in mixed process, pH value is maintained at about 8.0 or higher, (2) the described precipitation of roasting obtains the spinel composition of alkaline including earth metal and aluminium.Can also contain in the described composition and a kind ofly can promote SO
2Be oxidized to SO
3The additional metal component.Described additional metal component is selected from IB, IIB, IVB, VIA, VIB, VIIA and VIII family metal, rare earth metal, vanadium, tin, antimony and their mixture.
U.S.P.4,522,937 disclose the preparation method of the spinel composition of a kind of alkaline-earth metal and aluminium, comprise that (1) mix a kind of acidic aqueous solution of at least a alkaline earth metal component and aluminium wherein of containing with the alkaline aqueous solution that contains at least a al composition that anionic form exists, obtain containing the mixture of the precipitation of a kind of liquid phase and a kind of alkaline including earth metal and al composition, wherein, at least a in described acid solution and the alkaline solution contains at least a additional metal component, and the consumption of described additional metal component is enough to make contain in the composition of described alkaline including earth metal and al composition and can effectively promotes SO
2Be oxidized to SO
3At least a additional metal component, and, remain on the scope of 7.0-10.5, the resulting precipitation of (2) roasting at the pH value of liquid phase described in the mixed process.Described additional metal component is selected from IB in the periodic table of elements, IIB, IVB, VIA, VIB, VIIB and VIII family metal, rare earth metal vanadium, tin, antimony and their mixture.
In above-mentioned four pieces of patents, the spinel composition of alkaline including earth metal and aluminium all is to adopt acid alkaline earth metal solution and aluminium are wherein mixed with the aluminium alkaline solution that contains that anionic form exists, and precipitation obtains.Relate to Na among the preparation method of this co-precipitation
+In a large number harmful cationic washing such as ion, preparation technology is very loaded down with trivial details.And if adopt spray-dired forming method to prepare the spinelle microballoon, its scuff resistance is very poor, can not satisfy the instructions for use of catalytic cracking process.
U.S.P.4,497,902 disclose a kind of SO that removes from gas
xComposition, said composition contains a kind of inorganic oxide and at least a free or in conjunction with rare earth metal, described rare earth metal is selected from a group that is made up of lanthanum, cerium, praseodymium, samarium, dysprosium, described inorganic oxide compositions is selected from by magnesium aluminate spinel (MgAl
2O
4), a group of forming of the mixture of aluminium oxide and magnesian mixture and magnesia and spinelle.Do not provide the character and the preparation method of spinelle in the specification of this patent, from the example, find, magnesia, a water Alpha-alumina and calcium oxide are mixed, add nitric acid and mix and pinch, obtain a kind of magnesia, Ca of containing after the roasting
3Al
10O
18And magnesium aluminate spinel (MgAl
2O
4) mixture, and dipping goes up cerium, can obtain the described SO of taking off
xComposition.
U.S.P.4,728,635 disclose the spinel composition of a kind of alkaline including earth metal and aluminium, comprise that the acidic composition that there is a kind of aluminium wherein with positively charged group form in (1) and a kind of alkaline compositions of alkaline including earth metal mix, (2) mixture that obtains of roasting obtains the spinel composition of alkaline including earth metal and aluminium.Adopt this method to prepare the spinelle microballoon of alkaline including earth metal and aluminium, not only preparation technology is simple, and has solved the scuff resistance problem.
U.S.P.4 also discloses the sulfur transfer catalyst and preparation method thereof of composition of the spinelle of a kind of alkaline including earth metal and aluminium in 728,635.One of disclosed preparation method is the method by incipient impregnation, the composition of the spinelle of alkaline including earth metal and aluminium soaked earth solution (being preferably cerium solution) and/or contain the solution of vanadium, leave standstill, make sulfur transfer catalyst after dry, the roasting through the long period.Adopt this dipping method to prepare sulfur transfer catalyst, one of shortcoming is that the metal ion of load is difficult to diffuse in the hole of spinel composition, and the reactive metal oxides that forms after the roasting stops up the duct usually, thereby has reduced the SO of sulfur transfer catalyst
xAbsorption and desorption efficient; Two of shortcoming is to adopt this method to prepare sulfur transfer catalyst, if carry out large-scale industrial production, reactive metal oxides is difficult to realize evenly distributing on each microballoon, thereby the scale of process units is restricted; Three of shortcoming be behind the incipient impregnation long period leave standstill the continuity that directly has influence on production, thereby the production efficiency of sulfur transfer catalyst is low.
The preparation method of the sulfur transfer catalyst of the composition of the spinelle of disclosed another kind of alkaline including earth metal and aluminium is the compound that directly adds reactive metal oxides or can generate these reactive metal oxides in the preparation of compositions process of the spinelle of this alkaline including earth metal and aluminium after roasting in this patent.Adopt this method to prepare sulfur transfer catalyst, one of shortcoming be greatly reactive metal oxides be wrapped in the spinelle microballoon body mutually in and can not bring into play catalytic action, reduced the SO of sulfur transfer catalyst equally
xAbsorption and desorption efficient; Two of shortcoming is to contain the scuff resistance that this too much quasi-metal oxides or metallic salt can reduce the sulfur transfer catalyst microballoon greatly in the slurries before the spray-drying.
Summary of the invention
The object of the present invention is to provide a kind of sulfur transfer catalyst that contains the magnesium aluminate spinel composition and preparation method thereof, to overcome the existing in prior technology problem.
Sulfur transfer catalyst provided by the invention is characterized in that:
A, this sulfur transfer catalyst are is benchmark with the catalyst weight with the oxide of the cerium of 2～30 heavy % as active component, contains the magnesium aluminate spinel composition as carrier with 70～98 heavy %; Describedly contain the magnesium aluminate spinel composition to contain in said composition weight be the MgO with 5～70 heavy % of oxide of benchmark, the Al of 30～95 heavy %
2O
3, the rare-earth oxide except that cerium of 0～15 heavy %, the V of 0～10 heavy %
2O
5
The preparation method of b, this sulfur transfer catalyst is as follows:
(1) aluminium oxide and/or aluminium hydroxide, rare earth compound, deionized water and acid except that cerium are mixed and reaction at least 5 minutes, it is 1.5～4 that the addition of acid makes the pH value of the slurries that obtain, and it is 5～20 heavy % that the addition of deionized water, aluminium oxide and/or aluminium hydroxide and rare earth compound makes the solid content of the slurries that obtain;
(2) solution that will contain water-soluble vanadium compound adds in the above-mentioned slurries;
(3) magnesia or magnesium hydroxide are added in the above-mentioned slurries, reacted at least 5 minutes;
(4), obtain containing the magnesium aluminate spinel composition with above-mentioned slurry dried, roasting;
(5) contain the composition of magnesium aluminate spinel more than 5 minutes with containing the cerium solution of magnesium aluminate spinel composition saturated adsorption capacity more than 1.5 times at dipping under the condition of PH2～6;
(6) filter slurries, and filter cake is carried out drying, roasting.
Compared with prior art, the preparation method of sulfur transfer catalyst provided by the invention has the following advantages:
(a) owing to adopt the dipping method supported active metal oxide of excessive maceration extract, metal ion is easy to diffuse in the spinel composition hole, can not occur burning object blocking hole phenomenon after the roasting, thereby has improved the SO of sulfur transfer catalyst
xAbsorption and desorption efficient.
(b) adopt method provided by the invention to prepare sulfur transfer catalyst, reactive metal oxides is evenly distributed on each microballoon, thereby the scale of process units is unrestricted, be convenient to the large-scale industrial production of sulfur transfer catalyst, and do not need the process that leaves standstill of long period, improved production efficiency as incipient impregnation.
(c) adopt method provided by the invention to prepare sulfur transfer catalyst, be not wrapped in the interior mutually sulfur transfer catalyst SO that reduces of body of spinelle microballoon because of reactive metal oxides
xAbsorption and desorption efficient phenomenon.
(d) adopt method provided by the invention to prepare sulfur transfer catalyst, do not contain too much metal oxide or metal salt compound in the slurries before the spray-drying, the scuff resistance of sulfur transfer catalyst microballoon is not had influence.
The specific embodiment
Sulfur transfer catalyst of the present invention is benchmark in the catalyst weight with the oxide of the cerium of 2～30 heavy % as active component (with oxide), preferably with the oxide of the cerium of 2～25 heavy % as active component; The magnesium aluminate spinel composition that contains with 70～98 heavy % is a carrier, and preferably the magnesium aluminate spinel composition that contains with 75～95 heavy % is a carrier.
Of the present inventionly contain that to contain in said composition weight in the magnesium aluminate spinel composition be the MgO with 5～70 heavy % of oxide of benchmark, the Al of 30～95 heavy %
2O
3, the rare-earth oxide except that cerium of 0～15 heavy %, the V of 0～10 heavy %
2O
5Preferably contain the MgO of 20～65 heavy %, the Al of 20～79 heavy %
2O
3, the rare-earth oxide except that cerium of 0.5～10 heavy %, the V of 0.5～5 heavy %
2O
5
Aluminium oxide described in the present invention is selected from can be by in the aluminium oxide of sour peptization one or more, as in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, the θ-aluminium oxide one or more.Described aluminium hydroxide is also referred to as hydrated alumina, it can be selected from a gibbsite and the water aluminium oxide one or more, as in gibbsite, surge aluminium stone, promise diaspore, diaspore, thin aluminium stone, the boehmite (being vacation-boehmite) one or more.Described aluminium oxide and/or aluminium hydroxide is boehmite more preferably.
Described rare earth metal except that cerium is selected from one or more in lanthanum, praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium, more preferably lanthanum or rich lanthanum and be substantially free of the rare earth metal of cerium.
Described acid is selected from one or more in various organic acids and the inorganic acid, as nitric acid, hydrochloric acid, sulfuric acid, formic acid, acetate, oxalic acid etc., and wherein more preferably nitric acid and/or hydrochloric acid.
Drying in the described preparation of compositions that contains magnesium aluminate spinel can adopt conventional drying means, and as airing, oven dry, spray-dired method, baking temperature can be a room temperature to 300 ℃, preferably 100～200 ℃.
The temperature and time of the roasting in the described preparation of compositions that contains magnesium aluminate spinel is that this area prepares spinel composition sintering temperature and time commonly used, and sintering temperature is generally 550～850 ℃, preferably 650～800 ℃.Roasting time generally was not less than 0.5 hour, was preferably 0.5～6 hour, more preferably 1～4 hour.
Described vfanadium compound is selected from one or more in any water-soluble vanadium compound, preferably V
2O
5The oxalic acid complex compound.
According to sulfur transfer catalyst preparation method provided by the invention, the volume of the maceration extract in the described step (5) is not less than 1.5 times of the saturated adsorption capacity that contains the magnesium aluminate spinel composition, is preferably 3～8 times.
According to sulfur transfer catalyst preparation method provided by the invention, the pH value of the maceration extract in the described step (5) is not less than 2.0, and preferably 2.5～6.
According to sulfur transfer catalyst preparation method provided by the invention, the concentration of the maceration extract in the described step (5) is according to the load capacity of the required reactive metal oxides of sulfur transfer additive and contain in the carrier of magnesium aluminate spinel composition magnesian content and decide.
According to Preparation of catalysts method provided by the invention, described cerium compound is selected from one or more in any water-soluble cerium compound, comprise trivalent and ceric water soluble compound, wherein, preferred cerium compound is selected from the nitrate of cerium, in the chloride one or more.
According to sulfur transfer catalyst preparation method provided by the invention, the dip time in the described step (5) is greater than 5 minutes, preferably 10～60 minutes.
According to sulfur transfer catalyst preparation method provided by the invention, be filtered into the solid separation method that solid catalyst use in producing described in the step (6), such as belt filter, rotary drum filtration or the like.
According to sulfur transfer catalyst preparation method provided by the invention, conventional condition is adopted in the drying and the roasting of filter cake behind the middle dipping of described step (6) cerium, can be room temperature to 300 ℃ as baking temperature, preferred 100～200 ℃, sintering temperature is generally 550～800 ℃, be preferably 600～750 ℃, roasting time is 0.5～8 hour, preferred 1～5 hour.
Adopt the sulfur transfer catalyst of method preparation provided by the invention to be mixed together use with the FCC catalyst, generally speaking, sulfur transfer catalyst accounts for 0.1～10 heavy % of FCC catalyst and sulfur transfer catalyst mixture total weight amount, preferred 1～5 heavy %.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Embodiment 1
Adopt the sulfur transfer catalyst of method preparation provided by the present invention.
Microsphere supported (the ZT that contains the magnesium aluminate spinel composition
1) preparation: in a stirred tank, add 20.2 kilograms in decationized Y sieve water, stir and add 7.63 kilograms of boehmite slurries (Shandong Aluminum Plant produces, solid content 32.0 heavy %) down and 0.655 liter of chlorination mixed rare earth solution (contains rare earth oxide RE
2O
3244.1 grams per liter, wherein, the weight ratio of each rare earth component is La
2O
3: Sm
2O
3: Yb
2O
3: Lu
2O
3=79.0: 4.5: 1.9: 0.44, the chlorination mishmetal was produced by Shanghai allosaurus rare earth Co., Ltd), stir the hydrochloric acid that adds 0.80 liter of 18 heavy % down, stirred 30 minutes, obtain the acidic alumina slurries of pH value 1.65, slurry solid content is 8.85 heavy %.In slurries, add 1 liter of V
2O
5-oxalic acid complex solution was also pulled an oar 10 minutes.(technical grade contains magnesia 97 heavy %, 95 meters of specific surfaces to add 1.4 kilograms of light magnesium oxides in the slurries that obtain
2/ gram, produce in magnesium salts chemical plant, Yongchang, Xingtai) and 3.18 kilograms of slurries that the making beating of decationized Y sieve water forms, continued stirring reaction 30 minutes, obtain the slurries of pH value 9.0.Slurries are carried out spray-drying, then under 650 ℃ with resulting microballoon roasting 2 hours, obtain containing the microsphere supported ZT of magnesium aluminate spinel composition
1
Microsphere supported (the ZT that contains the magnesium aluminate spinel composition
2) preparation: remove feed intake in boehmite be 6.62 kilograms, outside 1.72 kilograms of the light magnesium oxides, 0.85 liter of 18 heavy % hydrochloric acid, other material inventory and preparation method and ZT
1Identical.
Microsphere supported (the ZT that contains the magnesium aluminate spinel composition
3) preparation: in a stirred tank, add 20.2 kilograms in decationized Y sieve water, stir and add 7.63 kilograms of boehmite slurries (Shandong Aluminum Plant's product down, solid content 32.0 heavy %), stir the hydrochloric acid that adds 0.80 liter of 18 heavy % down, stirred 30 minutes, obtain the acidic alumina slurries of pH value 1.65, slurry solid content is 8.53 heavy %.(technical grade contains magnesia 97 heavy %, 95 meters of specific surfaces to add 1.4 kilograms of light magnesium oxides in the slurries that obtain
2/ gram, produce in magnesium salts chemical plant, Yongchang, Xingtai) and 3.18 kilograms of slurries that the making beating of decationized Y sieve water forms, continued stirring reaction 30 minutes, obtain the slurries of pH value 9.0.Slurries are carried out spray-drying, then under 650 ℃ with resulting microballoon roasting 2 hours, obtain containing the microsphere supported ZT3 of magnesium aluminate spinel composition.
V in more than preparing
2O
5The preparation method of-oxalic acid complex solution is as follows: take by weighing 40 gram V
2O
5(analyze pure, chemical reagent work of Hunan coal science research institute produce) and 95 restrains oxalic acid (H
2C
2O
42H
2O analyzes purely, and Beijing company of China Drug Co. produces) and 1 liter of decationized Y sieve water and mixing, be warming up to 60 ℃ and reacted 1 hour under stirring, promptly generate navy blue V
2O
5-oxalic acid complex solution.
ZT
1, ZT
2And ZT
3Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Wherein, the chemical composition of composition is got by calculating.Specific surface, pore volume are measured with cryogenic nitrogen absorption BET method.Abrasion index adopts following standard method to measure: a certain amount of catalyst is put into fixture, blew mill 5 hours under constant gas, except that first hour, back four hours average abrasion percentage is called the abrasion index of catalyst, and unit is % hour
-1
Sulfur transfer catalyst (C
1) preparation: take by weighing 30 gram carrier ZT
1, stir the cerous chlorate solution that adds 81 milliliters of pH values 2.90 down and (contain CeCl
37H
2O7.4 gram, wherein CeCl
37H
2O is a technical grade, and Yaolong Non-ferrous Metal Co. Ltd., Shanghai produces), flood after 20 minutes, slurries are carried out vacuum filtration, filter cake is dried under 120 ℃ and 650 ℃ of following roastings 2 hours, is obtained sulfur transfer additive C
1C
1Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Cerium content is by x-ray fluorescence spectrometry in the sulfur transfer catalyst, and other chemical composition is got by calculating.
Embodiment 2
Adopt the sulfur transfer catalyst (C of method preparation provided by the present invention
2).
Prepare sulfur transfer catalyst by method among the embodiment 1 and immersion condition, different just carriers adopt ZT
2C
2Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Cerium content is by x-ray fluorescence spectrometry in the sulfur transfer catalyst, and other chemical composition is got by calculating.
Comparative Examples 1
Adopt the sulfur transfer catalyst (DB of the described method preparation of USP4728635
1).
Take by weighing carrier ZT
130 grams (contain CeCl with 13.5 milliliters of cerous chlorate solution
37H
2O7.68 gram, wherein CeCl
37H
2O is a technical grade, and Yaolong Non-ferrous Metal Co. Ltd., Shanghai produces) carry out incipient impregnation, dry the back down 650 ℃ of following roastings 2 hours, obtain sulfur transfer additive DB for 120 ℃
1DB
1Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Wherein chemical composition is got by calculating.
Comparative Examples 2
Adopt the sulfur transfer catalyst (DB of the described method preparation of USP4728635
2).
In a stirred tank, add 20.2 kilograms in decationized Y sieve water, stir 1.037 kilograms of CeCl of adding down
37H
2O, 7.63 kilograms of boehmite slurries (Shandong Aluminum Plant produces, solid content 32.0 heavy %), 0.655 liter of chlorination mixed rare earth solution (contain rare earth oxide RE
2O
3244.1 grams per liter, wherein, the weight ratio of each rare earth component is La
2O
3: Sm
2O
3: Yb
2O
3: Lu
2O
3=79.0: 4.5: 1.9: 0.44, the chlorination mishmetal was produced by Shanghai allosaurus rare earth Co., Ltd), stir the hydrochloric acid that adds 0.80 liter of 18 heavy % down, stirred 30 minutes, obtain the acidic alumina slurries of pH value 1.65.In slurries, add 1 liter of V
2O
5-oxalic acid complex solution.(technical grade contains magnesia 97 heavy %, 95 meters of specific surfaces to add 1.4 kilograms of light magnesium oxides in the slurries that obtain
2/ gram, produce in magnesium salts chemical plant, Yongchang, Xingtai) and 3.18 kilograms of slurries that the making beating of decationized Y sieve water forms, continued stirring reaction 30 minutes, obtain the slurries of pH value 9.0.Slurries are carried out spray-drying, then under 650 ℃ with resulting microballoon roasting 2 hours, obtain contrasting sulfur transfer catalyst DB
2DB
2Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Wherein chemical composition is got by calculating.
Comparative Examples 3
Adopt the sulfur transfer catalyst (DB of USP47286 35 described method preparations
3).
Prepare sulfur transfer catalyst by the method in the Comparative Examples 2, different is to adopt cerium oxalate precipitation (containing 0.478 kilogram of cerium) to substitute CeCl in feeding intake
37H
2O salt.DB
3Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Wherein chemical composition is got by calculating.
The preparation method of the cerium oxalate precipitation in the preparation is as follows: contain 1.037 kilograms of CeCl toward containing 2 liters under stirring
37H
2Add excessive saturated oxalic acid solution in the solution of O, filter and precipitate with promptly making cerium oxalate after the decationized Y sieve water washing.
Embodiment 3
Adopt the sulfur transfer catalyst (C of method preparation provided by the invention
3).
Prepare sulfur transfer catalyst by the method among the embodiment 1, different just CeCl
3The pH value of maceration extract is 5.C
3Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Cerium content is by x-ray fluorescence spectrometry in the sulfur transfer catalyst, and other chemical composition is got by calculating.
Embodiment 4
Adopt the sulfur transfer catalyst (C of method preparation provided by the invention
4).
Method by example 1 prepares composition and sulfur transfer catalyst, and different just dip times are 30 minutes.C
4Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Cerium content is by x-ray fluorescence spectrometry in the sulfur transfer catalyst, and other chemical composition is got by calculating.
Embodiment 5
Adopt the sulfur transfer catalyst (C of method preparation provided by the invention
5).
Prepare sulfur transfer catalyst by the method among the embodiment 1, different just CeCl
3The volume of maceration extract is 53 milliliters and (wherein contains CeCl
37H
2The O7.4 gram).C
5Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Cerium content is by x-ray fluorescence spectrometry in the sulfur transfer catalyst, and other chemical composition is got by calculating.
Embodiment 6
Adopt the sulfur transfer catalyst (C of method preparation provided by the invention
6).
Prepare sulfur transfer catalyst by the method among the embodiment 1, different just CeCl
3The volume of maceration extract is 81 milliliters and (wherein contains CeCl
37H
2The O14.28 gram).C
6Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Cerium content is by x-ray fluorescence spectrometry in the sulfur transfer catalyst, and other chemical composition is got by calculating.
Embodiment 7
Adopt the sulfur transfer catalyst (C of method preparation provided by the invention
7).
Prepare sulfur transfer catalyst by method among the embodiment 1 and immersion condition, different just carriers adopt ZT
3C
7Chemical composition, specific surface, pore volume and abrasion index list in the table 1.Cerium content is by x-ray fluorescence spectrometry in the sulfur transfer catalyst, and other chemical composition is got by calculating.
Table 1
| The catalyst numbering | Chemical composition, heavy % | Specific surface, rice 2/ gram | Pore volume, milliliter/gram | Abrasion index % hour -1 | ||||
| ?MgO | ??Al 2O 3 | ?RE 2O 3 | ?V 2O 5 | Cerium | ||||
| ????ZT 1????ZT 2????ZT 3 | ??34.64 ??42.59 ??36.44 | ??60.41 ??52.46 ??63.56 | ??3.96 ??3.96 ????/ | ??1.0 ??1.0 ??/ | ????- ????- ????/ | ????143 ????136 ????148 | ????0.30 ????0.29 ????0.31 | ????2.6 ????1.9 ????2.0 |
| ????C 1????C 2????C 3????C 4????C 5????C 6????C 7 | ??30.83 ??37.91 ??30.83 ??30.83 ??30.83 ??28.75 ??32.43 | ??53.76 ??46.69 ??53.76 ??53.76 ??53.76 ??50.14 ??56.57 | ??3.52 ??3.52 ??3.52 ??3.52 ??3.52 ??3.29 ????/ | ??0.89 ??0.89 ??0.89 ??0.89 ??0.89 ??0.83 ????/ | ????11 ????12 ????11 ????11 ????11 ????17 ????11 | ????118 ????110 ????116 ????118 ????117 ????91 ????120 | ????0.27 ????0.27 ????0.27 ????0.28 ????0.28 ????0.27 ????0.28 | ????2.6 ????1.9 ????1.9 ????2.6 ????2.6 ????2.5 ????2.0 |
| ????DB 1????DB 2????DB 3 | ??30.97 ??30.97 ??30.97 | ??54.01 ??54.01 ??54.01 | ??3.54 ??3.54 ??3.54 | ??0.89 ??0.89 ??0.89 | ????10.6 ????10.6 ????10.6 | ????97 ????49 ????70 | ????0.24 ????0.23 ????0.24 | ????2.6 ????4.9 ????5.5 |
As can be seen from Table 1, adopt equi-volume impregnating to prepare sulfur transfer catalyst and have tangible reactive metal oxides plug-hole phenomenon, adopt the dipping method of excessive maceration extract provided by the present invention reactive metal oxides plug-hole phenomenon then can not occur.It can also be seen that from table 1, cerium-containing compound is if add in containing magnesium aluminate spinel preparation of compositions process, specific surface and pore volume are reduced, and cause the scuff resistance variation of sulfur transfer catalyst, can not influence its scuff resistance and adopt the dipping method of excessive maceration extract provided by the present invention to prepare sulfur transfer catalyst.
Embodiment 8-12
Following example explanation: the oxidation absorption and the reducing/regenerating performance that adopt the sulfur transfer catalyst of method preparation provided by the invention.
Each 3 gram and 27 of sulfur transfer catalyst that are respectively charged into example 1,2,4,6,7 preparations in the fixed fluidized-bed reactor of 3 centimetres of internal diameters, 28 centimetres of length restrain commercial FCC catalyst, and (the industrial trade mark is Orbit-3000, Qilu Petrochemical company Zhou village catalyst plant product) mixture, feeding flow is the nitrogen of 1150 ml/min, make mixture be in the fluidisation attitude, be warming up to 600 ℃ simultaneously.After treating catalyst mixture bed constant temperature, switch the SO that contains 1900vppm
2, 5.0 body % oxygen, all the other are the gaseous mixture of nitrogen, adsorption reaction switches to nitrogen after 45 minutes again, purges 10 minutes.When adsorption process was carried out, tail gas was by the hydrogen peroxide solution of 1.2 heavy %, to absorb the SO that is not adsorbed
2, after absorption and purging are finished, be that the 0.2 NaOH aqueous solution droplets that weighs % is absorbed with SO surely with concentration
2Hydrogen peroxide solution, be calculated as follows SO in 45 minutes inner catalyst mixtures
2Absorption percentage (SO
2%):
SO
2%=(the SO that the 1-absorption liquid absorbs
2Total SO of mM number/by the catalyst mixture bed
2The mM number) * 100
=(1-V
Absorption/ V
Blank) * 100 wherein, V
BlankBe 25 milliliters of NaOH titrating solution volumes that absorption liquid consumed behind logical 45 minutes gaseous mixtures of empty reactor, V
AbsorptionBehind logical 45 minutes gaseous mixtures of the reactor of loading catalyst mixture, 25 milliliters of NaOH titrating solution volumes that absorption liquid consumed.Indicator is methyl red and methylene blue mixed indicator during titration.
Catalyst mixture was through 45 minutes SO
2Behind absorption and the 10 minutes nitrogen purging, be the high-purity hydrogen of 1150 ml/min, switch the nitrogen that flow is 1150 ml/min after 60 minutes again, purge after 10 minutes, switch successively by above identical method again and contain SO in same temperature incision change of current amount
2With gaseous mixture, the nitrogen of oxygen, and by the above-mentioned identical method calculating SO first time
2SO in the desorption rear catalyst mixture
2Absorption percentage SO
2(1) %.Carry out hydrogen reducing, SO equally once more
2After absorption and nitrogen purge, measure SO for the second time
2SO in the desorption rear catalyst mixture
2Absorption percentage SO
2(2) %.The oxidation absorption and the reducing/regenerating The performance test results of each sulfur transfer catalyst are listed in the table 2.
Comparative Examples 4-6
Following Comparative Examples explanation: the oxidation absorption of reference sulfur transfer catalyst and reducing/regenerating performance.
Press the method for example 7 and measure SO
2%, SO
2(1) % and SO
2(2) %, different is that used sulfur transfer catalyst is respectively the reference sulfur transfer catalyst DB by the preparation of the method in Comparative Examples 1, Comparative Examples 2 and the Comparative Examples 3
1, DB
2And DB
3, the results are shown in Table 2.
Table 2 oxidation absorption and reducing/regenerating performance
| Example number | Sulfur transfer catalyst | ????SO 2％ | ???SO 2(1)％ | ???SO 2(2) ????％ |
| ????8 | ????C 1 | ????85.50 | ????38.98 | ????27.15 |
| ????9 | ????C 2 | ????93.52 | ????58.43 | ????31.35 |
| ????10 | ????C 4 | ????85.80 | ????39.00 | ????27.45 |
| ????11 | ????C 6 | ????88.56 | ????41.27 | ????29.44 |
| ????12 | ????C 7 | ????84.50 | ????35.80 | ????25.60 |
| Comparative Examples 4 | ????DB 1 | ????80.93 | ????32.55 | ????20.25 |
| Comparative Examples 5 | ????DB 2 | ????70.25 | ????25.25 | ????14.19 |
| Comparative Examples 6 | ????DB 3 | ????71.39 | ????27.54 | ????14.95 |
From the result of table 2 as can be seen, adopt method preparation provided by the present invention fresh sulfur transfer catalyst its to SO
2The oxidation adsorption capacity obviously be better than the close fresh reference sulfur transfer catalyst of cerium content, and through the reduction once with twice after, it is to SO
2The oxidation adsorption capacity still apparently higher than the reference sulfur transfer catalyst.This explanation compared with prior art, adopts the sulfur transfer catalyst of method preparation provided by the present invention to have better SO
2Oxidation absorption and reducing/regenerating performance.
Claims (13)
1, a kind of sulfur transfer catalyst is characterized in that:
A, this sulfur transfer catalyst are is benchmark with the catalyst weight with the oxide of the cerium of 2～30 heavy % as active component, contains the magnesium aluminate spinel composition as carrier with 70～98 heavy %; Describedly contain the magnesium aluminate spinel composition to contain in said composition weight be the MgO with 5～70 heavy % of oxide of benchmark, the Al of 30～95 heavy %
2O
3, the rare-earth oxide except that cerium of 0～15 heavy %, the V of 0～10 heavy %
2O
5
The preparation method of b, this sulfur transfer catalyst is as follows:
(1) aluminium oxide and/or aluminium hydroxide, rare earth compound, deionized water and acid except that cerium are mixed and reaction at least 5 minutes, it is 1.5～4 that the addition of acid makes the pH value of the slurries that obtain, and it is 5～20 heavy % that the addition of deionized water, aluminium oxide and/or aluminium hydroxide and rare earth compound makes the solid content of the slurries that obtain;
(2) solution that will contain water-soluble vanadium compound adds in the above-mentioned slurries;
(3) magnesia or magnesium hydroxide are added in the above-mentioned slurries, reacted at least 5 minutes;
(4), obtain containing the magnesium aluminate spinel composition with above-mentioned slurry dried, roasting;
(5) contain the composition of magnesium aluminate spinel more than 5 minutes with containing the cerium solution of magnesium aluminate spinel composition saturated adsorption capacity more than 1.5 times at dipping under the condition of PH2～6;
(6) filter slurries, and filter cake is carried out drying, roasting.
2, according to the described sulfur transfer catalyst of claim 1, it is characterized in that this catalyst is is benchmark with the catalyst weight with the oxide of the cerium of 2～25 heavy % as active component, contain the magnesium aluminate spinel composition as carrier with 75～95 heavy %;
3,, it is characterized in that describedly containing that to contain in said composition weight in the magnesium aluminate spinel composition be the MgO with 20～65 heavy % of oxide of benchmark, the Al of 20～79 heavy % according to claim 1 or 2 described sulfur transfer catalysts
2O
3, the rare-earth oxide except that cerium of 0.5～10 heavy %, the V of 0.5～5 heavy %
2O
5
4,, it is characterized in that aluminium oxide is selected from described in the step (1): one or more in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, the θ-aluminium oxide according to the described sulfur transfer catalyst of claim 1; Described aluminium hydroxide is selected from: one or more in gibbsite, surge aluminium stone, promise diaspore, diaspore, thin aluminium stone, the boehmite.
5,, it is characterized in that the rare earth metal except that cerium described in the step (1) is selected from: one or more in lanthanum, praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium according to the described sulfur transfer catalyst of claim 1.
6,, it is characterized in that the rare earth metal except that cerium described in the step (1) is lanthanum or rich lanthanum and do not conform to the rare earth metal of cerium basically according to the described sulfur transfer catalyst of claim 5.
7,, it is characterized in that the acid described in the step (1) is selected from one or more the mixture in nitric acid, hydrochloric acid, sulfuric acid, formic acid, acetate, the oxalic acid according to the described sulfur transfer catalyst of claim 1.
8,, it is characterized in that the acid described in the step (1) is selected from nitric acid and/or hydrochloric acid according to the described sulfur transfer catalyst of claim 7.
9,, it is characterized in that the water-soluble vanadium compound described in the step (2) is V according to the described sulfur transfer catalyst of claim 1
2O
5The oxalic acid complex compound.
10, according to the described sulfur transfer catalyst of claim 1, the volume that it is characterized in that cerium solution described in the step (5) is 3～8 times of saturated adsorption capacity that contain the magnesium aluminate spinel composition, and it floods the composition 10～60 minutes that contains magnesium aluminate spinel under the condition of PH2.5～6.
11,, it is characterized in that cerium solution described in the step (5) is the solution that comprises the water soluble compound that contains one or more ceriums of trivalent and quadrivalent cerium according to the described sulfur transfer catalyst of claim 1.
12,, it is characterized in that cerium solution described in the step (5) is to contain the nitrate of cerium, one or more the solution in the chloride according to the described sulfur transfer catalyst of claim 11.
13, according to the described sulfur transfer catalyst of claim 1, it is characterized in that this sulfur transfer catalyst and FCC catalyst are mixed together use, sulfur transfer catalyst accounts for 0.1～10 heavy % of FCC catalyst and sulfur transfer catalyst mixture total weight amount.
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