CN1142015C - Sulfur transfer catalyst and its preparing process - Google Patents
Sulfur transfer catalyst and its preparing process Download PDFInfo
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- CN1142015C CN1142015C CNB001207458A CN00120745A CN1142015C CN 1142015 C CN1142015 C CN 1142015C CN B001207458 A CNB001207458 A CN B001207458A CN 00120745 A CN00120745 A CN 00120745A CN 1142015 C CN1142015 C CN 1142015C
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Abstract
The present inveniton relates to a sulfur transfer catalyst which comprises: 70 to 98 wt% of composition containing magnesium and aluminum spinel, and 2 to 30 wt% of cerium and (or) vanadium oxide, wherein the composition containing the magnesium and aluminum spinel contains 25 to 30 wt% of magnesium oxide, 60 to 70 wt% of alumina and 5 to 15 wt% of rare earth oxide except for cerium; magnesium and aluminum form a spinel structure, and free magnesium oxide content is lower than 5 wt% of the total amount of the composition containing the magnesium aluminum spinel, and the diameter of the smallest hole of the composition containing the magnesium aluminum spinel is not smaller than 100 angstrom. The catalyst has good reduction reproducing property.
Description
Technical field
The invention relates to a kind of sulfur transfer catalyst and preparation method thereof, more specifically say so about a kind of sulfur transfer catalyst that contains the magnesium-aluminium spinel composition and preparation method thereof.
Background technology
Fluid catalytic cracking (FCC) is a main method of being obtained gasoline, the contour use value light-end products of diesel oil by heavy raw oil.FCC apparatus is made up of a riser reactor and a revivifier usually, in operating process, cracking catalyst microballoon and heavier feedstocks oil with cracking activity carry out the pyrolytic cracking reaction in riser reactor, generate lightweight oil and gas products, meanwhile, cracking catalyst also loses cracking activity because of coking.The cracking catalyst of inactivation need enter in the revivifier, in revivifier, carries out high temperature and burn in the presence of air, makes catalyst regeneration.Because of containing a large amount of sulphur compounds in the catalyst surface coke, therefore, in burning process, can generate 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 pollution can be caused after entering atmosphere with regenerator flue gas, therefore, otherwise effective technique must be adopted, control SO
xDischarging.
At present, control SO
xA kind of effective means of discharging is to add a small amount of fluidizing performance SO close with cracking catalyst in catalytic cracking catalyst
xSorbing material (sulfur transfer catalyst), sulfur transfer catalyst can promote SO in the FCC catalyst regeneration process
2Be oxidized to SO
3, and with SO
3Be adsorbed on the surface and form metal sulfate, be adsorbed with SO
3Sulfur transfer catalyst with regeneration after catalyzer enter riser reactor, under the reductive condition in reactor, the metal sulfate that is adsorbed on the sulfur transfer catalyst 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 sulfur transfer catalyst obtains regeneration simultaneously, and is circulated to revivifier again with decaying catalyst, performance absorption SO
xEffect.
In addition, other commercial run is as SO in the Industrial Boiler
xSulfur transfer catalyst is also usually adopted in the control discharging.
US4,472,532 disclose the preparation method of the spinel composition of a kind of alkaline including 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 basic 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 mixing process, (2) the described precipitation of roasting obtains the spinel composition of alkaline including earth metal and aluminium.This method can also comprise with at least a additional metal component dipping said composition or sedimentary process.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, iron, tin, antimony and their mixture.
US4,476,245 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, this method comprises that (1) mix a kind of acidic solution and a kind of wherein aluminium with the basic solution that contains at least a al composition that anionic form exists, (2) with the product and the aqueous solution that contains at least a alkaline earth metal component, the precipitation that (3) roasting obtains that obtain.Can also further described precipitation or spinel composition be contacted with at least a additional metal component in this method, in said composition in the load significant quantity can under oxidizing condition, promote SO
2Be oxidized to SO
3The additional metal component, described additional metal group also is selected from IB, IIB, IVB, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.
US4,492,677 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, this method comprise (1) with a kind of acidic medium that contains at least a alkaline earth metal component, at least aly have the organic compound of inherent alkalescence and aluminium wherein mixes with the aluminium basic solution that contains that anionic form exists, obtain a kind of sedimentary material that contains liquid phase and alkaline-earth metal and aluminium, in the mixing process, the pH value is maintained at about 8.0 or higher, (2) the described precipitation of roasting obtains the spinel composition of alkali metal containing and aluminium.Can also contain in the described composition and a kind ofly can promote SO
2Oxidation or SO
3The additional metal component, described additional metal component is selected from IB, IIB, IVB, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.
US4,522,937 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, comprise that (1) mix a kind of acidic solution that contains at least a alkaline earth metal component and at least a wherein aluminium with the alkaline aqueous solution that contains at least a al composition that anionic form exists, obtain containing the sedimentary material of a kind of liquid phase and a kind of alkaline including earth metal and al composition, wherein, at least a in described acidic solution and the basic 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
2Oxidation or SO
3At least a additional metal component of amount, and, remain on the scope of 7.0-10.5, the precipitation that (2) roasting obtains in the pH of liquid phase described in mixing process value.Described additional metal component is selected from IB, IIB, IVB, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.
In above-mentioned four pieces of patents, the spinel composition of alkaline including earth metal and aluminium adopts all that the aluminium basic solution mixes, precipitation obtains containing of existing with anionic form with acid alkaline earth metal solution and aluminium wherein, and the aperture of the composition of this spinel is less.
US4,497,902 disclose a kind of SO that removes from gas
xComposition, said composition contains a kind of inorganic oxide compositions and at least a free or bonded rare earth metal, described rare earth metal is selected from one group that is made up of lanthanum, cerium, praseodymium, samarium, dysprosium, and described inorganic oxide compositions is selected from by magnesium-aluminium spinel (MgAl
2O
4), a group of forming of the mixture of aluminum oxide and magnesian mixture and magnesium oxide and spinel.Do not provide the character and the preparation method of spinel in the specification sheets of this patent, find from the example, with calcium oxide, a water Alpha-alumina and magnesium oxide mix, and adding nitric acid mixes to be pinched, and obtains a kind of magnesium oxide, Ca of containing after the roasting
3Al
10O
18And magnesium-aluminium spinel (MgAl
2O
4) mixture, roasting, and dipping goes up cerium, can obtain the described SO of taking off
xComposition.
US4,728,635 disclose the preparation method of 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.This method is easy to be easy to get, but the aperture of the spinel composition of preparing is still less, as sulfur transfer catalyst, active not high enough.
As previously mentioned, sulfur transfer catalyst as the control sulphur emissions, must have good adsorption sulphur performance (under oxidizing condition) and good desorption sulphur performance (restoring under the condition) simultaneously, simultaneously, what is more important, because this catalyzer circulates with catalytic cracking catalyst and repeatedly uses, this catalyzer also must have good reducing/regenerating performance, the catalyzer that promptly is adsorbed with oxysulfide is behind reducing/regenerating, must have higher absorption sulphur activity, and the catalyst reduction regenerability that prior art compositions is made is all bad.
Summary of the invention
The objective of the invention is on the prior art basis, a kind of new sulfur transfer catalyst with better reducing/regenerating performance is provided, another object of the present invention provides this Preparation of catalysts method.
Sulfur transfer catalyst provided by the invention contains the composition that contains magnesium-aluminium spinel and the cerium of the heavy % of 2-30 and/or the oxide compound of vanadium of the heavy % of 70-98, the described composition that contains magnesium-aluminium spinel contains the magnesium oxide of the heavy % of 25-30, the rare-earth oxide except that cerium of the aluminum oxide of the heavy % of 60-70 and the heavy % of 5-15, wherein, magnesium and aluminium form spinel structure, the content of free magnesium is lower than the described 5 heavy % that contain the total composition of magnesium-aluminium spinel, and the described most probable bore dia that contains the composition of magnesium-aluminium spinel is not less than 100 dusts.
The preparation method of sulfur transfer catalyst provided by the invention comprises with a kind of composition that contains magnesium-aluminium spinel of solution impregnation that contains cerium and/or vanadium compound, dry also roasting, wherein, the described composition that contains magnesium-aluminium spinel contains the magnesium oxide of the heavy % of 25-30, the rare-earth oxide except that cerium of the aluminum oxide of the heavy % of 60-70 and the heavy % of 5-15, wherein, magnesium and aluminium form spinel structure, the content of free magnesium is lower than the described 5 heavy % that contain the total composition of magnesium-aluminium spinel, the described most probable bore dia that contains the composition of magnesium-aluminium spinel is not less than 100 dusts, the preparation method of said composition comprises that (1) is with aluminum oxide and/or aluminium hydroxide, rare earth compound except that cerium, deionized water and acid mix, reaction is at least 5 minutes under 40-100 ℃ temperature, the add-on of acid makes the pH value of the slurries that obtain be 1.5-4, water, it is the heavy % of 5-20 that the add-on of aluminum oxide and/or aluminium hydroxide and described rare earth compound makes the solid content of the slurries that obtain, and, make the aluminum oxide that contains containing of obtaining the heavy % of 60-70 in magnesium and the aluminate composition and the rare-earth oxide except that cerium of the heavy % of 5-15, (2) in the slurries that obtain, add magnesium oxide and/or magnesium hydroxide, reaction is at least 5 minutes under 40-100 ℃ temperature, the add-on of magnesium oxide and/or magnesium hydroxide makes the composition that contains magnesium-aluminium spinel that obtains contain the magnesium oxide that 25-30 weighs %, the product that (3) are dry and roasting obtains.
Compared with prior art, in the catalyzer provided by the invention, the described composition that contains magnesium-aluminium spinel has bigger aperture and lower free MgO content, therefore, sulfur transfer catalyst provided by the invention has better reducing/regenerating performance, for example, and with CeO with same amount
2, V
2O
5Existing sulfur transfer catalyst compare, sulfur transfer catalyst provided by the invention through the reduction once with twice after, it adsorbs SO
2Ability be much higher than existing catalyzer.
Embodiment
According to sulfur transfer catalyst provided by the invention, the described content that contains the composition of magnesium-aluminium spinel is the heavy % of 70-98, and the heavy % of preferred 75-95, the content of the oxide compound of described cerium and/or vanadium are the heavy % of 2-30, the heavy % of preferred 5-25.
The described most probable bore dia that contains the composition of magnesium-aluminium spinel is preferably the 100-200 dust, and specific surface is not less than 100 meters
2/ gram, pore volume is preferably 0.3-0.5 milliliter/gram at least 0.2 milliliter/gram.
The content of described free magnesium preferably is lower than the described 3 heavy % that contain the total composition of magnesium-aluminium spinel
The content of the rare-earth oxide in the described composition that contains magnesium-aluminium spinel except that cerium is preferably the heavy % of 5-10.
Preparation method according to sulfur transfer catalyst provided by the invention, described aluminum oxide is selected from can be by in the aluminum oxide of sour peptization one or more, as in ρ-aluminum oxide, χ-aluminum oxide, η-aluminum oxide, gama-alumina, κ-aluminum oxide, δ-aluminum oxide and the θ-aluminum oxide one or more.Described aluminium hydroxide is also referred to as hydrated aluminum oxide, and it can be selected from an alumina trihydrate and the water aluminum oxide one or more, as in gibbsite, surge aluminium stone, promise diaspore, diasporite, boehmite, the pseudo-boehmite one or more.
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 can be selected from one or more in various organic acids and the mineral acid, as nitric acid, hydrochloric acid, sulfuric acid, acetate, oxalic acid etc., wherein, more preferably nitric acid and/or hydrochloric acid.
Among the preparation method of sulfur transfer catalyst provided by the invention, when preparation contains the composition of magnesium-aluminium spinel, temperature of reaction is very important, when temperature of reaction is lower than 40 ℃, the aperture of the composition that obtains is less, does not reach purpose of the present invention, and is not easy to operation when being higher than 100 ℃, therefore the temperature of reaction in (1) step and (2) step is 40-90 ℃, is preferably 50-80 ℃.Reaction times too weak point can not make that reaction carries out fully, therefore, (1) step or described reaction times in (2) step should all be not less than 5 minutes, the reaction times is preferably 5-60 minute, more preferably 10-30 minute.
To achieve the object of the present invention, the described pH value of (1) step reaction also is very important, and reaction pH value is 1.5-4, is preferably 2-3.
The solid content of described slurries of (1) step is preferably the heavy % of 7-15.
The described drying that contains the composition of magnesium-aluminium spinel can adopt conventional drying means, and as airing, oven dry, spray-dired method, the exsiccant temperature can be a room temperature to 400 ℃, preferred 100-400 ℃.
The described temperature and time that contains the composition roasting of magnesium-aluminium spinel is that this area prepares spinel composition maturing temperature and time commonly used, maturing temperature is generally 550-850 ℃, be preferably 650-800 ℃, roasting time generally was not less than 0.5 hour, be preferably 0.5-6 hour, more preferably 1-4 hour.
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 cpds, wherein, preferred cerium compound is selected from the nitrate of cerium, in the muriate one or more, and preferred cerium compound is a cerous nitrate.
Described vanadium compound is selected from one or more in any water-soluble vanadium compound, preferred V
2O
5The oxalic acid complex compound.
Described dipping can adopt various existing dipping methods, as saturated pickling process, and unsaturated pickling process.When dipping cerium and vanadium, described dipping can flood simultaneously, also can flood a kind of, dry or moist in cerium and the vanadium earlier, and dipping is another kind of again.
Conventional condition is adopted in drying and roasting after dipping cerium and/or the vanadium, can be room temperature to 400 ℃ as drying temperature, and preferred 100-300 ℃, maturing temperature is generally 550-800 ℃, is preferably 600-750 ℃, and roasting time is 0.5-8 hour, preferred 1-5 hour.
Sulfur transfer catalyst provided by the invention can be mixed together use with the FCC catalyzer, and generally speaking, sulfur transfer catalyst accounts for the heavy % of 0.5-10 of FCC catalyzer and sulfur transfer catalyst mixture total weight amount.
The following examples will the present invention will be further described.
Example 1
Sulfur transfer catalyst provided by the invention and preparation thereof.
In a stirred pot, add 600 ml deionized water, under agitation add 240 gram pseudo-boehmite slurries (Shandong Aluminum Plant produces, and solid content is 32.0 heavy %) and 12.9 gram LaCl
37H
2O, be warming up to 60 ℃, under agitation adding 23 ml concns is the hydrochloric acid (chemical pure of 18 heavy %, chemical reagent factory of Beijing Xinhua produces), continuation is 60 ℃ of stirring reactions 15 minutes, obtains the pH value and be 2.30 slurries, and the solid content of slurries is 9.4 heavy %, (analytical pure, specific surface are 95 meters to add 31 gram magnesium oxide in the slurries that obtain
2/ gram, the Beijing Chemical Plant produces) and the slurries that form of 60 ml deionized water making beating, continuation was 60 ℃ of following stirring reactions 15 minutes, obtain the pH value and be 8.2 slurries, slurries 120 ℃ of oven dry, then 760 ℃ of roastings 4 hours, are obtained containing the composition Z of magnesium-aluminium spinel
1Composition Z
1Composition, specific surface, pore volume, the most probable bore dia is listed in the table 1.Wherein, the composition of composition is got by calculating, and specific surface, pore volume, most probable aperture are measured with cryogenic nitrogen absorption BET method, and free magnesium content is measured with the X-ray diffraction method.
Take by weighing 10 gram 100-200 purpose carrier Z
1, with 12.840 gram cerous nitrate-V
2O
5Oxalic acid complex compound mixing solutions mixes, and 120 ℃ of oven dry down, then, 720 ℃ of following roastings 1.5 hours, obtains sulfur transfer catalyst C provided by the invention
1, C
1In contain composition Z
185.03 heavy %, CeO
213.18 heavy %, V
2O
51.64 heavy %.Carrier, CeO
2, V
2O
5Content gets by calculating.
Wherein, cerous nitrate-V
2O
5Contain CeO in the oxalic acid complex compound mixing solutions
211.77 heavy %, V
2O
52.13 heavy %, the preparation method of this mixing solutions is as follows: take by weighing 21 gram V
2O
5(analytical pure, chemical reagent work of Hunan coal science institute produces) and 72 gram oxalic acid (H
2C
2O
4H
2O, analytical pure, Beijing company of China Drug Co. produces), mix with 300 ml deionized water, be heated with stirring to 40-50 ℃, until generating mazarine V
2O
5The oxalic acid complex solution.The V that is generating
2O
5Add 391 gram cerous nitrate (Ce (NO in the oxalic acid complex solution
3)
36H
2O, analytical pure, the Beijing Chemical Plant produces) with the cerous nitrate aqueous solution that 300 ml deionized water mix, add 200 ml deionized water again, mix, obtain cerous nitrate-V
2O
5Oxalic acid complex compound mixing solutions.
Comparative Examples 1
Reference sulfur transfer catalyst and preparation thereof.
Press US4,728,635 method prepares the magnesium-aluminium spinel composition.Method by example 1 prepares composition, and different is not add LaCl
37H
2O, reaction is at room temperature carried out, and obtains reference magnesium-aluminium spinel composition Z B
1, ZB
1Composition, specific surface, pore volume, most probable aperture list in the table 1.
By the method identical, with identical cerous nitrate-V with example 1
2O
5The reference magnesium-aluminium spinel composition Z B of oxalic acid complex compound mixing solutions dipping same amount
1, and drying and roasting under identical condition, obtain reference sulfur transfer catalyst CB
1CB
1In contain composition Z B
185.03 heavy %, CeO
213.18 heavy %, V
2O
51.79 heavy %.
Comparative Examples 2
The preparation of reference sulfur transfer catalyst.
Method by example 1 prepares composition and sulfur transfer catalyst, and different is pseudo-boehmite slurries, LaCl
37H
2Stirring reaction behind the stirring reaction of O and hydrochloric acid and the adding magnesium oxide all carries out under room temperature (25 ℃), and reference composition that obtains and reference catalyst are designated as ZB respectively
2And CB
2ZB
2Composition, specific surface, pore volume, most probable bore dia list in the table 1.Reference catalyst CB
2Contain composition Z B
285.03 heavy %, CeO
213.18 heavy %, V
2O
51.79 heavy %.
Example 2
Sulfur transfer catalyst provided by the invention and preparation thereof.
In a stirred pot, add 600 milliliters of deionizations, under agitation add 240 gram pseudo-boehmite slurries (specification and the place of production are with example 1) and 23.3 milliliters of rich lanthanum chlorination mixed rare earth solutions (1) and (contain rare earth oxide RE
2O
3302 grams per liters, 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 company limited), be warming up to 70 ℃, under agitation adding 22 ml concns is the hydrochloric acid of 18 heavy %.Continue under agitation to react 25 minutes, obtain the pH value and be 2.75 slurries.Under agitation add and contain the 31 magnesian slurries of gram (with example 1) and continue, obtain the pH value and be 8.95 slurries, slurries 120 ℃ of oven dry, then 700 ℃ of following roastings 4 hours, must be contained the composition Z of magnesium-aluminium spinel 70 ℃ of following stirring reactions 20 minutes
2
Take by weighing 10 gram 100-200 purpose carrier Z
2, with 12.840 gram examples, 1 described cerous nitrate-V
2O
5Oxalic acid complex compound mixing solutions mixes, 120 ℃ of oven dry, and 700 ℃ of roastings 2 hours obtain sulfur transfer catalyst C provided by the invention
2C
2In contain composition Z
285.03 heavy %, CeO
213.18 heavy %, V
2O
51.79 heavy %.
Example 3
Sulfur transfer catalyst provided by the invention and preparation thereof.
Method by example 2 prepares composition and sulfur transfer catalyst, and different just changing 23.3 milliliters of rich lanthanum chlorination mixed rare earth solutions (1) into 32.4 milliliters of rich lanthanum chlorination mixed rare earth solutions (2) (contains rare earth oxide RE
2O
3241 grams per liters, the weight ratio of each rare earth component are La
2O
3: Pr
6O
11=70.5: 24.5, the chlorination mishmetal is produced by Shanghai allosaurus rare earth company limited), the add-on of hydrochloric acid is 21.5 milliliters, and the pH value of first set reaction rear slurry is 2.60, and the pH value of reacting rear slurry for the second time is 8.5, obtains containing the composition Z of magnesium-aluminium spinel
3With sulfur transfer catalyst C provided by the invention
3Z
3Composition, specific surface, pore volume, most probable aperture list in the table 1.C
3In contain composition Z
385.03 heavy %, CeO
213.18 heavy %, V
2O
51.79 heavy %.
Example 4
Sulfur transfer catalyst provided by the invention and preparation thereof.
Method by example 1 prepares composition and sulfur transfer catalyst, and different is with containing CeO
2Cerium nitrate solution 8.8 grams of 12 heavy % replace 12.840 gram cerous nitrate-V
2O
5Oxalic acid complex compound mixing solutions obtains sulfur transfer catalyst C provided by the invention
4, C
4In contain composition Z
190.45 heavy %, CeO
29.55 heavy %.
Example 5
The preparation of sulfur transfer catalyst provided by the invention.
Method by example 1 prepares composition and sulfur transfer catalyst, and different is with containing CeO
2Cerium nitrate solution 22 grams of 12 heavy % replace 12.840 gram cerous nitrate-V
2O
5Oxalic acid complex compound mixing solutions obtains sulfur transfer catalyst C provided by the invention
5, C
5In contain composition Z
179.11 heavy %, CeO
220.89 heavy %.
Table 1
| Example number | Composition no | Composition is formed, heavy % | Free MgO, heavy % | The most probable bore dia, A | Specific surface, rice 2/ gram | Pore volume, milliliter/gram | ||
| MgO | Al 2O 3 | RE 2O 3 | ||||||
| 1 | Z1 | 27.30 | 67.70 | 5.00 | 1.8 | 195 | 117 | 0.43 |
| Comparative Examples 1 | ZB 1 | 44.24 | 55.76 | - | 18 | 70 | 146 | 0.35 |
| Comparative Examples 2 | ZB 2 | 27.30 | 67.70 | 5.00 | 5.5 | 80 | 135 | 0.35 |
| 2 | Z 2 | 27.00 | 66.90 | 6.10 | 1.0 | 150 | 100 | 0.38 |
| 3 | Z 3 | 26.82 | 66.43 | 6.75 | 1.3 | 119 | 125 | 0.38 |
Example 6-10
Following example illustrates the reducing/regenerating performance of sulfur transfer catalyst provided by the invention.
3 centimetres of internal diameters, be respectively charged into the sulfur transfer catalyst C of example 1-5 preparation in long 28 centimetres the fixed fluidized-bed reactor
1-C
5(the industrial trade mark is OB-3000 to each 3 gram with the commercial FCC catalyzer of 27 grams, Qilu Petrochemical main office Zhou village catalyst plant product) mixture, feeding flow is the nitrogen of 1150 ml/min, make mixture be in fluidized, be warming up to 600 ℃ simultaneously, after treating catalyst mixture bed constant temperature, switching contains 1900ppm SO
2, 5.0 body % oxygen, all the other are the gas mixture of nitrogen, adsorb after 45 minutes, switch to nitrogen again, purge 10 minutes.When adsorption process was carried out, tail gas was by the aqueous 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 titration that weighs % is absorbed with SO with concentration
2Aqueous hydrogen peroxide solution, be calculated as follows SO in 45 minutes inner catalyst mixtures
2Absorption percentage ratio (SO
2%).
SO
2%=(the SO that the 1-absorption liquid absorbs
2Total SO of mmole number/by the catalyst mixture bed
2
The mmole number) * 100%
=(1-V
Absorption/ V
Blank) * 100%
Wherein, V
BlankBehind logical 45 minutes gas mixtures of empty reactor, 25 milliliters of NaOH titrating solution volumes that absorption liquid consumed, V
AbsorptionBehind logical 45 minutes gas 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 mixture indicator during titration.
Catalyst mixture was through 45 minutes SO
2Behind absorption and the 10 minutes nitrogen purgings, switch high-purity hydrogen under same temperature, the flow of high-purity hydrogen is 1150 ml/min, after 60 minutes, again switch the nitrogen that flow is 1150 ml/min, purge after 10 minutes, switch successively by above identical method again and contain SO
2With gas 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 ratio SO
2(1) %.Carry out hydrogen reducing, SO equally once more
2Behind absorption and the nitrogen purging, determine SO for the second time
2SO in the desorption rear catalyst mixture
2Absorption percentage ratio SO
2(2) %.The results are shown in Table 2.
Comparative Examples 3-4
The reducing/regenerating performance of following Comparative Examples explanation reference sulfur transfer catalyst.
Press the method for example 6 and measure SO
2%, SO
2(1) % and SO
2(2) %, that different is the reference sulfur transfer catalyst CB that used sulfur transfer catalyst is respectively Comparative Examples 1 and Comparative Examples 2 preparations
1And CB
2, the results are shown in Table 2.
Table 2
| Example number | The sulfur transfer additive numbering | SO 2％ | SO 2(1)％ | SO 2(2)％ |
| 6 | C 1 | 85.13 | 40.50 | 20.67 |
| 7 | C 2 | 86.65 | 39.36 | 25.25 |
| 8 | C 3 | 86.65 | 47.94 | 39.36 |
| 9 | C 4 | 85.10 | 39.60 | 20.50 |
| 10 | C 5 | 86.88 | 42.50 | 30.40 |
| Comparative Examples 1 | CB 1 | 87.22 | 37.83 | 15.33 |
| Comparative Examples 2 | CB 2 | 82.07 | 37.45 | 8.84 |
From the result of table 2 as can be seen, sulfur transfer catalyst provided by the invention is after reduction is once with twice, and it adsorbs SO
2Ability apparently higher than the reference sulfur transfer catalyst, this explanation, compared with prior art, sulfur transfer catalyst provided by the invention has much higher reducing/regenerating performance.
Claims (16)
1. sulfur transfer catalyst, it is characterized in that, this catalyzer contains the composition that contains magnesium-aluminium spinel and the cerium of the heavy % of 2-30 and/or the oxide compound of vanadium of the heavy % of 70-98, the described composition that contains magnesium-aluminium spinel contains the magnesium oxide of the heavy % of 25-30, the rare-earth oxide except that cerium of the aluminum oxide of the heavy % of 60-70 and the heavy % of 5-10, wherein, magnesium and aluminium form spinel structure, the content of free magnesium is lower than the described 5 heavy % that contain the total composition of magnesium-aluminium spinel, and the described most probable bore dia that contains the composition of magnesium-aluminium spinel is the 100-200 dust.
2. catalyzer according to claim 1 is characterized in that, the described composition levels that contains magnesium-aluminium spinel is the heavy % of 75-95, and cerium and/or barium oxide content are the heavy % of 5-25.
3. catalyzer according to claim 1 is characterized in that, the content of described free magnesium is lower than the described 3 heavy % that contain the total composition of magnesium-aluminium spinel.
4. catalyzer according to claim 1 is characterized in that, described rare earth metal except that cerium is selected from lanthanum or rich lanthanum and does not contain the mischmetall of cerium.
5. catalyzer according to claim 1 is characterized in that, the specific surface of described composition is not less than 100 meters
2/ gram, pore volume is 0.3-0.5 milliliter/gram.
6. claim 1 Preparation of catalysts method, comprise with a kind of composition that contains magnesium-aluminium spinel of solution impregnation that contains cerium and/or vanadium compound, dry also roasting, it is characterized in that, the described composition that contains magnesium-aluminium spinel contains the magnesium oxide of the heavy % of 25-30, the rare-earth oxide except that cerium of the aluminum oxide of the heavy % of 60-70 and the heavy % of 5-10, wherein, magnesium and aluminium form spinel structure, the content of free magnesium is lower than the described 5 heavy % that contain the total composition of magnesium-aluminium spinel, the described most probable bore dia that contains the composition of magnesium-aluminium spinel is the 100-200 dust, the preparation method of said composition comprises that (1) is with aluminum oxide and/or aluminium hydroxide, rare earth compound except that cerium, deionized water and acid mix, reaction is at least 5 minutes under 40-100 ℃ temperature, the add-on of acid makes the pH value of the slurries that obtain be 1.5-4, water, it is the heavy % of 5-20 that the add-on of aluminum oxide and/or aluminium hydroxide and described rare earth compound makes the solid content of the slurries that obtain, and, make the aluminum oxide that contains containing of obtaining the heavy % of 60-70 in magnesium and the aluminate composition and the rare-earth oxide except that cerium of the heavy % of 5-10, (2) in the slurries that obtain, add magnesium oxide and/or magnesium hydroxide, reaction is at least 5 minutes under 40-100 ℃ temperature, the add-on of magnesium oxide and/or magnesium hydroxide makes the composition that contains magnesium-aluminium spinel that obtains contain the magnesium oxide that 25-30 weighs %, the product that (3) are dry and roasting obtains.
7. method according to claim 6 is characterized in that, described aluminum oxide is selected from can be by in the aluminum oxide of sour peptization one or more, and described aluminium hydroxide is selected from one or more in an alumina trihydrate and the water aluminum oxide.
8. method according to claim 7 is characterized in that described aluminum oxide is selected from one or more in ρ-aluminum oxide, χ-aluminum oxide, η-aluminum oxide, gama-alumina, κ-aluminum oxide, δ-aluminum oxide and the θ-aluminum oxide; Described aluminium hydroxide is selected from one or more in gibbsite, surge aluminium stone, promise diaspore, diasporite, boehmite, the pseudo-boehmite.
9. method according to claim 8 is characterized in that described aluminum oxide and/or aluminium hydroxide refer to pseudo-boehmite.
10. method according to claim 6 is characterized in that, described rare earth metal except that cerium refers to lanthanum or rich lanthanum and do not contain the rare earth metal of cerium.
11. method according to claim 6 is characterized in that, described acid is selected from nitric acid and/or hydrochloric acid.
12. method according to claim 6 is characterized in that, the temperature of reaction in described step (1) or (2) is 50-80 ℃, and the reaction times is 5-60 minute.
13. method according to claim 12 is characterized in that, the described reaction times is 10-30 minute.
14. method according to claim 6 is characterized in that, the pH value of slurries is 2-3 described in the step (1).
15. method according to claim 6 is characterized in that, the described drying temperature of step (3) is 100-400 ℃, and maturing temperature is 650-800 ℃, and roasting time is 1-4 hour.
16. method according to claim 6 is characterized in that, contains after the composition of magnesium-aluminium spinel with containing cerium and/or vanadium solution dipping, the exsiccant temperature is 100-300 ℃, and maturing temperature is 600-750 ℃, and roasting time is 1-5 hour.
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| CNB001207458A CN1142015C (en) | 2000-07-13 | 2000-07-13 | Sulfur transfer catalyst and its preparing process |
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| CNB001207458A CN1142015C (en) | 2000-07-13 | 2000-07-13 | Sulfur transfer catalyst and its preparing process |
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| CN1142015C true CN1142015C (en) | 2004-03-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1333044C (en) | 2003-09-28 | 2007-08-22 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| US7347930B2 (en) | 2003-10-16 | 2008-03-25 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| CN100425339C (en) * | 2004-07-14 | 2008-10-15 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and its preparation method |
| CN101555416B (en) * | 2008-04-07 | 2013-09-11 | 北京三聚环保新材料股份有限公司 | Method for improving abrasion resistance of catalytic cracking microphere sulfur transfer agent and high strength microphere sulfur transfer agent prepared by using same |
| CN101564692B (en) * | 2009-06-01 | 2011-05-25 | 西北大学 | Benzyl alcohol selective oxidation catalyst, preparation method and application thereof |
| CN102839010A (en) * | 2011-06-23 | 2012-12-26 | 中国石油天然气集团公司 | Preparation method for modified magnesium aluminum spinel having acidity and alkality |
| CN102974331B (en) * | 2011-09-06 | 2014-10-01 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent and preparation method thereof |
| CN103182311B (en) * | 2011-12-29 | 2014-12-03 | 北京三聚环保新材料股份有限公司 | Preparation method of sulfur-resistant carbon monoxide shift catalyst carrier |
| CN103897722B (en) * | 2012-12-27 | 2015-10-14 | 北京三聚环保新材料股份有限公司 | A kind of technique preparing FCC desulfurizing assistant agent |
| CN103920455B (en) * | 2013-01-14 | 2016-03-30 | 北京三聚环保新材料股份有限公司 | The preparation method of a kind of high activity and high-wearing feature microphere sulfur transfer agent |
| CN103861436B (en) * | 2014-03-20 | 2016-03-30 | 中国石油大学(华东) | Catalytic cracking fuel gas sulfur transfer additive of multiphase and preparation method thereof and application |
| JP2024533436A (en) | 2021-09-09 | 2024-09-12 | 中国石油化工股▲ふん▼有限公司 | CATALYST FOR REDUCING SOx AND NOX IN EXHAUST GAS, METHOD FOR PREPARING SAME, AND METHOD FOR REMOVING SOx AND NOX FROM EXHAUST GAS |
| CN115055203A (en) * | 2022-07-20 | 2022-09-16 | 成都蓉澄石化科技有限公司 | Heavy oil catalytic cracking catalyst |
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