CN106925295A - A kind of co-catalyst of reduction FCC regenerated flue gas pollutant emissions and its application - Google Patents
A kind of co-catalyst of reduction FCC regenerated flue gas pollutant emissions and its application Download PDFInfo
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- B01D53/34—Chemical or biological purification of waste gases
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Abstract
Co-catalyst and its application the present invention relates to a kind of reduction FCC regenerated flue gas pollutant emissions.The co-catalyst includes microsphere particle A and microsphere particle B；Counted with the weight of microsphere particle A as 100%, the microsphere particle A is included：80 98% aluminum oxide, 0.1 10% silica, 1 15% oxide and the oxide of 0.1 3% rare earth element selected from one or two metals in group vib and IB races；Counted with the weight of microsphere particle B as 100%, the microsphere particle B is included：50 80% aluminum oxide, 10 50% oxide and the oxide of 0.1 10% rare earth element selected from one or more metals in Group IIA, Group IVB and VIII.The co-catalyst is applied to reduce the discharge of nitrogen-containing pollutant, can substantially reduce the discharge of the atmosphere pollution such as NOx, SOx and CO in regenerated flue gas.
Description
Technical field
The present invention relates to a kind of for reducing the Air Pollutant Emission such as NOx, SOx and CO in FCC apparatus regenerated flue gas
Co-catalyst and its application.
Background technology
Fluid catalytic cracking (hereinafter referred to as FCC) device is one of important heavy oil lighting device of oil plant, is production
The core apparatus of light oil particularly high-knock rating gasoline, are also the important process for producing the Organic Chemicals such as low-carbon alkene.
But containing a certain amount of SOx, NOx and CO etc. to the disagreeableness contaminant gases of environment in FCC regenerated flue gas.According to statistics, refine
The 6%-7% and 10% of total release in SOx and NOx the difference duty gas of oily enterprise's discharge, the overwhelming majority therein comes from
FCC apparatus.
NOx and SOx in FCC regenerated flue gas are mainly derived from nitrogen-containing compound and sulfur-containing compound in feedstock oil.
In FCC riser reactors, while feedstock oil cracking, the small part coke laydown of generation inactivates it in catalyst surface,
Part sulphur and nitrogen enter coke, when carrying out catalyst coke burning regeneration process in a regenerator, sulphur, nitrogen oxidation transformation into
SOx and NOx, is discharged into air with regenerated flue gas.There is correlative study to show (Jin S Yoo, John
A.Karch.Catalytic SOx abatement:The role of magnesium aluminate spinel in the
removal of SOx from fluid catalytic cracking(FCC)flue gas[J].Ind Eng Chem
Res,1988,27:1356-1360), the sulfur content in catalytically cracked material is generally 0.3 weight %-3.0 weight %, in residual oil
Sulfur content is up to 4.0 weight %.After cracked, the weight %-45 weight % of sulphur about 35 in raw material is with H2The form of S enters gas
Product, 50 weight %-60 weight % enter fluid product, and 2 weight %-5 weight % enter coke, in a regenerator in coke
Sulphur is all oxidized to SOx.Nitrogen content in feedstock oil is general very low, about 0.05 weight %-0.5 weight %.In cracking
In course of reaction, basic nitrogen compound is adsorbed on the acid centre of catalyst and forms coke, and neutral nitrogen compound is then
It is considered as entering in product, the nitrogen in raw material close to half enters coke.In catalyst regeneration burning process, the nitrogen on coke
Only 3%-25% enters flue gas in the form of NO, and remaining is then converted into N2Form exist.NOx in FCC regenerated flue gas
Concentration is 0.005v%-0.05v%, mainly NO (about 90%), and a small amount of NO is contained simultaneously2；SOx is dense in FCC regenerated flue gas
It is 0.02v%-0.1v% to spend, wherein about 90% is SO2, about 10% is SO3.It is same in FCC regenerated flue gas in addition to NOx and SOx
Shi Hanyou O2、CO2, CO and H2O, the concentration of these gases is influenceed to change greatly by operating condition.
With environmental regulation increasingly stricter both at home and abroad, to reduce atmosphere pollution, the flue gas desulfurization of FCC apparatus, denitration
And the thing that CO discharges are increasingly paid attention to as industry is reduced, FCC regenerated flue gas pollution reduction pressure is increasingly urgent.Many
Reduce in the technology of NOx, SOx and CO pollutant emission in FCC regenerated flue gas, be most have using co-catalyst (abbreviation auxiliary agent)
Effect, most economical method.Therefore, a kind of multiple-effect co-catalyst is developed, NOx, SOx and CO are dirty in can simultaneously reducing regenerated flue gas
Dye thing discharge is study hotspot in recent years.Sanju Environment Protection New Material Co., Ltd., Beijing proposes the sulphur transfer combustion-supporting triple effect of denitrogenation
Agent and its production and use (number of patent application is CN02153284.2) simultaneously reports commercial Application situation (catalytic cracking cigarette
Gas turns the commercial Application of sulphur denitrogenation and combustion-supporting three functions catalyst FP-DSN, Chen Zhi etc., oil refining design, 2002,32 (11):7-
11), the co-catalyst has the ability of SOx and NOx in stronger removing flue gas, while there is CO combustion-supporting effects.During application test, then
The average removal efficiency of SOx is up to 72.85% (SOx initial concentrations 736mg/m in raw device flue gas3), the average removal efficiency of NOx reaches
85.90% (NOx initial concentrations 269mg/m3)；Additionally, Tianjin Tuo get petroleum technologies Development Co., Ltd also have developed a kind of cigarette
Desulfurization, denitration, combustion-supporting triple effect auxiliary agent have simultaneously carried out commercial Application (triple effect auxiliary agent answering in catalytic cracking unit flue gas desulfurization
With Zhou Jianwen etc. refines oil engineering and technology, 2015,45 (3)：43-45；The combustion-supporting triple effect auxiliary agent of sulfur transfer additive coordinated desulfurization denitration
Application on catalytic cracking unit, white clouds ripple etc., Speciality Petrochemicals, 2016,33 (1)：50-55).Triple effect auxiliary agent accounts for system
During about 2.90 weight % of total catalyst reserve, flue gas desulphuization rate is 76.98% (SOx initial concentrations 821.7-983.3mg/m3),
Significant desulfurization effect；Flue-gas denitrification rate is 61.11% (NOx initial concentrations 99.0-119.0mg/m3)；Triple effect auxiliary agent is combustion-supporting simultaneously
Work well, alternative CO combustion adjuvants.At present, the development of triple effect co-catalyst and application reduces FCC dresses to a certain extent
The discharge of flue gas pollutant is put, but totally apparently, the triple effect co-catalyst in commercial Application report is mainly de- SOx, uses
Occasion is mostly that, in NOx initial concentrations device not high, the use of these co-catalysts is also not reaching under the conditions of high concentrate NOx
The target of efficient removal SOx.
Research finds dense-phase bed exit CO, CO2、O2Content be respectively 1.7%, 14.2%, 1.9%；And regenerator
CO, CO in the flue gas of outlet2、O2Content be respectively 0.1%, 16.3%, 1.0%, even if this explanation in situation about burning completely
Under, the oxidation that regenerator dense-phase bed still has the carbon monoxide of high level, CO occurs mainly in dilute phase bed.Because
The uneven distribution of gas and combustion adjuvant in fluid bed, causes oxygen to transmit uneven, dense-phase bed O2Content is low, CO contents compared with
(catalytic cracking process and engineering, Chen Junwu etc., Sinopec publishing house, 1995, P944) high.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of reduction FCC regenerated flue gas pollutant emissions
Co-catalyst and its application, the purpose of the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas is substantially reduced to reach.
In order to achieve the above object, the invention provides a kind of co-catalyst of reduction FCC regenerated flue gas pollutant emissions,
The co-catalyst includes microsphere particle A and microsphere particle B；
Counted with the weight of microsphere particle A as 100%, microsphere particle A is included：The aluminum oxide of 80-98%, the oxygen of 0.1-10%
SiClx, the oxygen of the rare earth element of the oxide and 0.1-3% selected from one or two metals in group vib and IB races of 1-15%
Compound；
Counted with the weight of microsphere particle B as 100%, microsphere particle B is included：The aluminum oxide of 50-80%, the choosing of 10-50%
The oxide of the oxide of one or more metals from Group IIA, Group IVB and VIII and the rare earth element of 0.1-10%.
In above-mentioned co-catalyst, it is preferable that the weight ratio of microsphere particle A and microsphere particle B is (1:3)-(3:1).
In above-mentioned co-catalyst, it is preferable that the heap density of microsphere particle A is 0.85-1.00g/mL, microsphere particle B's
Heap density is 0.75-0.85g/mL.
In above-mentioned co-catalyst, it is preferable that the sieve of microsphere particle A is grouped into 0-20 μm<0.1 weight %, microballoon
The sieve of grain B is grouped into 0-20 μm<4.0 weight %.
In above-mentioned co-catalyst, it is preferable that in microsphere particle A：
Metal in group vib is one or two the combination in Mo and W, and the percentage by weight of its oxide is no more than micro-
The 10% of ball particle A；
Metal in IB races is Ag, and the percentage by weight of its oxide is no more than the 3% of microsphere particle A；
Rare earth element is Ce, and the percentage by weight of its oxide accounts for the 0.2-2% of microsphere particle A.
In above-mentioned co-catalyst, it is preferable that in microsphere particle B：
The metal of Group IIA is Mg, and the percentage by weight of its oxide is no more than the 50% of microsphere particle B；
The metal of Group IVB is V, and the percentage by weight of its oxide is no more than the 5% of microsphere particle B；
The metal of VIII is Fe and Pd, and the percentage by weight of its oxide is no more than the 4% of microsphere particle B；
Rare earth element is Ce, and the percentage by weight of its oxide is no more than the 6% of microsphere particle A.
Specific embodiment of the invention, it is preferable that microsphere particle A is prepared by following steps：To contain
The silicon source for having aluminum oxide is beaten, and controls slurries pH, and mashing is then mixed with the silicon source containing silica, then is spray-dried, is calcined,
Microsphere particle carrier is obtained, by microsphere particle carrier is with the salting liquid selected from one or two metals in VB races, IB races and contains
There is the salt solution impregnation of rare earth element, microsphere particle A is obtained after drying, roasting；
Wherein, microsphere particle B is prepared by following steps：Silicon source containing aluminum oxide is carried out into mashing plastic,
Control slurries pH, is subsequently adding the oxide selected from one or more metals in Group IIA, Group IVB and VIII, and mixing is beaten
Slurry, then be spray-dried, be calcined, microsphere particle carrier is obtained, by microsphere particle carrier with selected from Group IIA, Group IVB and VIII
One or more metals salting liquid and containing rare earth element metal salt solution dipping, through drying, roasting after obtain microballoon
Particle B.
In the preparation process of above-mentioned co-catalyst, it is preferable that when mashing is mixed, component of the regulation containing silica
Addition, the heap density for making microsphere particle A is 0.85-1.00g/mL；In the same manner, when mashing is mixed, regulation contains Group IIA
The addition of oxide, the heap density for making microsphere particle B is 0.75-0.85g/mL.
In the preparation process of above-mentioned co-catalyst, it is preferable that it is 1.2-2.0 to control slurries pH；Dry temperature is
120-280 DEG C, the dry time is 1-3 hours；It is highly preferred that dry temperature is 180-200 DEG C, the dry time is 1-2
Hour；
The temperature of roasting is 500-800 DEG C, time 1-4 hours of roasting；It is highly preferred that the temperature of roasting is 600-700
DEG C, the time of roasting is 2-3 hours.
In the preparation method of microsphere particle A and microsphere particle B, mashing plastic, spray drying, dipping, drying, roasting,
Method for sieving is conventional catalyst process technology, does not have particular/special requirement.
Above-mentioned co-catalyst can apply to reduce the discharge of nitrogen-containing pollutant, it is preferable that the present invention is according to regenerated flue gas
Middle NOxThe volume ratio of/SOx is mixed as co-catalysis microsphere particle A and microsphere particle B according to same ratio (weight ratio)
Agent is used, and the co-catalyst is with (1:99)-(6:94) ratio is used in mixed way with industrial poising agent.
The characteristics of present invention coexists according to NOx in regenerator dense-phase bed and CO, NOx reducing agents are made with CO, there is provided a kind of
Heap density is distributed in fluid bed dense-phase bed probability slightly larger than the microsphere particle A of FCC catalyst using the big microsphere particle of heap density
Big characteristic, selects suitable active component to make it in dense-phase bed to reaction NO+CO → N2+CO2Have catalysis activity high and
Selectivity, while in view of in dense-phase bed coke institute's sulfur-containing compound burning generation SOx, SOx easily makes catalyst poisoning, so
The microsphere particle A of offer has the ability that sulfur resistive oxide poisons；And a kind of heap density is provided and is slightly less than the micro- of FCC catalyst
Ball particle B, using heap density minimicrosphere distribution of particles in the big characteristic of fluid bed dilute phase bed probability, selects suitable activearm
Dividing makes it in dilute phase bed to reaction CO+O2→CO2、SO2+O2→SO3And MxOy+SO3→Mx(SO4)Z(SO3In microsphere particle B
Upper and active component MxOy reacting generating salt Mx (SO4) z) there is catalysis activity and selectivity high, and on microsphere particle B
The sulfate of formation is susceptible to M in riser reactorx(SO4)Z+H2(C3H8)→MxOyReaction and realize reduction.And
To two kinds of microsphere particles A and B providing, the content according to NOx, SOx and CO pollutant in regenerated flue gas is according to different ratios
Be mixed to form co-catalyst, in FCC regenerators using can strengthen respectively removing NOx, SOx that dilute, dense-phase bed occurs and
The reaction of CO, significantly reduces the discharge of the atmosphere pollution such as NOx, SOx and CO in regenerated flue gas.
Can be by the NOx in regenerated flue gas from 500mg/m using above-mentioned co-catalyst in FCC apparatus3It is reduced to 95mg/m3,
Removal efficiency reaches 81%；SO in flue gasXFrom 685mg/m3It is reduced to 101mg/m3, removal efficiency reaches 85.3%；CO in flue gas
Content reduces 9.3% compared with using Pt combustion adjuvants；And the addition of co-catalyst is to FCC total liquid yields and light receipts without negative shadow
Ring, the yield of main purpose product is basically unchanged.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.
Raw materials used in each embodiment is the slaine of market sale, for example cobalt nitrate (Co (NO3)2·6H2O) it is Tianjin
The production of recovery development in science and technology Co., Ltd of city；Silver nitrate (AgNO3) it is the production of Zhengzhou Hua Mao chemical products Co., Ltd；Palladium nitrate
(Pd(NO3)2·2H2O) it is the production of Tianjin recovery fine chemistry industry research institute；Cerous nitrate (Ce (NO3)3·6H2O) for Zibo is auspicious rich
Health rare earth material Co., Ltd produces；Ferric nitrate (Fe (NO3)3·9H2O) it is the prosperous beautiful peaking plant produced in Taiyuan City；Or market pin
Sell solvable and water and heat resolve turns into the metallic salt of oxide, such as ammonium metavanadate (NH4VO3) it is pure, the Tianjin light of analysis
Multiple development in science and technology Co., Ltd production, ammonium metatungstate ((NH4)6W7O24·6H2O) for analysis is pure, Chinese medicines group chemical reagent is limited
Company produces；Ammonium molybdate ((NH4)6Mo7O24·4(H2O)) for analysis is pure, the life of Shanghai Aladdin biochemical technology limited company
Produce；The boehmite (the wherein weight % of alumina content 60) of Shandong Aluminium Industrial Corp's production；Kaolin is Suzhou China kaolinite
God in charge of the Earth department produces (SiO2The weight % of content 56), hydrochloric acid (the weight % of concentration 36.5, chemistry is pure) used, Beijing Chemical Plant's production；
Magnesia (MgO) produce for Weifang Xu Hui new materials Co., Ltd (>The weight % of content 98).
Embodiment 1
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst includes microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.576 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.097 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained.The microsphere particle carrier is salic
94.57 weight %, the weight % of silica 5.43.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 63.4 grams of ammonium metatungstates, 13.4 grams of ammonium molybdates, 16 grams
Silver nitrate, 27.6 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, in 700 DEG C be calcined 120 minutes, obtain microsphere particle A.
Screening microsphere particle A, is grouped into the sieve of microsphere particle A：0-20 μm of particle<0.1 weight %.Finally, it is micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 87.0 weight % aluminum oxide, 5.0 weight % silica,
5.0 weight % tungsten oxides, 1.0 weight % molybdenum oxides, 1.0 weight % silver oxides, 1.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.491 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.107 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；70-90 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 600 DEG C, 1 kilogram of microsphere particle carrier is obtained.Microsphere particle carrier composition is oxygen-containing
Change the weight % of aluminium 89.45, the weight % of magnesia 10.55.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 2.7 grams of ammonium metavanadates, 107.3 grams of ferric nitrates, 0.9 gram
Palladium nitrate, 80.2 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, in 700 DEG C be calcined 120 minutes, obtain microsphere particle B.
Screening microsphere particle B, is grouped into the sieve of microsphere particle B：0-20 μm of particle<4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 84.76 weight % aluminum oxide, 10.0 weight % magnesia,
0.2 weight % vanadium oxides, 2.0 weight % iron oxide, the weight % of palladium oxide 0.04,3.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the co-catalyst:1.
Embodiment 2
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst includes microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.665 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.002 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained.The microsphere particle carrier is salic
99.90 weight %, the weight % of silica 0.1.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 24 grams of ammonium metatungstates, 6.3 grams of ammonium molybdates, 1.5 grams of nitre
Sour silver, 5.2 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 DEG C are impregnated with solution saturation
Drying 120 minutes, is calcined 120 minutes in 700 DEG C, obtains microsphere particle A.
Screening microsphere particle A, is grouped into the sieve of microsphere particle A：0-20 μm of particle<0.1 weight %.Finally, it is micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 97.1 weight % aluminum oxide, 0.1 weight % silica,
2.0 weight % tungsten oxides, 0.5 weight % molybdenum oxides, 0.1 weight % silver oxides, 0.2 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 0.883 kilogram of mashing of boehmite is subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.48 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；70-90 DEG C is heated to, aging about 120 minutes is stood simultaneously
Continue to stir 30 minutes, then by the colloid material after mashing with spray drying system is pumped into, obtain microsphere particle carrier, will
Microsphere particle carrier is calcined 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier constitutes oxygen-containingization
The weight % of aluminium 52.97, the weight % of magnesia 47.03.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 53.9 grams of ammonium metavanadates, 5.3 grams of ferric nitrates, 0.5 gram
Palladium nitrate, 5.3 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, in 700 DEG C be calcined 120 minutes, obtain microsphere particle B.
Screening microsphere particle B, is grouped into the sieve of microsphere particle B：0-20 μm of particle<4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 50.68 weight % aluminum oxide, 45.0 weight % magnesia,
4.0 weight % vanadium oxides, 0.1 weight % iron oxide, the weight % of palladium oxide 0.02,0.2 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the co-catalyst:1.
Embodiment 3
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst includes microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.468 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.213 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained.The microsphere particle carrier is salic
88.10 weight %, the weight % of silica 11.90.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 125 grams of ammonium metatungstates, 43.9 ammonium molybdates, 35.1 grams of nitre
Sour silver, 60.4 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 DEG C are impregnated with solution saturation
Drying 120 minutes, is calcined 120 minutes in 700 DEG C, obtains microsphere particle A.
Screening microsphere particle A, is grouped into the sieve of microsphere particle A：0-20 μm of particle<0.1 weight %.Finally, it is micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 74.0 weight % aluminum oxide, 10.0 weight % silica,
9.0 weight % tungsten oxides, 3.0 weight % molybdenum oxides, 2.0 weight % silver oxides, 2.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.104 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.344 kilogram of magnesia is added to be beaten in stirred tank about 60 minutes；Mashing about 60 minutes；70-90 DEG C is heated to, is stood old
Change about 120 minutes and continue stirring 30 minutes, the colloid material after mashing is then obtained micro- with spray drying system is pumped into
Ball particle carrier, 1 kilogram of microsphere particle carrier is obtained for 120 minutes by microsphere particle carrier in 600 DEG C of roastings, and the microsphere particle is carried
Body constitutes salic 66.27 weight %, the weight % of magnesia 33.73.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 29 grams of ammonium metavanadates, 17.2 ferric nitrates, 1.5 grams of nitric acid
Palladium, 17.1 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier is impregnated with solution saturation, then 180 DEG C of bakings
It is dry 120 minutes, it is calcined 120 minutes in 700 DEG C, obtain microsphere particle B.
Screening microsphere particle B, makes the particle of 0-20 μm of the screening composition of microsphere particle B<4 weight %.Finally, microsphere particle
The heap density of B is 0.8g/mL, and the composition of microsphere particle B contains 58.94 weight % aluminum oxide, 30.0 weight % magnesia, 2.0 weights
Amount % vanadium oxides, 3.0 weight % iron oxide, the weight % of palladium oxide 0.06,6.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the co-catalyst:1.
Embodiment 4
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst includes microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.468 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.213 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained.The microsphere particle carrier is salic
88.10 weight %, the weight % of silica 11.90.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 125 grams of ammonium metatungstates, 43.9 ammonium molybdates, 35.1 grams of nitre
Sour silver, 60.4 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 DEG C are impregnated with solution saturation
Drying 120 minutes, is calcined 120 minutes in 700 DEG C, obtains microsphere particle A.
Screening microsphere particle A, is grouped into the sieve of microsphere particle A：0-20 μm of particle<0.1 weight %.Finally, it is micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 74.0 weight % aluminum oxide, 10.0 weight % silica,
9.0 weight % tungsten oxides, 3.0 weight % molybdenum oxides, 2.0 weight % silver oxides, 2.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.491 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.107 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；70-90 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 600 DEG C, 1 kilogram of microsphere particle carrier is obtained.Microsphere particle carrier composition is oxygen-containing
Change the weight % of aluminium 89.45, the weight % of magnesia 10.55.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 2.7 grams of ammonium metavanadates, 107.3 grams of ferric nitrates, 0.9 gram
Palladium nitrate, 80.2 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, in 700 DEG C be calcined 120 minutes, obtain microsphere particle B.
Screening microsphere particle B, is grouped into the sieve of microsphere particle B：0-20 μm of particle<4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 84.76 weight % aluminum oxide, 10.0 weight % magnesia,
0.2 weight % vanadium oxides, 2.0 weight % iron oxide, the weight % of palladium oxide 0.04,3.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the co-catalyst:1.37.
Embodiment 5
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst includes microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.468 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.213 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained.The microsphere particle carrier is salic
88.10 weight %, the weight % of silica 11.90.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 125 grams of ammonium metatungstates, 43.9 ammonium molybdates, 35.1 grams of nitre
Sour silver, 60.4 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 DEG C are impregnated with solution saturation
Drying 120 minutes, is calcined 120 minutes in 700 DEG C, obtains microsphere particle A.
Screening microsphere particle A, is grouped into the sieve of microsphere particle A：0-20 μm of particle<0.1 weight %.Finally, it is micro-
The heap density of ball particle A is 0.9g/mL, and the composition of microsphere particle A contains 74.0 weight % aluminum oxide, 10.0 weight % silica,
9.0 weight % tungsten oxides, 3.0 weight % molybdenum oxides, 2.0 weight % silver oxides, 2.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 0.883 kilogram of mashing of boehmite is subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.48 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；70-90 DEG C is heated to, aging about 120 minutes is stood simultaneously
Continue to stir 30 minutes, then by the colloid material after mashing with spray drying system is pumped into, obtain microsphere particle carrier, will
Microsphere particle carrier is calcined 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier constitutes oxygen-containingization
The weight % of aluminium 52.97, the weight % of magnesia 47.03.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 53.9 grams of ammonium metavanadates, 5.3 grams of ferric nitrates, 0.5 gram
Palladium nitrate, 5.3 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, in 700 DEG C be calcined 120 minutes, obtain microsphere particle B.
Screening microsphere particle B, is grouped into the sieve of microsphere particle B：0-20 μm of particle<4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 50.68 weight % aluminum oxide, 45.0 weight % magnesia,
4.0 weight % vanadium oxides, 0.1 weight % iron oxide, the weight % of palladium oxide 0.02,0.2 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the co-catalyst:1.37.
Embodiment 6
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst includes microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.576 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.097 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained.The microsphere particle carrier is salic
94.57 weight %, the weight % of silica 5.43.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 63.4 grams of ammonium metatungstates, 13.4 grams of ammonium molybdates, 16 grams
Silver nitrate, 27.6 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, in 700 DEG C be calcined 120 minutes, obtain microsphere particle A.
Screening microsphere particle A, is grouped into the sieve of microsphere particle A：0-20 μm of particle<0.1 weight %.Finally, it is micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 87.0 weight % aluminum oxide, 5.0 weight % silica,
5.0 weight % tungsten oxides, 1.0 weight % molybdenum oxides, 1.0 weight % silver oxides, 1.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 0.883 kilogram of mashing of boehmite is subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.48 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；70-90 DEG C is heated to, aging about 120 minutes is stood simultaneously
Continue to stir 30 minutes, then by the colloid material after mashing with spray drying system is pumped into, obtain microsphere particle carrier, will
Microsphere particle carrier is calcined 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier constitutes oxygen-containingization
The weight % of aluminium 52.97, the weight % of magnesia 47.03.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 53.9 grams of ammonium metavanadates, 5.3 grams of ferric nitrates, 0.5 gram
Palladium nitrate, 5.3 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, in 700 DEG C be calcined 120 minutes, obtain microsphere particle B.
Screening microsphere particle B, is grouped into the sieve of microsphere particle B：0-20 μm of particle<4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 50.68 weight % aluminum oxide, 45.0 weight % magnesia,
4.0 weight % vanadium oxides, 0.1 weight % iron oxide, the weight % of palladium oxide 0.02,0.2 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the co-catalyst:1.37.
Embodiment 7
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst only includes microsphere particle A.The preparation method of microsphere particle A is shown in embodiment 4.
Embodiment 8
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emission such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst only includes microsphere particle B.The preparation method of microsphere particle B is shown in embodiment 4.
Comparative example 1
The co-catalyst of the selection of comparative example 1 is the commodity for having been used to commercial Application in the prior art：CO combustion adjuvants (Shandong
Jun Fei Chemical Co., Ltd.s).
Comparative example 2
The co-catalyst of the selection of comparative example 2 is the commodity for having been used to commercial Application in the prior art：TUD-DNS3 auxiliary agents
(Tianjin Tuo get petroleum technologies Development Co., Ltd).
Comparative example 3
The co-catalyst of the selection of comparative example 3 is the commodity for having been used to commercial Application in the prior art：FP-DSN auxiliary agents (north
Capital trimerization environmental friendly material limited company).
Experimental performance evaluation result
The chemical composition of the co-catalyst in each embodiment and comparative example is by x-ray fluorescence spectrometry.
Flue gas is analyzed with German MRU companies E8500 Portable smoke analysis instrument to constitute, including O2, NO, NOx, SOx, CO and
CO2Content.
The co-catalyst for being used for performance evaluation in each embodiment and comparative example is needed in advance in fluid bed hydrothermal aging device
800 DEG C, aging 10 hours of 100% vapor are carried out, then (sinopec catalyst Chang Ling branch company gives birth to FCC industry poising agent
The CDC catalytic cracking catalysts of product) mixing, co-catalyst is 3 with FCC industry poising agent weight ratios:97, in successive reaction-again
Evaluated on the medium-sized experimental provision of raw catalytic cracking, 10 kilograms of co-catalyst loading amount, 500 DEG C of reaction temperature, co-catalyst is again
Raw 700 DEG C of temperature.
1st, the raw material oil nature that the present invention is used is as shown in table 1.
Table 1
| Project | Data | Project | Data |
| Elementary analysis, m% | Density (20 DEG C), g/cm3 | 0.921 | |
| C | 86.77 | Carbon residue, m% | 4.51 |
| H | 12.64 | Race constitutes, m% | |
| S | 0.24 | Saturation point | 42.1 |
| N | 0.15 | Aromatic hydrocarbons point | 33.6 |
| Tenor, ug/g | Colloid | 24.1 | |
| Fe | 5.94 | Asphalitine | 0.2 |
| Ni | 11.60 | ||
| V | 4.15 | ||
| Na | 0.50 |
Material density 0.921g/cm3, carbon residue 4.51wt%, S, N element composition are in higher level, are refinings at present
The typical case that factory uses urges raw material again.NOx, SOx and CO content are higher in flue gas during catalyst regeneration process.2nd, co-catalyst and change
Learn composition as shown in table 2.
Table 2
3rd, the co-catalyst in Application Example and comparative example, the concentration of major pollutants and change in regenerated flue gas, such as
Shown in table 3.
Embodiment 1-6 is played a role to NOx, SOx and CO in reduction flue gas, and wherein embodiment 4 is contrasted with blank assay
Example 1 compares, and NOx, SOx and the CO in flue gas reduce 81.0%, 85.3% and 9.3% respectively, shows good taking off
Except effect.In embodiment 7 and 8, be used alone A particles or B particles, removing NOx, SOx and and CO in terms of have one respectively
Fixed limitation, without the effect that performance is optimal.
Table 3
4th, the co-catalyst in embodiment and comparative example is as shown in table 4 to the performance of catalytic cracking product.
Table 4
The addition of institute's cocatalyst is had little to no effect to product slates, and wherein the dry gas of embodiment 3,4 and coke are produced
Rate is lower slightly, better than other co-catalysts.
Claims (10)
1. in a kind of reduction FCC regenerated flue gas nitrogen-containing pollutant discharge co-catalyst, the co-catalyst comprising microsphere particle A and
Microsphere particle B；
Counted with the weight of microsphere particle A as 100%, the microsphere particle A is included：The aluminum oxide of 80-98%, the oxygen of 0.1-10%
SiClx, the oxygen of the rare earth element of the oxide and 0.1-3% selected from one or two metals in group vib and IB races of 1-15%
Compound；
Counted with the weight of microsphere particle B as 100%, the microsphere particle B is included：The aluminum oxide of 50-80%, the choosing of 10-50%
The oxide of the oxide of one or more metals from Group IIA, Group IVB and VIII and the rare earth element of 0.1-10%.
2. co-catalyst as claimed in claim 1, wherein, the weight ratio of the microsphere particle A and microsphere particle B is (1:3)-
(3:1)。
3. co-catalyst as claimed in claim 1 or 2, wherein, the heap density of the microsphere particle A is 0.85-1.00g/mL,
The heap density of the microsphere particle B is 0.75-0.85g/mL.
4. the co-catalyst as any one of claim 1-3, wherein, the sieve of the microsphere particle A is grouped into 0-20 μ
m<0.1 weight %, the sieve of the microsphere particle B is grouped into 0-20 μm<4.0 weight %.
5. the co-catalyst as any one of claim 1-4, wherein, in microsphere particle A：
Metal in the group vib is one or two the combination in Mo and W, and the percentage by weight of its oxide is no more than institute
State the 10% of microsphere particle A；
Metal in the IB races is Ag, and the percentage by weight of its oxide is no more than the 3% of the microsphere particle A；
The rare earth element is Ce, and the percentage by weight of its oxide accounts for the 0.2-2% of the microsphere particle A.
6. the co-catalyst as any one of claim 1-5, wherein, in microsphere particle B：
The metal of the Group IIA is Mg, and the percentage by weight of its oxide is no more than the 50% of the microsphere particle B；
The metal of the Group IVB is V, and the percentage by weight of its oxide is no more than the 5% of the microsphere particle B；
The metal of the VIII is Fe and Pd, and the percentage by weight of its oxide is no more than the 4% of the microsphere particle B；
The rare earth element is Ce, and the percentage by weight of its oxide is no more than the 6% of the microsphere particle A.
7. the co-catalyst as any one of claim 1-6, wherein, the microsphere particle A is prepared by following steps
Obtain：Silicon source containing the aluminum oxide is beaten, slurries pH is controlled, is then mixed with the silicon source containing the silica and is beaten
Slurry, then be spray-dried, be calcined, microsphere particle carrier is obtained, by the microsphere particle carrier with described selected from VB races, IB races
The salting liquid of one or two metals and the salt solution impregnation containing the rare earth element, microballoon is obtained after drying, roasting
Grain A；
Wherein, the microsphere particle B is prepared by following steps：Silicon source containing the aluminum oxide is beaten into
Glue, controls slurries pH, is subsequently adding the oxide selected from one or more metals in Group IIA, Group IVB and VIII, mixes
Mashing, then is spray-dried, is calcined, and obtains microsphere particle carrier, by the microsphere particle carrier with selected from Group IIA, Group IVB and
The salting liquid of one or more metals in VIII and the metal salt solution containing the rare earth element impregnate, through drying, roasting
Microsphere particle B is obtained after burning.
8. co-catalyst as claimed in claim 7, wherein, when mashing is mixed, the regulation component containing silica
Addition, the heap density for making the microsphere particle A is 0.85-1.00g/mL；
Wherein, when mashing is mixed, the addition of the oxide containing Group IIA is adjusted, the heap density for making the microsphere particle B is
0.75-0.85g/mL。
9. co-catalyst as claimed in claim 7 or 8, wherein, the pH is 1.2-2.0；The dry temperature is 120-
280 DEG C, the dry time is 1-3 hours；Preferably, the dry temperature is 180-200 DEG C, and the dry time is that 1-2 is small
When；
The temperature of the roasting is 500-800 DEG C, and the time of roasting is 1-4 hours；Preferably, the temperature of the roasting is 600-
700 DEG C, the time of roasting is 2-3 hours.
10. the air such as NOx, SOx and CO in FCC` regenerated flue gas are reduced of the co-catalyst any one of claim 1-9
Application in pollutant emission, it is preferable that the co-catalyst is with (1:99)-(6:94) ratio mixes with industrial poising agent
Use.
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