CN101757944B - Cracking additive for increasing production of liquid gas and preparation method thereof - Google Patents
Cracking additive for increasing production of liquid gas and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cracking additive for increasing the production of liquid gas. The cracking additive has the following characteristics that: the additive contains a ZSM-5 molecular sieve grown in-situ on microspheres, Ni and V, the cracking additive uses discharged catalytic cracking equilibrium catalyst as material, inorganic base, silicon source, template agent and water are added, and after crystallization, the cracking additive is obtained; and with the total amount of the cracking additive as a reference and measured as simple substance, the Ni and the V account for 0.1 percent and 5 percent by weight. The cracking additive has high cracking activity and liquid gas selectivity, and can reduce the content of sulfur in gasoline product.
Description
Invention field
The invention relates to a kind of auxiliary agent that is used for catalytic cracking and preparation method thereof, further saying so has increasing production of liquid gas, reduces the cracking additive of product content of sulfur in gasoline and draws off the preparation method that agent is a raw material from the balance that contains Y zeolite that fluidized catalytic cracker draws off about a kind of.
Background technology
Catalytic cracking is important crude oil secondary operations technology, and the cracking under the solid acid catalyst effect of big molecular raw material oil generates industrial chemicals such as automobile-used fuel such as gasoline, diesel oil and propylene, butylene.Catalytic cracking catalyst mainly is made up of molecular sieve, binding agent and clay filled agent; In the catalyst use under reaction condition coking deactivation; Thereby need coke burning regeneration under oxygen-containing atmosphere; Reaction-the regeneration cycle of so continuous experience under the high-temperature water heat condition, wherein continuous avalanche of molecular sieve structure and destruction make activity of such catalysts reduce.And in the feedstock oil heavy metal deposition on catalyst; The activated centre of not only poisoning; And aggravation molecular sieve structure destruction, the metal catalytic effect impels the reaction selectivity variation, causes the product distribution and the product quality of this technology to change; Hydrogen and coke output increase greatly, and the productive rate of light-end products such as conversion ratio and gasoline significantly descends.Along with crude oil heaviness and poor qualityization day by day; Heavy metal contaminants content also has the trend that rises year by year; This catalyst poisoning and the inactivation that causes because of heavy metal pollution shows more outstandingly, makes to keeping constantly fresh makeup catalyst of catalytic activity, increases poising agent and unloads output.Owing to contain harmful heavy metal such as V, Ni and Sb etc. in the poising agent that draws off; Also can cause severe contamination when adopting traditional landfill method to handle capital and soil resource; Handle if do not do antiseepage when burying, these poising agents also can cause water resource pollution after overflow by the rainwater pouring.Therefore,, alleviate environmental pollution, have reality far-reaching significance again if, can practice thrift fresh catalyst with recycling again after these dead catalyst demetalizations.
Relevant catalytic cracking balance draws off the existing a large amount of reports of the demetallated research of agent, but mainly concentrates on the demetalization research of poising agent.Demetallated method can be divided into two big types on type, i.e. magnetic separating and recovering technology and chemical regeneration method.In the catalyzed cracking processing process, the heavy metal in the catalytic cracking unit charging (mainly being nickel, vanadium, calcium and iron) major part is deposited on the catalyst, makes catalyst produce magnetic strength property.Under the effect of high-intensity magnetic field; Can be selectively from catalyst inventory, reject degree of aging high, receive the far-gone catalyst granules of heavy metal pollution; Make that tenor is lower, the lighter catalyst of poisoning is higher with tenor, the heavier catalyst of poisoning is able to separate, and carries out reuse.Use few metallic pollution, the active high part return mechanism of magnetic separation technique such as Magna Cat technology [Hettinger W P.CatalToday 1992,13 (1): 157-189] and use, still will discard active low ferromagnetism partial equilibrium agent.And the complicated power consumption of magnetic separating apparatus is big, and cost is high.Therefore, magnetic separation technique has just improved the service efficiency of catalyst to a certain extent, can't fundamentally solve the handling problem that draws off catalyst.
The chemical regeneration method is that the catalytic cracking poising agent is contacted with a series of chemical reagent; Make the heavy metal such as the noxious material generation chemical reactions such as vanadium, nickel that are deposited on the catalyst; It is cleaned out or reduces its toxicity, make blocked passage obtain cleaning simultaneously, and the performances such as specific area and hole of catalyst are restored; Therefore through the chemical regeneration method active part of catalytic cracking equilibrium catalyst loss is restored, thereby obtains reuse.Poising agent activity after the chemical regeneration method is handled can access part and recover, and contains ammonia or fluorine containing waste water but can produce.Such as DEMET technology [Yoo J S.Ind Eng Chem Prod Res Rev1986; 25 (4): 549] utilize complicated chemical method to remove the pollution metal in the useless agent; Make the situation before its part returns to metallic pollution; Use as catalyst or auxiliary agent then, but the poor stability of activating catalyst.In addition, also have a lot of reports to adopt strong acid treatment to carry out process for reactivation, stress extrusion rate of heavy metals, be easy to the destruction to crystal structure of molecular sieve, its activity can decrease on the contrary.
The in use most important deactivation cause of catalytic cracking poising agent causes loss of activity from the molecular sieve structure avalanche; Above physics or chemical treatment method do not have head it off; Therefore can not the full recovery catalyst activity, and the catalyst activated activity stability is also not enough.Because poising agent in use physical property makes moderate progress, therefore there is research to extend in-situ crystallization technology, with its crystallization again, improve catalytic activity.
USP4,784,980 disclose the method for utilizing spent FCC catalyst to prepare molecular sieve, adopt poising agent under hydrothermal condition, in the solution of alkali metal containing oxide and sodium aluminate, to carry out crystallization, 25～150 ℃ of crystallization temperatures, time 1～24h prepares A type molecular sieve.
The regrow method of Y zeolite of the disclosed employing of WO93/08911 FCC poising agent is that the FCC poising agent is being contained crystal seed, silicon source, aluminium source and Na
+Crystallization under the condition that exists " regrows " to having the Y zeolite of higher crystallinity the Y zeolite that is damaged in the poising agent.
The disclosed poising agent of GB1342977 is the crystallization processing method again, is at crystal seed, NaOH, Na with the poising agent after the roasting dehydration
2SiO
3Under the existence condition, under 80 ℃～120 ℃, carry out crystallization, make the poising agent activity obtain bigger raising, poising agent microballoon abrasion resistance does not reduce simultaneously.
[Yang Xiaoming, Luo Jinge. chemistry of fuel journal .2001,29,225-230] reported and adopted NaOH alkali lye to handle the method that increases the poising agent molecular sieve content, but needing through harsh hydrothermal aging preliminary treatment, the molecular sieve amount increases few after the activation.
The CN1974008A report is a kind of to containing the Retreatment method of Y zeolite poising agent; This method comprises mixes making beating with said poising agent with the solution of a kind of oxyacid, oxyacid ammonium salt and another kind of water-soluble metal salt; Oven dry back roasting selectivity makes heavy metal contaminants iron, nickel and other metal form solable matter; Through pulping and washing, filtration, then with a kind of Na that contains
2O source and SiO
2The aqueous solution in source obtains reactivating catalyst presetting to regenerate under the guiding of crystal seed.Reactivating catalyst has good catalytic activity, selectivity, good abrasion resistance and preventing from heavy metal pollution ability; The function that has certain reduction content of sulfur in gasoline simultaneously; Can use with conventional FCC catalyst fusion, also can be used for the recirculation of catalytic cracking process process separately and use.
Said method has been considered the regeneration of Y zeolite on the poising agent; Improved the cracking activity of FCC poising agent to a certain extent, be poising agent process for reactivation preferably, but be limited by crystallization mode under the highly basic condition; Other molecular sieve crystals in the meeting destruction of balance agent in the synthetic Y molecular sieve process; Like the ZSM-5 molecular sieve, so selection of catalysts property also is affected, and reduces such as light olefin selectivity such as propylene in the cracked gas.
The ZSM-5 molecular sieve from 1972 by U.S. Mobil company reported first (USP3702886); Because its unique pore passage structure and shape selective catalysis effect; Current FCC catalyst majority is added with the ZSM-5 molecular sieve, distributes in order to improve catalyst performance and then to improve product.The technology that has occurred in-situ crystallization technology preparation ZSM-5 molecular sieve in recent years.
USP6; 908; 603 disclose a kind of method that adopts the synthetic ZSM-5 of kaolin microsphere original position after the roasting, and this technology is at first carried out high-temperature roasting to kaolin microsphere, and the aluminium in the kaolin is converted into activated aluminum; Kaolin microsphere after the roasting is carried out the hydrothermal crystallizing reaction in the seed-solution of Y zeolite and silicon source solution, prepared the ZSM-5 molecular sieve at the microsphere surface in-situ crystallization.
EP0; 068; 817 disclose the method for the synthetic ZSM-5 of the acid-treated metakaolin of a kind of usefulness; This technology makes the aluminium oxide in the metakaolin separate out through the effect of strong acid example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and in the presence of 4-propyl bromide, the ZSM-5 molecular sieve is synthesized in acid-treated metakaolin and NaOH effect.
USP6,004,527 discloses the method through the synthetic ZSM-5 of pure silicon microballoon.This method aluminium source and sodium source are added by separately pin hydrochlorate dipping through the initial humidity infusion process.Adopting TPAOH in this method is directed agents, and zeolite product degree of crystallinity is 25%, and product has kept the shape and size of pure silicon microballoon.
USP4,522,705 disclose the Preparation of catalysts method that is obtained containing ZSM-5 molecular sieve additive by the clay agglomerates in-situ crystallization.Clay microphere is handled through the aqueous solution of NaOH and organic formwork agent, comprises the crystal seed of ZSM-5 molecular sieve in the preformed microballoon, and crystallization is under the condition of NaOH and the existence of propyl group amine, to carry out.
The method of the synthetic ZSM-5 molecular sieve of in-situ crystallization is strict to material choice, and clay activation process needs high-temperature roasting, and cost is high.Usually the auxiliary agent of raising the output cracked gas mixes the spray-dried auxiliary agent that is prepared in back by the molecular sieve modified back of the synthetic ZSM-5 of gel method with components such as binding agent, clays.
CN1796496A discloses a kind of assistant for calalytic cracking, can in the catalytic cracking of petroleum hydrocarbon process, increase liquefied gas yield and density of propylene.This auxiliary agent is made up of one or more metallic addition and the phosphorus additive of the heavy % of 2-25 that is selected from the VIII family metal of the inorganic oxide binder of the clay of the modified zsm-5 zeolite of the heavy % of 10-65, the heavy % of 0-60, the heavy % of 15-60, the heavy % of 0.5-15 by butt; Wherein, said modified zsm-5 zeolite through phosphorus be selected from the metal-modified of one of Fe, Co or Ni.
[E.Tangstad, T.Myrstad, and A.I.Spjelkavik, et al.Appl.Catal.A, 299 (2006) 243] report, the catalyst aid of the conventional increasing light olefin yield of adding has side effect to the sulfur content that reduces in the gasoline in the catalytic cracking process.Make gasoline yield descend owing to add auxiliary agent, make that the sulfide concentration in the gasoline concentrates, thereby sulfur content raises on the contrary.Therefore, a kind of increasing light olefin yield simultaneously of exploitation is the work with practical significance of satisfying current clean gasoline production with the auxiliary agent that reduces content of sulfur in gasoline.
Summary of the invention
The objective of the invention is to the deficiency to prior art, provide a kind of can increasing production of liquid gas and reduce the assistant for calalytic cracking of content of sulfur in gasoline and its preparation method is provided.
Cracking additive provided by the invention; It is characterized in that this auxiliary agent contains ZSM-5 molecular sieve and the Ni and the V of growth in situ on microballoon; This cracking additive is that to draw off poising agent (be called for short cracking draw off agent) with catalytic cracking be raw material, adds inorganic base, silicon source, template and water, obtains through the crystallization processing; With the auxiliary agent total amount is benchmark, and said Ni and V account for 0.1～5 weight % in simple substance.
The present invention also provides the preparation method of this auxiliary agent, and this method is that cracking is drawn off agent and adds the silicon source and be mixed into microspheroidal, under vapourizing temperature, contacts with the steam that contains organic formwork agent then and carries out crystallization, comprises the steps:
A) catalytic cracking is drawn off agent after 300～1000 ℃ of roastings, mix with inorganic base, silicon source and water, obtaining mole proportioning is SiO
2/ Al
2O
3=1～200, Na
2O/SiO
2=0.03～0.5 mixture microballoon places on the gas permeability screen cloth on agitated reactor top as the reaction solid phase;
B) organic formwork agent is placed the agitated reactor still as the reaction liquid phase at the bottom of, its liquid level is contact procedure mixture microballoon a) not;
C) sealed reactor was warming up under the 130-250 ℃ of condition crystallization 10-200 hour, obtained product and activation.
Compared with prior art, the present invention has the following advantages:
1, drawing off poising agent by the catalytic cracking of high heavy metal pollution is raw material, has opened up an approach for the recycle that draws off poising agent, has avoided drawing off the pollution that poising agent causes to environment, and process is simple.
2, the ZSM-5 molecular sieve is grown directly upon the big hole surface of microballoon, as cracking additive, has reduced the diffusional resistance of reactant and product, thereby has improved reaction efficiency, has to improve the effect that liquefied gas yield is light olefin productive rate and reduction content of sulfur in gasoline simultaneously.
Description of drawings
Fig. 1 is the X-ray diffractogram that draws off catalytic cracking poising agent A.
Fig. 2 draws off the X-ray diffractogram of agent behind in-situ crystallization for embodiment 1.
Fig. 3 is the sem photograph that draws off catalytic cracking poising agent A.
Fig. 4 draws off the sem photograph of agent behind in-situ crystallization for embodiment 1.
Fig. 5 is the sem photograph that draws off catalytic cracking poising agent B.
Fig. 6 draws off the sem photograph of agent behind in-situ crystallization for embodiment 3.
The specific embodiment
Cracking additive provided by the invention is that to draw off agent with the catalytic cracking balance be raw material, handles through in-situ crystallization, obtains growing in microsphere surface, the higher ZSM-5 molecular sieve of degree of crystallinity, and keeps original microballoon physical property constant basically.In more detail, this cracking additive product has the MFI crystalline phase, characterize by X-ray diffractogram (XRD), and be that 100% relative crystallinity is between 10%～100% in the degree of crystallinity of standard sample; Pattern through ESEM (SEM) characterizes is visible, and part ZSM-5 molecular sieve " growth " is in drawing off the agent microsphere surface.
In the chemical composition of this assistant for calalytic cracking, be benchmark with the auxiliary agent total amount, the total content of V and Ni is counted the heavy % in 0.1 heavy %～5 with simple substance, the heavy % in preferred 0.5 heavy %～2.
Cracking additive provided by the invention has advantages of high catalytic activity and liquefied gas selectivity.And, utilize metals such as the Ni draw off in the agent, V as desulphurizing activated center, make in catalytic cracking process, to have the effect that reduces sulfur content of catalytic cracking gasoline.
Preparation method provided by the invention is that catalytic cracking is drawn off agent and adds the silicon source and be mixed into microspheroidal, under vapourizing temperature, contacts with the steam that contains organic formwork agent then to carry out crystallization and obtain.
Method provided by the invention, in the said step (a), it is the FCC poising agent that contains metals such as a certain amount of V, Ni that the catalytic cracking balance that is suitable for draws off agent, its V and Ni content are counted the heavy % in 0.1 heavy %～5 with simple substance, the heavy % in preferred 0.5 heavy %～3.Said sintering temperature is 300 ℃～1000 ℃, and preferred 500 ℃～800 ℃, roasting time is 0.1～10 hour, preferred 1～3 hour.In the said reactant mixture, each component by the mole ratio range of its oxide is: SiO
2/ Al
2O
3=1～200, Na
2O/SiO
2=0.03～0.5, preferred SiO
2/ Al
2O
3=2～50, Na
2O/SiO
2=0.05～0.3.
In the method provided by the invention, usually provide reaction required whole aluminium source by drawing off agent, when promptly preparing reaction mixture gel, need not extra adding aluminium source material, just can satisfy the requirement of mole proportioning in the reactant mixture.Certainly, method provided by the invention is not got rid of can add extra aluminium source material, adds the aluminium source if desired, and described aluminium source is compound or the mixture that sodium metaaluminate, boehmite, aluminum sulfate, aluminum nitrate, aluminium chloride, aluminium hydroxide etc. contain aluminium.
In the method provided by the invention; By drawing off agent part silicon source is provided; And the silicon source that draws off outside the agent is siliceous compound or mixture, and like waterglass, Ludox, sodium metasilicate, tetraethyl orthosilicate, white carbon black etc., wherein preferred silicon source is waterglass, Ludox.
In the method provided by the invention, said inorganic base is preferably NaOH.
Method provided by the invention, in the said step (b), said organic formwork agent is the NH described in the prior art
3Derivative, can be that general formula is R (NH
2)
nAlkylamine, wherein R is that carbon number is 1～6 alkyl, n=1～2 are like in ethamine, n-propylamine, n-butylamine, di-n-propylamine, tripropyl amine (TPA), triethylamine, the ethylenediamine etc. one or more.Said template can with water or alcohol organic solvent, form mixture as liquid phase like ethanol, isopropyl alcohol etc. because the crystallization solid phase directly do not contact and easy separation with liquid phase, so kettle base solution also can repeatedly recycle mutually.
Method provided by the invention; In the said step (c), crystallization condition is had no particular limits, can under the common condition of prior art, carry out; The general crystallization temperature that adopts is 130～250 ℃, preferred 150～200 ℃, and crystallization time is 10～200 hours, preferred 20～80 hours.Said activation process also is familiar with by those skilled in the art; Promptly as required crystallization product is carried out the process of modification; Generally include: roasting removes the process of organic formwork agent, the process that sodium is taken off in the ammonium salt solution exchange, and the process of metal and nonmetalloid modification etc.In the process of modification; In metals such as said metal and nonmetalloid can comprise in nonmetal one or more of IIA family metal, IIIA family metal, transition metal and VA family, rare earths such as wherein preferred Mg, Al, Cu, Zn, V, Ni, Fe, La, Ce and the phosphorus one or more.
When auxiliary agent provided by the invention is used for catalytic cracking process, can in catalyst cracker or regenerator, add separately, also can mix the back with other catalytic cracking catalysts and use.Under the general steady running situation, add the heavy % of 1-25 that auxiliary agent provided by the invention accounts for catalytic cracking unit catalyst mixture total amount, be preferably the heavy % of 3-15.
Cracking additive provided by the invention can be used for the processing of various hydrocarbon ils; Said hydrocarbon ils is formed can be from oil process or crude each cut; Comprise crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil; In deasphalted oil, wax tailings and the coal liquefaction product one or more.The not special restriction of the content of impurity such as heavy metal such as nickel, vanadium and sulphur, nitrogen is particularly useful for the higher hydrocarbon oil crude material of sulfur content in the said hydrocarbon ils.
Auxiliary agent provided by the invention is used for catalytic cracking process, and it is 400-650 ℃ that the cracking hydrocarbon oil condition is generally reaction temperature, and agent oil is 1-1000 second time of contact, and the agent weight of oil is than being 1-20, and regeneration temperature is 550-800 ℃.Cracking additive provided by the invention can be used for all kinds catalyst cracker, comprises fixed bed reactors, fluidized-bed reactor, riser reactor etc.
Through embodiment the present invention is described further below, but does not therefore limit content of the present invention.
Among the embodiment, the element composition analysis adopts x ray fluorescence spectrometry (XRF) to measure; Molecular sieve thing phase and degree of crystallinity adopt X-ray diffraction (XRD) appearance to measure, and analysis condition is: Cu-Ka, tube voltage 35kv, tube current 40mA; ESEM (SEM) evaluation is adopted in the analysis of catalyst microscopic appearance; Specific area adopts cryogenic nitrogen adsorption capacity method to analyze, and adopts BET formula to calculate.
Embodiment 1
Catalytic cracking draws off agent A, element set prejudice table 1.
Table 1
| Na 2O，％ | Al 2O 3，％ | RE 2O 3，％ | Ni，％ | V，％ |
| 0.44 | 46.9 | 3.6 | 0.73 | 0.59 |
Characterize (see figure 1) through XRD, the thing that draws off the catalytic cracking poising agent is Y zeolite mutually, because the ZSM-5 molecular sieve content is low on the microballoon, can not detect ZSM-5 molecular sieve thing phase.Observe from the surface topography of sem photograph (see figure 3), due to wearing and tearing and sintering in long-term the use, microsphere features smooth surface.
0.21 gram NaOH is dissolved in the 5 gram deionized waters, and (the Chang Ling catalyst plant is produced, SiO under agitation to add 9.92 gram Ludox
2Concentration 25.6 heavy %, pH value 9.7) and 10 gram waterglass (production of Shandong catalyst plant, SiO
2Account for 20 heavy %, Na
2O accounts for 6.22 heavy %), add 9.87 grams again through 800 ℃, the catalytic cracking of 2 hours calcination process draws off agent A.Evenly mix, with the gained mixture 120 ℃ dry 4 hours down, the reaction solid phase microballoon that obtains, it is formed mole proportioning and is: 0.30Na
2O: 3SiO
2: 1Al
2O
3
With 93.7 gram ethylenediamines, 836.14 gram triethylamines and 70.6 gram water wiring solution-formings, fully stir, obtain reacting liquid phase, its mole is formed ethylenediamine: 5.3 triethylamines: 2.5 water.
Reaction solid phase microballoon is placed on the upper screen of 5L crystallizing kettle, put back at the bottom of the still and answer liquid solution, liquid level does not contact microballoon, and the agitated reactor sealing was heated to 160 ℃ of crystallization 72 hours, dry, roasting.
Characterize (see figure 2) through XRD, the thing of crystallization microballoon product be ZSM-5 molecular sieve thing phase mutually, detects less than Y zeolite thing phase, shows in the crystallization process that original Y zeolite transforms generation ZSM-5 molecular sieve on the microballoon.The relative crystallinity of gained ZSM-5 molecular sieve is 38%.
The sem photograph (see figure 4) is visible, and the superficial growth of microballoon product goes out molecular sieve crystal, reflects the characteristic of in-situ crystallization reaction.
Activation process: microballoon places Muffle furnace through 550 ℃, 6h calcination process, removes the organic formwork agent in the synthetic ZSM-5 molecular sieve.Get 20 grams then and take off the amine microballoon, add aqueous ammonium chloride solution 200 grams of 10 heavy %, add ammonium dihydrogen phosphate (ADP) solid 0.6 gram again, be warming up to 80 ℃ under stirring and keep 30min, filter washing, oven dry.Products therefrom is numbered A1, Na during its element is formed
2O accounts for 0.19 heavy %, P
2O
5Account for 0.94 heavy %, V accounts for 0.36 heavy %, and Ni accounts for 0.47 heavy %.
Embodiment 2
20 gram waterglass are added 10 grams again through 800 ℃, and the catalytic cracking of 2 hours calcination process draws off agent A, evenly mix, with the gained mixture 120 ℃ dry 16 hours down, the reaction solid phase microballoon that obtains, it is formed mole proportioning and is: 0.45Na
2O: 2.78SiO
2: 1Al
2O
3
With 194 gram ethylenediamines, 650 gram triethylamines and 76 gram water wiring solution-formings, fully stir, obtain reacting liquid phase, its mole is formed ethylenediamine: 1.98 triethylamines: 1.3 water.
Reaction solid phase microballoon is placed on the upper screen of 5L crystallizing kettle, put back at the bottom of the still and answer liquid solution, liquid level does not contact microballoon, and the agitated reactor sealing was heated to 160 ℃ of crystallization 140 hours, drying, roasting.
Thus obtained microsphere product thing has the characteristic of Fig. 2 mutually, and the relative crystallinity of gained ZSM-5 molecular sieve is 39.9%.
Sem photograph has the characteristic of Fig. 4.
Activation process: get the crystallization product microballoon and place Muffle furnace, get 20 grams then and take off the amine microballoon, add ammonium sulfate solution 200 grams of 10 heavy % through 550 ℃, 10h calcination process; Be warming up to 80 ℃ under stirring and keep 30min; Filter, washing, repeated exchanged dry after once the microballoon product.Get ZnO (chemical pure, Beijing Chemical Plant) 0.3 gram, be dispersed in the 30 gram deionized waters; Hydrochloric acid to the solution that under agitation splashes into 20 heavy % is clarified, and adds ammonium dihydrogen phosphate (ADP) 0.95 gram again, constantly stirs to add above-mentioned oven dry microballoon 15 grams (butt) down; Making beating 0.5h is in 120 ℃ of oven dry 16h, again in 700 ℃ of roasting 1h; Products therefrom is numbered A-2, Na during its element is formed
2O accounts for 0.18 heavy %, P
2O
5Account for 3.94 heavy %, ZnO accounts for 1.84 heavy %, and V accounts for 0.48 heavy %, and Ni accounts for 0.51 heavy %.
Embodiment 3
Catalytic cracking draws off agent B, element set prejudice table 2.
Table 2
| Na 2O，％ | Al 2O 3，％ | RE 2O 3，％ | ?Ni，％ | ?V，％ |
| 0.33 | 49.9 | 2.0 | ?0.70 | ?0.74 |
Characterize through XRD, the thing that draws off the catalytic cracking poising agent is Y zeolite mutually, because the ZSM-5 molecular sieve content is low on the microballoon, can not detect ZSM-5 molecular sieve thing phase.Observe from the surface topography of sem photograph (see figure 5), microsphere surface is not seen the molecular sieve pattern.
The preparation process: through 850 ℃, the catalytic cracking of 2 hours calcination process draws off agent B and evenly mixes with 50 gram waterglass and 10 grams, with the gained mixture 160 ℃ dry 4 hours down, the reaction solid phase microballoon that obtains, it is formed mole proportioning and is: 1.04Na
2O: 4.80SiO
2: 1Al
2O
3
With 800 gram triethylamines and 237.2 gram isopropyl alcohol wiring solution-formings, fully stir, obtain reacting liquid phase, its mole is formed 2 triethylamines: 1 isopropyl alcohol.
Reaction solid phase microballoon is placed on the upper screen of 5L crystallizing kettle, put back at the bottom of the still and answer liquid solution, liquid level does not contact microballoon, and the agitated reactor sealing was heated to 180 ℃ of crystallization 70 hours, dry, roasting.
Characterize through XRD, the thing of crystallization microballoon product be ZSM-5 molecular sieve thing phase mutually, detects less than Y zeolite thing phase, shows in the crystallization process that original Y zeolite transforms generation ZSM-5 molecular sieve on the microballoon.The relative crystallinity of gained ZSM-5 molecular sieve is 32%.
The sem photograph (see figure 6) is visible, and the superficial growth of microballoon product goes out molecular sieve crystal, reflects the characteristic of in-situ crystallization reaction.
Activation process: place Muffle furnace through 600 ℃, 4h calcination process microballoon, remove the organic formwork agent in the synthetic ZSM-5 molecular sieve.Get 20 grams then and take off the amine microballoon, add ammonium sulfate solution 200 grams of 10 heavy %, be warming up to 80 ℃ under stirring and keep 30min, filter washing; Ammonium dihydrogen phosphate (ADP) solid 1.2 grams are added 30 milliliters of FeCl that always are under stirring
3(wherein contain 0.25 gram Fe in the aqueous solution
2O
3) making beating, the microballoon that adds behind the above-mentioned filtration washing mixes, oven dry, and products therefrom is numbered A3, Na during its element is formed
2O accounts for 0.15 heavy %, P
2O
5Account for 1.94 heavy %, Fe
2O
3Account for 2.56 heavy %, V accounts for 0.26 heavy %, and Ni accounts for 0.27 heavy %.
Embodiment 4
Preparation process: 3.2 gram NaOH are dissolved in the 20 gram deionized waters; Under agitation add 40 gram Ludox, add 16.8 grams again through 700 ℃, the catalytic cracking of 2 hours calcination process draws off agent B; Evenly mix; The gained mixture was descended dry 16 hours at 120 ℃, the reaction solid phase microballoon that obtains, its composition mole proportioning is: 0.52Na
2O: 3.46SiO
2: 1Al
2O
3
With 194 gram ethylenediamines, 650 gram triethylamines and 76 gram water wiring solution-formings, fully stir, obtain reacting liquid phase, its mole is formed ethylenediamine: 1.98 triethylamines: 1.3 water.
Reaction solid phase microballoon is placed on the upper screen of 5L crystallizing kettle, put back at the bottom of the still and answer liquid solution, liquid level does not contact microballoon, and the agitated reactor sealing was heated to 180 ℃ of crystallization 70 hours, dry, roasting.
Characterize through XRD, the thing of crystallization microballoon product be ZSM-5 molecular sieve thing phase mutually, detects less than Y zeolite thing phase, shows in the crystallization process that original Y zeolite transforms generation ZSM-5 molecular sieve on the microballoon.The relative crystallinity of gained ZSM-5 molecular sieve is 35%.
Sem photograph is with the characteristic of Fig. 6, and the superficial growth of microballoon product goes out molecular sieve crystal, reflects the characteristic of in-situ crystallization reaction.
Activation process: place Muffle furnace through 550 ℃, 4h calcination process microballoon, remove the organic formwork agent in the synthetic ZSM-5 molecular sieve.Get 20 grams then and take off the amine microballoon, add ammonium sulfate solution 200 grams of 10 heavy %, add ammonium dihydrogen phosphate (ADP) solid 1.2 grams again, be warming up to 80 ℃ under stirring and keep 30min, filter, washing, oven dry, products therefrom is numbered A4, Na during its element is formed
2O accounts for 0.13 heavy %, P
2O
5Account for 1.54 heavy %, V accounts for 0.52 heavy %, and Ni accounts for 0.48 heavy %.
Comparative Examples
This Comparative Examples is to press the assistant for calalytic cracking of the increase liquefied gas yield of CN1796496A process preparation.
(the Shandong catalyst plant is produced modified zsm-5 zeolite, wherein Fe to get 1.84 kilograms of (butt) ZSP molecular sieves
2O
3Account for 2.4 weights, P
2O
5Account for 4.0 heavy %), 1.33 kilograms of (butt) kaolin and 0.98 kilogram of (butt) boehmite add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols were pulled an oar 120 minutes, stir to add 1 liter of FeCl down
3.6H
2The aqueous solution of O (wherein contains 250 gram Fe
2O
3).Mixture is continued 45 fens kinds of making beating,, obtain average particulate diameter and be 65 microns microballoon then with the slurries spray-drying that obtains.With microballoon in 500 ℃ of following roastings 1 hour.Get 1 kilogram of thus obtained microsphere product (butt), add 10 liters of decationized Y sieve water and 100 gram phosphoric acid hydrogen two are pressed, be warming up to 60 ℃ under stirring; Behind the constant temperature 20 minutes, with dope filtration, drying, then in 500 ℃ of following roastings 2 hours; Make the assistant for calalytic cracking of liquefied gas yield, be numbered DB.
Estimate embodiment
Following examples explanation is with the cracking reaction effect of sample of the present invention as auxiliary agent.
The auxiliary agent of embodiment 1-4, hydrothermal aging is used for the sulfur-bearing oil hydrocarbon catalytic cracking after handling.
With fresh dose of DOCP (Chang Ling catalyst plant commercial production) on the fixed fluidized bed hydrothermal aging device under 800 ℃, the condition of 100% water vapour deactivation 17 hours, as base catalyst.The A1-A4 auxiliary agent of embodiment 1-4 and the DB auxiliary agent in the Comparative Examples is on the fixed bed hydrothermal aging device under 800 ℃, the condition of 100% water vapour aging 17 hours, subsequent use as estimating.
The evaluation of sulfur-bearing oil hydrocarbon catalytic cracking is carried out on WFS-5A fixed bed catalytic cracking heavy oil microreactor (production of Beijing information automation Co., Ltd); Be packed into reactor after auxiliary agent mixed by 100: 6 by aging back DOCP bodying agent with after wearing out, appreciation condition and feedstock oil character are seen table 3 and table 4 respectively.
Also it forms metering cracked gas volume with gc analysis, and product oil is through the content of each cut of gas Chromatographic Simulation way of distillation mensuration, and coke is measured by infrared carbometer.The gasoline fraction sulfur content is by the gas chromatograph for determination of band AED detector.
Evaluation result is listed in table 5.
Table 3
| Reaction temperature, ℃ | 500 |
| Regeneration temperature, ℃ | 600 |
| Air speed, h -1 | 16 |
| Oil ratio | 3.2 |
| The catalyst loading amount, |
5 |
| Aging bodying agent: aging auxiliary agent | 100∶6 |
Table 4
| Project | Assay value | Project | Assay value |
| Density, g/cm3 | 0.9154 | Element is formed | |
| Viscosity, mm2/S | 6.962(100℃) | C，％ | 85.38 |
| Carbon residue, % | 0.18 | H，％ | 12.03 |
| Boiling range | S，％ | 2.0 | |
| IBP，℃ | 329 | N，％ | 0.16 |
| 10％，℃ | 378 | Four |
|
| 30％，℃ | 410 | Saturated hydrocarbons, % | 64.0 |
| 50％，℃ | 436 | Aromatic hydrocarbons, % | 32.0 |
| 70％，℃ | 462 | Colloid, % | 4.0 |
| 85％，℃ | 518(95％) | Asphalitine, % | 0.0 |
Table 5
Visible from the result of table 5; After adding auxiliary agent on the bodying agent; The conversion ratio of feedstock oil all improves to some extent; Embody being apparent that liquefied gas yield is significantly improved most, wherein the productivity of propylene increase rate is bigger, has met or exceeded the Comparative Examples auxiliary agent of the special production-increase liquefied gas that adopts the semisynthesis preparation.
Also visible in addition; Compare with the Comparative Examples auxiliary agent; After adding auxiliary agent of the present invention; Can be so that the sulfide concentration in the gasoline boiling range reduces; This is because auxiliary agent of the present invention is the higher ZSM-5 molecular sieve of degree of crystallinity that on the poising agent microballoon, regrows out, utilizes metals such as the Ni that deposits on the poising agent, V to promote the conversion of sulfide as desulphurizing activated center simultaneously, has overcome to add general propylene enhancing auxiliary agent and impel gasoline to concentrate the unfavorable factor of bringing sulfide concentration to rise; Therefore auxiliary agent of the present invention not only can provide the approach of the rational and efficient use of a high pollution poising agent, and a kind of high value added product that satisfies the market demand of clean gasoline production can be provided.
Claims (6)
1. the cracking additive of an increasing production of liquid gas; It is characterized in that this auxiliary agent contains ZSM-5 molecular sieve and the Ni and the V of growth in situ on microballoon; With the cracking additive total amount is benchmark, and Ni and V account for 0.1～5 weight % in simple substance, and this auxiliary agent is to be prepared by the method that comprises the steps:
A) the catalytic cracking balance is drawn off agent after 300～1000 ℃ of roastings, mix with inorganic base, silicon source and water, obtaining mole proportioning is SiO
2/ Al
2O
3=1～200, Na
2O/SiO
2=0.03～0.5 mixture microballoon places on the gas permeability screen cloth on agitated reactor top as the reaction solid phase, and it is the FCC poising agent that contains V, Ni metal that said catalytic cracking balance draws off agent, and its V and Ni content are counted 0.1 weight %～5 weight % with simple substance;
B) organic formwork agent is placed the agitated reactor still as the reaction liquid phase at the bottom of, its liquid level is contact procedure mixture microballoon a) not;
C) sealed reactor was warming up under 130～250 ℃ of conditions crystallization 10～200 hours, obtained product and the activated cracking additive that obtains.
2. according to the cracking additive of claim 1, it is characterized in that with the cracking additive total amount be benchmark, wherein said Ni and V account for 0.5～2 weight %.
3. according to the cracking additive of claim 1, it is characterized in that said SiO
2/ Al
2O
3=2～50; Na
2O/SiO
2=0.05～0.3.
4. according to the cracking additive of claim 1, wherein said organic formwork agent is that general formula is R (NH
2)
nAlkylamine, wherein R is that carbon number is 1～6 alkyl, n=1～2.
5. according to the cracking additive of claim 1, wherein said organic formwork agent is selected from one or more in ethamine, n-propylamine, n-butylamine, di-n-propylamine, tripropyl amine (TPA), triethylamine, the ethylenediamine.
6. the cracking method for hydrocarbon oil of an increasing production of liquid gas; It is characterized in that in the presence of the auxiliary agent of one of claim 1 to 5; The cracking reaction condition is that temperature is 400-650 ℃, and agent oil is 1-1000 second time of contact, and the agent weight of oil is than being 1-20; Regeneration temperature is 550-800 ℃, and said auxiliary agent accounts for the 1-25 weight % of catalytic cracking unit catalyst mixture total amount.
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|---|---|---|---|---|
| US4784980A (en) * | 1987-07-15 | 1988-11-15 | Amoco Corporation | Process for preparing zeolite A from spent cracking catalyst |
| US5182243A (en) * | 1991-11-01 | 1993-01-26 | Englehard Corporation | Process for preparing fluidized cracking catalysts from equilibrium fluidized cracking catalysts |
| CN1245091A (en) * | 1998-08-14 | 2000-02-23 | 中国石油化工集团公司 | Process for regenerating deactivated catalyst containing Y-type zeolite |
| CN1974008A (en) * | 2006-10-31 | 2007-06-06 | 华东理工大学 | Re-activating treatment process of poiser containing type-Y molecular sieve |
| CN101108363A (en) * | 2007-06-11 | 2008-01-23 | 大连理工大学 | Manufacturing method of catalyzer used for low quality light oil catalytic reforming and application thereof |
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2008
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4784980A (en) * | 1987-07-15 | 1988-11-15 | Amoco Corporation | Process for preparing zeolite A from spent cracking catalyst |
| US5182243A (en) * | 1991-11-01 | 1993-01-26 | Englehard Corporation | Process for preparing fluidized cracking catalysts from equilibrium fluidized cracking catalysts |
| CN1245091A (en) * | 1998-08-14 | 2000-02-23 | 中国石油化工集团公司 | Process for regenerating deactivated catalyst containing Y-type zeolite |
| CN1974008A (en) * | 2006-10-31 | 2007-06-06 | 华东理工大学 | Re-activating treatment process of poiser containing type-Y molecular sieve |
| CN101108363A (en) * | 2007-06-11 | 2008-01-23 | 大连理工大学 | Manufacturing method of catalyzer used for low quality light oil catalytic reforming and application thereof |
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