CN1022465C - Hydrocarbon cracking catalyst containing phosphorus - Google Patents
Hydrocarbon cracking catalyst containing phosphorus Download PDFInfo
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- CN1022465C CN1022465C CN 90107910 CN90107910A CN1022465C CN 1022465 C CN1022465 C CN 1022465C CN 90107910 CN90107910 CN 90107910 CN 90107910 A CN90107910 A CN 90107910A CN 1022465 C CN1022465 C CN 1022465C
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Abstract
The present invention relates to a phosphorus-containing hydrocarbon cracking catalyst which comprises 5 to 50 wt% of zeolite, 20 to 85 wt% of clay, 0.05 to 5.0 wt% of phosphorus and a surplus quantity of pseudo boehmite or aluminum collosol binding agent (measured by Al2O3), wherein phosphorus atoms uniformly distributed on the surface of catalyst granules form an alumina-phosphoric acid aluminium film. The preparation method of the catalyst comprises: the catalyst is obtained after the zeolite, the clay and the aluminum collosol binding agent are uniformly mixed, atomized, dried, washed, treated with a solution of a phosphorus-containing compound and dried. The catalyst has the advantages of favorable abrasion resisting performance, favorable activity and high thermal stability.
Description
The present invention relates to a kind of phosphorous hydrocarbon cracking catalyzer, specifically relate to a kind of phosphorous hydrocarbon cracking catalyzer with high abrasion resistance strength.
See that from bibliographical information phosphorous hydrocarbon cracking catalyzer (hereinafter to be referred as Cracking catalyst or catalyst) roughly can divide two classes: a class is to contain aluminum phosphate (AP) or aluminium oxide-aluminum phosphate (AAP) part (USP4179358 as matrix or matrix the catalyst, USP4210560, USP4222896, USP4228036, USP4376067, USP4765884 etc.), the Cracking catalyst of reporting among the EP323735A contains inorganic oxides such as zeolite, silica one aluminium oxide or silica one zirconia and is coated in the material that being used on the catalyst granules caught metal; The material that is used for catching metal is one or more a mixture of rare earth oxide, aluminium oxide and aluminum phosphate, it is to be coated on the catalyst by spraying and dry method, this material can be caught the metal that nickel, iron, copper, sodium and vanadium etc. in the raw material make catalyst poisoning in reaction, improved conversion ratio effectively.Another kind of is to handle molecular sieve, matrix or bonding agent with phosphoric acid, phosphorous acid and ammonium salt thereof in catalyst preparation process, to improve activity of such catalysts, selectivity, hydrothermal stability, preventing from heavy metal pollution performance and mechanical strength.
All be to handle the y-type zeolite catalyst of making by the carclazyte converted in-situ in USP4454241, USP4465780 and USP4504382, to improve its catalytic activity with biphosphate ion, dihydrogen phosphite ion or its ammonium salt.
In USP4567152 and USP4584091, handle aluminium oxide with ammonium dihydrogen phosphate (ADP), phosphorous acid or dihydrogen phosphite ammonium etc., again this phosphorus-containing alumina is mixed mutually with ultrastable, silicon-aluminum sol and carclazyte, spray-dried and make catalyst.
The report ultrastable is mixed and made into catalyst with inorganic oxide carrier again among the EP252761 after phosphoric acid or phosphorous acid or its esters processing.
Reported in aging boehmite in the China CN86104860 patent disclosure specification to add phosphoric acid solution, mixed with zeolite and clay again, spray-drying, roasting promptly gets catalyst.The scuff resistance measurement result of this catalyst shows that the adding of phosphoric acid descends the wear rate of catalyst to some extent.
Compound with phosphorus among the Japanese kokai publication sho 61-215206 adds in the alumine hydroxide colloid, to improve the mechanical strength of aluminium oxide.Among the USP3867279 acid phosphate (as the acid magnesium phosphate) of ammonium phosphate or monovalence or polyvalent metal is joined in the mixture of the zeolite of part combination at least and Ludox to improve its mechanical strength.
Scuff resistance is one of important indicator of weighing the Cracking catalyst performance, and it directly has influence on equilibrium activity and the consumption of catalyst in catalytic cracking unit.Along with the commercial Application of the especially middle ultrastable of crystalline aluminosilicate salt zeolite, just higher to the requirement of the wear-resisting intensity of such catalyst.
The Cracking catalyst aluminium base binding agent commonly used that the commercial scale manufacturing contains zeolite has thin water diaspore of plan and colloidal sol containing chloride and aluminium.The boehmite low price, but adhesive property is relatively poor, only be applicable to the Preparation of catalysts process that zeolite content is lower, otherwise the scuff resistance of catalyst can not meet the demands.Though the caking property of aluminium colloidal sol is better, but in the catalyst manufacture process, introduced chlorion, can emit most of chlorine during spray-dried catalyst, but still have small amounts of chlorine to stay in the catalyst, this part chlorine must be removed, otherwise can form hydrochloric acid and etching apparatus in the presence of the water vapour in catalytic cracking unit, if pollute the environment with the flue gas discharge.
In order to reduce the chlorinity in the catalyst, USP4458023 has increased calcination steps after being reported in zeolitic cracking catalyst manufacture process spray-drying.By roasting remaining chlorine in the catalyst is overflowed with the form of hydrogen chloride.The shortcoming of this method is that hydrogen chloride still has corrosiveness to roasting apparatus, and environment is on every side still had contamination.
The USP4542118 patent has adopted the contacted method of catalyst after ammonia and the spray-drying to the dechlorination that contains aluminium colloidal sol Cracking catalyst, makes wherein contained chlorine and ammonia act as ammonium chloride, washes with water and removes.
Disclose among the RD293070 in achievement in research,, recommend to replace colloidal sol containing chloride and aluminium with the aluminium colloidal sol that contains nitrate anion in order to prevent that fluid bed from use disengaging hydrochloric acid with Cracking catalyst and causing harmful corrosion.
In order to solve problems of the prior art, the object of the present invention is to provide with the boehmite is the catalyst with good abrasion resistance of binding agent, and provide with aluminium colloidal sol, especially colloidal sol containing chloride and aluminium is the catalyst with good abrasion resistance of binding agent, and no hydrogen chloride gas etching apparatus and problem of environment pollution caused in its preparation process.
Cracking catalyst provided by the invention contains 5～50 heavy % zeolites, 20～85 heavy % clays, 0.05～5.0 heavy % phosphorus and surplus (with Al
2O
3Meter) boehmite or aluminium sol adhesive, wherein phosphorus is to be distributed on the surface of catalyst granules.
Said zeolite is a zeolite of doing active component of cracking catalyst commonly used, can be X type zeolite, y-type zeolite, zeolite beta, ZSM zeolite or modenite, through rare earth or other cation exchange or other physics or the chemical method above-mentioned zeolite after handling, or the mixture of more than one the above zeolite.Said clay is a clay of doing Cracking catalyst matrix commonly used, can be various clays such as kaolin, imvite, halloysite, sepiolite, attapulgite.
When adopting boehmite to be binding agent, catalyst preferably contains 5～35 heavy % zeolites, 30～80 heavy % clays, 10～35 heavy %(with Al
2O
3Meter), boehmite and 0.05～3.5 heavy %, best 0.3～2.5 heavy % phosphorus.
When adopting aluminium colloidal sol to be binding agent, the aluminium sol content preferably 5～30 weighs %(with Al in the catalyst
2O
3Meter), phosphorus content is 0.05～3.5 heavy %, best 0.3～2.5 heavy %.
Catalyst can also contain the MgO of 0.05～3.0 heavy % and the RE of 0.05～3.0 heavy % again
2O
3
Production of cracking catalyst provided by the invention is:
1. an amount of zeolite, clay and boehmite or aluminium colloidal sol are mixed spray-drying by the conventional preparation method of hydrocarbon cracking catalyzer.
2. be that 30～70 ℃ ammoniacal liquor is with liquid-solid 10～60(weight ratio that turns to temperature) consumption wash the 1st step products therefrom, the pH value of ammoniacal liquor is 4～10 to be advisable filtration with control slurries final pH value.
3. compound concentration is 0.02～17.5 heavy %, best 0.05～2.5 heavy %(is in P) the aqueous solution of phosphorus-containing compound, the pH value of solution is 0.5～10, and is best 3～9, in room temperature～100 ℃, under best 50～90 ℃ of temperature, Gu in liquid/than being 0.2～60(weight ratio) ratio the phosphorous aqueous solution and the 2nd step products therefrom mixed and constantly stir, after 3～120 minutes, filtration, 90～130 ℃ of dryings, this step can repeat 0～5 time so that the phosphorus on the catalyst reaches predetermined content.
Said zeolite is the zeolite that is commonly used for active component of cracking catalyst, can be zeolites such as X type, Y type, ZSM type, zeolite beta or modenite, can also can be the mixture of more than one above-mentioned zeolites through the zeolites such as X type, Y type, ZSM type, zeolite beta or modenite after rare earth or other cation exchange or other chemistry or the physical method processing.
Said clay is a clay of doing Cracking catalyst matrix commonly used, can be clays such as kaolin, halloysite, imvite, sepiolite, attapulgite.
Said aluminium colloidal sol can be the aluminium colloidal sol that conventional method makes, preferably chloride aluminum solutions.
Said phosphorus-containing compound can be orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid or phosphorous acid, or the ammonium salt of above-mentioned each phosphoric acid, or the mixture of above-mentioned each phosphoric acid and ammoniacal liquor, or phosphorus pentoxide, or the mixture of more than one materials noted earlier.
When the routine that has satisfied Cracking catalyst when the content of the contained soluble impurity of the 1st step gains among the said preparation method requires, can save the 2nd step.
The 2nd step can be exchanged with the 3rd step among the said preparation method, carries out after being placed on for the 3rd step again, passes through dry run again, promptly gets catalyst.
The 3rd step among the said preparation method can repeat repeatedly, so that the phosphorus on the catalyst reaches needed content.
In preparation method's the 3rd step, when phosphorus-containing compound was a kind of foregoing phosphoric acid, this step also can adopt the method for spraying that solution containing phosphate is coated onto on the 2nd step products therefrom.
When catalyst also contains MgO or RE
2O
3The time, after the 3rd step, also to carry out the 4th following step among the said preparation method:
4. infusion process is routinely handled the 3rd step gains with magnesium salts or compounds containing rare earth solution, and drying promptly gets catalyst again.
Phosphorus in the catalyst provided by the invention is to be distributed on the surfaces externally and internally of catalyst granules, and with lip-deep aluminium chemical action has taken place, rather than merely adsorb from the teeth outwards, this can obtain explanation by nuclear magnetic resonance (NMR) spectrogram and the photoelectron spectroscopy figure of catalyst.
Fig. 1 is that catalyst of the present invention (contains dealuminzation and stablizes y-type zeolite 39.33 heavy %, aluminium colloidal sol 13.11 heavy %(with Al
2O
3Meter), kaolin 46.13 heavy % and phosphorus 1.43 heavy %) the P-31NMR spectrogram, Fig. 2 and Fig. 3 are respectively its Al-27NMR spectrogram and photoelectron spectroscopy figure.
At chang ﹠amp; Luthra(J.Catal. speak of in the article, 109,163,1988): if during, the P-31NMR signal can not occur on the NMR spectrogram of the phosphorus-containing alumina of gained, promptly not have strong chemical action between phosphorus and the aluminium oxide with the phosphate impregnation aluminium oxide.As seen from Figure 1, catalyst provided by the invention has tangible P-31NMR signal, and the catalyst of other composition provided by the invention also has similar P-31NMR signal, and illustrating has strong chemical action between phosphorus and the catalyst surface.
People such as the P-31 of catalyst of the present invention and Al-27NMR spectrogram (Fig. 1 and Fig. 2) and Cheung are at J.catal., 102,10, P/Al is than the P-31 and the Al-27NMR signal similar that are 0.2 aluminum phosphate (the glue method makes altogether) in 1986 articles, so can think that chemical action has taken place aluminium oxide in phosphorus on the catalyst and the carrier.
As seen from Figure 3, the 2P electron binding energy is that the position of 137ev has tangible peak on the photoelectron spectroscopy figure, this peak was higher when phosphorus content was high, when phosphorus content is lower than 0.5 weight %, this peak buries in noise signal, and this locational peak is not phosphatic (their 2P electron binding energy is all near the 132～133ev) of potassium and sodium, and may be the phosphatic of aluminium, illustrate that phosphorus is not to be adsorbed on the catalyst surface merely, but formed compound with it.
(Fig. 4～Figure 10), can see that phosphorus is uniformly in the distribution of catalyst surface, catalyst surface wants fine and close and smooth than the catalyst surface of prior art for preparing from the result of electron probe and ESEM in addition.
Fig. 4 is the electron probe phosphorus section distribution map (a) and the phosphorus line distribution map (b) of the catalyst of the present invention of phosphorous 1.37 heavy %, Fig. 5 is the phosphorus section distribution map (a) and the line distribution map (b) of phosphorous 1.83 heavy % catalyst of the present invention, and phosphorus distributes very even on the catalyst as we can see from the figure.
Fig. 6 and Fig. 7 are respectively that the stereoscan photograph of catalyst of prior art for preparing and this catalyst are through 600 ℃, stereoscan photograph after the roasting in 2 hours (a: amplify 100 times, b: amplify 760 times), Fig. 8 and Fig. 9 are respectively that the stereoscan photograph of catalyst of the present invention and this catalyst are through 600 ℃, stereoscan photograph after the roasting in 2 hours (a: amplify 100 times, b: amplify 760 times), Figure 10 carries out (microsphere particle handle with solution containing phosphate earlier after washing again) and the stereoscan photograph (a: amplify 100 times, b: amplify 760 times) of the catalyst of the present invention that gets in the 2nd step of when preparation after the 3rd step.The catalyst that can be found out prior art for preparing by Fig. 7～Figure 10 is at 600 ℃, and the roasting rear surface was loosely organized in 2 hours, and shape is rule inadequately, and catalyst roasting of the present invention rear surface smoother, densification has kept the spherical of rule.
Catalyst provided by the invention has good scuff resistance, when binding agent is boehmite, the wear extent of catalyst only is that half of existing similar catalyst is to 1/5th, overcome the shortcoming that zeolite content increase catalyst strength just can not meet the demands when being binding agent with the boehmite, the possibility that reduces boehmite content in the catalyst and replace aluminium colloidal sol to synthesize the high zeolite content catalyst with boehmite is provided, above-mentioned all points all help reducing the abrasion loss of catalyst in catalytic cracking unit, thereby have reduced the clean or white production cost.In addition, handling the process of microsphere particle with phosphorus-containing compound, also is the process that cation in the solution and the sodium ion on the microballoon carry out ion-exchange, and its result not only makes the sodium content of catalyst descend, but also makes it have the character of some h-type zeolite.
When with aluminium colloidal sol, when especially colloidal sol containing chloride and aluminium is as binding agent, Preparation of catalysts method of the present invention washes process with water and gets final product dechlorination, the intensity of the catalyst that its scuff resistance of while still can make with the roasting dechlorination is suitable, even it is better, overcome etching apparatus and the contaminated environment brought with the roasting process dechlorination in the prior art, and the shortcoming of the wear-resisting intensity of water-washing process dechlorination meeting reduction catalyst, energy consumption reduced in addition.
Phosphorus-containing catalyst provided by the invention also has good activity and hydrothermal stability.
When catalyst of the present invention also contains MgO or RE
2O
3The time, its scuff resistance is still very good, and does not contain MgO or RE
2O
3The scuff resistance of catalyst of the present invention close.
Below will the present invention will be further described by embodiment.
With the boehmite is the adhesive preparation catalyst.
1. with 17.0 kilograms of kaolin (solid content 83.0 heavy %, Suzhou china clay company machine selects No. 2), 0.74 being technical hydrochloric acid and 40 kilograms of deionized waters of 31 heavy %, kilogram concentration mixes, after 1 hour, (solid content is 33.3 heavy % to add 9 kilograms of boehmites, Shandong aluminium stone is produced), stirred 1 hour, add dealuminzation and stablize y-type zeolite DASY(solid content 80.0 heavy %, Qilu Petrochemical company Zhou village catalyst plant is produced), stirred 1.5 hours, with high-pressure pump these slurries are sent into and to be carried out spray-drying in the spray drying tower, promptly get and contain DASY zeolite 15.1 heavy %, boehmite is (with Al
2O
3Meter) microsphere particle of 14.9 heavy % and kaolin 70.0 heavy %.
2.6.2 gram ammonium phosphate (NH
4)
3PO
43H
2The O(chemical pure) dissolve in the 2 liter decationized Y sieve water, the pH value of solution value is 8.39, and solution is warming up to 60 ℃, and 100 grams the 1st step products therefrom is added in the above-mentioned solution, stirs after 10 minutes, filters, and 110 ℃ of dryings promptly get the catalyst A of phosphorous 0.76 weight %.
The 1st step products therefrom was promptly got comparative sample Ac in 2 hours 540 ℃ of following roastings.
With the chlorine and the sodium content of conventional chemical method survey catalyst,, survey the fluidisation wear rate of catalyst with conventional method with the specific surface and the pore volume of low-temperature nitrogen adsorption method survey catalyst; Catalyst is estimated active on the light oil micro-reactor after certain hour through 800 ℃, 100% steam aging, reaction condition is: reaction raw materials is huge port light diesel fuel (235～337 ℃ of fraction), and 460 ℃ of reaction temperatures are during weight space velocity 16
-1, oil ratio 3.2 the results are shown in Table 1.
Table 1
Catalyst A Ac
Chlorine, heavy % 0.04/
Sodium oxide molybdena, heavy % 0.14/
Specific surface, rice
2/ gram 146 164
Pore volume, milliliter/gram 0.15 0.18
Wear rate, % hour
-12.6 5.3
Aging 4 hours 60 56
Micro-activity, %
Aging 17 hours 38 37
As seen from Table 1, the anti-wear performance of catalyst of the present invention, catalytic activity and hydrothermal stability all are better than the comparative catalyst.This just provides possibility for improving catalyst mesolite content.
With the boehmite is the adhesive preparation catalyst.
Example 2:
1. contain zeolite 25.0 heavy % by the preparation of example 1 the 1st one step process, boehmite is (with Al
2O
3Meter) microsphere particle of 17.6 heavy % and kaolin 57.4 heavy %.
2. in 8 liter decationized Y sieve water, add ammonium phosphate (NH
4)
3PO
43H
2O
248 grams and phosphoric acid (concentration 85 heavy %) 34.4 grams, this pH value of solution value is 2.68, solution is warming up to 80 ℃, adds 400 grams the 1st step products therefrom, stirs after 10 minutes, filtration immediately, 110 ℃ of dryings promptly get the phosphorous 1.65 catalysis B that weigh %.
Embodiment 3:
1. identical with example 2 the 1st step.
2.36.5 gram ammonium dihydrogen phosphate (ADP) (analyzing pure) adds in 150 milliliters of decationized Y sieve water, make whole dissolvings, take out 100 milliliters of these solution and at room temperature add 200 grams the 1st step gains, and constantly stir, following dry 2 hours after 30 minutes in 120 ℃, add 50 milliliters of above-mentioned solution after the cooling again, stir after 10 minutes in 120 ℃ dry down, promptly get the catalyst C of phosphorous 4.0 weight %.
Get the 1st step of example 2 products therefrom 540 ℃ of following roastings 2 hours, promptly get comparative catalyst Bc.
Table 2 has been listed physical and chemical performance and the catalytic activity of catalyst B, C and Bc, and catalyst of the present invention as seen from the table has good scuff resistance, catalytic activity and heat endurance.
Table 2
Catalyst B C Bc
Chlorine, heavy % 0.06 //
Sodium oxide molybdena, heavy % 0.14 0.26/
Wear rate, % hour
-17.4 3.5 20
Micro-activity, aging 4 hours 64 67 58
Aging 17 hours 46/39 of %
Embodiment 4
With aluminium colloidal sol is the adhesive preparation catalyst.
1. with 11.3 kilograms of kaolin and 12.6 kilograms of aluminium colloidal sol (aluminium 11.2 heavy %, Al/Cl=1.24, Qilu Petrochemical company Zhou village catalyst plant is produced) mix, stirred 45 minutes, the mixed serum that adds 10 kilograms and 16.1 kilograms decationized Y sieve water of DASY zeolite, stirred 1.5 hours, spray-drying promptly gets and contains the heavy % of DASY zeolite 39.9, aluminium colloidal sol (with Al
2O
3Meter) microsphere particle of 13.3 heavy % and kaolin 46.8 heavy % kaolin 46.8 heavy %.
2. be that 60 ℃, pH value are that 8.92 ammonia spirit washs 100 grams the 1st step products therefrom with 2 intensification degree, slurry pH value is 4.12, filters.
3.6.2 gram ammonium phosphate (NH
4)
3PO
43H
2O and 8.6 gram concentration are that the phosphoric acid of 85 heavy % adds in the 2 liter decationized Y sieve water, and the pH value of solution value is 2.60, is warming up to 60 ℃, add the 2nd step gains, stir after 10 minutes, filter, and 120 ℃ of dryings promptly get the catalyst D of phosphorous 1.43 weight %.
Get the 1st step products therefrom 540 ℃ of following roastings 2 hours, promptly get comparative catalyst D
cIt is dry under 120 ℃ to get the 2nd step products therefrom, promptly gets comparative catalyst D
w
The physical and chemical performance and the activity rating of above-mentioned catalyst the results are shown in Table 3.
Table 3
Catalyst D Dc Dw
Chlorine, heavy % 0.33 0.21 0.47
Sodium oxide molybdena, heavy % 0.13 0.33 0.18
Specific surface, rice
2/ gram 209 242 263
Pore volume, milliliter/gram 0.13 0.17 0.24
Abrasion index, % hour
-13.7＞6 8.5
Aging 4 hours 69 62 63
Micro-activity, %
Aging 17 hours 48 37 45
By table as seen, the comparative catalyst with the washing dechlorination compares with the roasting dechlorination, and catalyst of the present invention has good scuff resistance, catalytic activity and hydrothermal stability.
Embodiment 5～6
With aluminium colloidal sol is the adhesive preparation catalyst.
Prepare the catalyst E of phosphorous 1.36 heavy % by the method for example 4, just the 1st step products therefrom contains DASY zeolite 35.1 heavy %, and aluminium colloidal sol is (with Al
2O
3Meter) 15.6 heavy % and kaolin 49.3 heavy %, ammoniacal liquor pH value is 9.6 in the 2nd step, slurry pH value is 7.69.
Prepare the catalyst F of phosphorous 0.83 heavy % by the method for example 4, just the 1st step products therefrom contains DASY zeolite 25.0 heavy %, and aluminium colloidal sol is (with Al
2O
3Meter) 12.5 heavy % and kaolin 63.0 heavy %; The pH value of ammoniacal liquor is 10.55 in the 2nd step, and slurries final pH value is 4.92; Solution containing phosphate is to mix by 10: 1 weight ratio with the 2nd step products therefrom in the 3rd step.
According to the preparation method of comparative catalyst Dc and Dw, the 1st step or the 2nd step gains of getting example 5 or 6 make comparative catalyst Ec, Ew, Fc and Fw respectively.
The physical and chemical performance of above-mentioned catalyst and the evaluation result of catalytic activity see Table 4.(table 4 is seen the literary composition back)
As seen from table, the chlorine of catalyst provided by the invention and sodium content are lower than or are close with the comparative catalyst, and the comparative catalyst of scuff resistance and roasting dechlorination is close, are better than washing the comparative catalyst of dechlorination.
With aluminium colloidal sol is the adhesive preparation catalyst.
Get an amount of rare earth Y type zeolite REY(Qilu Petrochemical company catalyst plant industrial products), kaolin and aluminium colloidal sol prepares the catalyst G of phosphorous 1.21 heavy % and the catalyst H of phosphorous 0.45 heavy % by the method for example 4, just the 1st step products therefrom all contains 15.3 heavy %REY zeolites, and 8.7 heavy % aluminium colloidal sols are (with Al
2O
3Count) and 76.0 heavy % kaolin; When preparing catalyst G in addition, the pH value of ammoniacal liquor is 10.5 in the 2nd step, and the whole pH value of slurries is that solution containing phosphate is the mixture of phosphoric acid and ammoniacal liquor in 8.94, the 3 steps, solution phosphorous 0.16 heavy %, and its pH value is 2.52; During preparation catalyst H, ammoniacal liquor pH value is 9.63 in the 2nd step, is that solution containing phosphate is the mixture of phosphoric acid and ammoniacal liquor in 6.56, the 3 steps with the whole pH value of liquid, solution phosphorous 0.047 heavy %, and its pH value is 8.0.
Get the 1st step gains of example 7 respectively, prepare comparative catalyst Gc and Dw according to the preparation method of comparative catalyst Dc and Dw.
The physical and chemical performance and the catalytically active assessment of above-mentioned catalyst the results are shown in Table 5.(table 5 is seen the literary composition back)
By table 5 as seen, the scuff resistance of catalyst of the present invention is better than the comparative catalyst, and the chlorinity of catalyst is far below comparative catalyst's chlorinity.
With aluminium colloidal sol is the adhesive preparation catalyst.
Example 9:
The 1 method preparation by the 1st step of example 4 contains DASY zeolite 35.1 and gets %, aluminium colloidal sol (with Al
2O
3Meter) microsphere particle of 15.6 heavy % and kaolin 49.3 heavy %.
2 is identical with the 3rd step of example 4, and just solution containing phosphate phosphorous 0.08 weighs %, and the pH value is 3.53, and temperature is 70 ℃.
4 liters of pH values of 3 usefulness are 10.73, temperature is 40 ℃ the 2nd step of ammonia scrubbing gains, and the whole pH value of slurries is 9.36, filter, and 120 ℃ of dryings promptly get the catalyst I of phosphorous 0.82 weight %.
Example 10:
Prepare the catalyst J of phosphorous 0.38 heavy % by the method for example 9, just the 1st step gains contain DASY zeolite 25.0 heavy %, aluminium colloidal sol (with Al
2O
3Meter) 12.0 heavy % and kaolin 63.0 heavy %, the pH value of solution containing phosphate is that the whole pH value of slurries is 8.97 in 2.73, the 3 steps in the 2nd step.
Get example 9～10 the 1st step gains respectively and make comparative catalyst Ic and Jc by the preparation method of comparative catalyst Dc.
The physical and chemical performance and the catalytically active assessment of above-mentioned catalyst the results are shown in Table 6.(table 6 is seen the literary composition back)
Because 6 as seen, the chlorinity of catalyst provided by the invention and sodium content all are lower than the comparative catalyst of roasting dechlorination, and scuff resistance and comparative catalyst are quite or better, activity is higher than the comparative catalyst.
In 10 liter decationized Y sieve water, add 31 gram ammonium phosphate (NH
4)
3PO
43H
2O and 43 gram concentration are the phosphoric acid of 85 heavy %, the pH value of solution value is 3.57, be heated to 80 ℃, (with ultrastable and ZSM-5 zeolite is active component to the addingization catalyst, Qilu Petrochemical company catalyst plant is produced) 500 grams, stirred 30 minutes, filter while hot, 110～120 ℃ of dryings promptly get the catalyst K of phosphorous 1.71 heavy %.
21.76 gram Mg(NO
3)
26H
2O(purity 98%) be dissolved in 60 ml waters, add 200 gram catalyst K, mix, after 10 minutes, 110 ℃ dry down, promptly gets the catalyst L of phosphorous 1.67 heavy % and magnesia 1.6 heavy %.
Compound concentration is 18.2 milliliters of the solution of the rare earth trichloride of 161.48 grams per liters, adds 200 gram catalyst K, mix, after 10 minutes, in 100 ℃ dry down, promptly get the catalyst M that phosphorous 1.61 heavy % and rare earth oxide 2.6 weigh %.
Intensity and the catalytic activity of catalyst K, L and M see Table 7, and wherein the comparative catalyst is the 1st step gains.(table 7 is seen the literary composition back)
Its scuff resistance remained unchanged after catalyst was used the solution-treated that contains magnesium salts or rare earth compound as known from Table 7.
Table 4
E Ec Ew F Fc Fw
Chlorine, heavy % 0.08 0.34 0.62 0.85 0.40 1.05
Sodium oxide molybdena, heavy % 0.13 0.34 0.16 0.06 0.24 0.09
Specific surface, rice
2/ gram 234 224 245 159 162 190
Pore volume, milliliter/gram 0.24 0.16 0.25 0.13 0.13 0.22
Wear rate, % hour
-11.5 1.7 3.3 1.5 1.3 2.6
Aging 4 hours 69 60 60 56 52 57
Micro-activity, %
Aging 17 hours 52 35 44 40 35 41
Table 5
G H Gc Gw
Chlorine, heavy % 0.03 0.07 0.22 0.21
Sodium oxide molybdena, heavy % 0.11 0.075 0.29 0.14
Specific surface, rice
2/ gram 141 123 114 138
Pore volume, milliliter/gram 0.21 0.15 0.1 0.20
Wear rate, % hour
-11.6 2.3 2.4 3.6
Aging 4 hours 76 76 77 78
Micro-activity, %
Aging 17 hours 53 64 31 66
Table 6
Catalyst I Ic J Jc
Chlorine, heavy % 0.15 0.34 0.38 0.4
Sodium oxide molybdena, heavy % 0.12 0.34 0.07 0.24
Specific surface, rice
2/ gram 207 224 194 162
Pore volume, milliliter/gram 0.15 0.16 0.24 0.13
Wear rate, % hour
-10.9 1.7 1.2 1.3
Aging 4 hours 68 60 57 52
Micro-activity, %
Aging 17 hours 35 35
Table 7
K L M contrast
Wear rate, % hour
-11.2 1.2 1.2 4.8
Aging micro-activity after four hours, % 62 31 68
Claims (10)
1, a kind of phosphorous hydrocarbon cracking catalyzer is characterized in that it contains 5～50 heavy % zeolites, 20～85 heavy % clays, 0.05～5.0 heavy % phosphorus and 3～35 heavy % (with Al
2O
3Meter) boehmite or aluminium sol adhesive, phosphorus wherein is distributed in the surface of catalyst granules, and this Preparation of catalysts method is:
(1) an amount of zeolite, clay and boehmite or aluminium colloidal sol are mixed spray-drying by the conventional preparation method of hydrocarbon cracking catalyzer;
(2) be that 30～70 ℃ ammoniacal liquor is (1) step of the consumption washing products therefrom of 10～60 (weight ratios) with liquid-solid ratio with temperature, the pH value of ammoniacal liquor is advisable filtration with control slurries final pH 4～10;
(3) compound concentration is the aqueous solution of the phosphorus-containing compound of 0.02～17.5 heavy % (in P), the pH value of solution value is 0.5～10, under the temperature of room temperature～100 ℃, Gu be that 0.2～60 ratio is mixed the phosphorous aqueous solution and (2) step products therefrom and constantly stirring in liquid/than (weight ratio), after 3～120 minutes, filter 90～130 ℃ of dryings; This step can repeat 0～5 time so that the phosphorus on the catalyst reaches predetermined content.
2, by the described catalyst of claim 1, it is characterized in that the zeolite content in the catalyst is 5～35 heavy %, clay content is 30～80% weight %, boehmite content is 10～35 heavy %, (with Al
2O
3Meter), phosphorus content is 0.05～3.5 heavy %.
3,, it is characterized in that the aluminium sol content in the catalyst is that 5～30% heavy %(are with Al by the described catalyst of claim 1
2O
3Meter), phosphorus content is 0.05～3.5 heavy %.
4, according to the described catalyst of claim 1, it is characterized in that said zeolite is one or more the mixture that is used as usually in the various zeolites of catalyst activity component, comprise X type, Y type, β type, ZSM type zeolite, modenite, with through above-mentioned zeolite rare earth ion or other cation exchange or that other physics or chemical method were handled, said clay is a clay of doing catalyst substrates commonly used, comprises kaolin, halloysite, imvite, sepiolite, attapulgite.
5, by the described catalyst of claim 1, it is characterized in that said aluminium colloidal sol is chloride aluminium colloidal sol in the method for preparing catalyst.
6, by the described catalyst of claim 1, it is characterized in that said phosphorus-containing compound is orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid or phosphorous acid in the method for preparing catalyst, or the ammonium salt of above-mentioned various phosphoric acid, or the mixture of above-mentioned various phosphoric acid and ammoniacal liquor, or phosphorus pentoxide, or the mixture of more than one materials noted earlier.
7,, it is characterized in that to save (2) step when among the preparation method said (1) when going on foot routine that the contained soluble impurity content of products therefrom satisfied Cracking catalyst and requiring by the described catalyst of claim 1.
8, by the described catalyst of claim 1, it is characterized in that (2) step is carried out after can being placed on (3) step among the said preparation method, the drying process promptly gets catalyst again.
9, by the described catalyst of claim 1, it is characterized in that containing in the catalyst 0.3～2.5 heavy % phosphorus, phosphorus-containing compound solution concentration (in P) is 0.05～2.5 heavy % in (3) step of its preparation method, and the pH value is 3～9, and temperature is 50～90 ℃.
10,, it is characterized in that catalyst can also contain the MgO of 0.05～3.0 heavy % or the RE of 0.05～3.0 heavy % by the described catalyst of claim 1
2O
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107910 CN1022465C (en) | 1990-09-27 | 1990-09-27 | Hydrocarbon cracking catalyst containing phosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107910 CN1022465C (en) | 1990-09-27 | 1990-09-27 | Hydrocarbon cracking catalyst containing phosphorus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1060304A CN1060304A (en) | 1992-04-15 |
| CN1022465C true CN1022465C (en) | 1993-10-20 |
Family
ID=4880764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90107910 Expired - Lifetime CN1022465C (en) | 1990-09-27 | 1990-09-27 | Hydrocarbon cracking catalyst containing phosphorus |
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| Country | Link |
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| CN (1) | CN1022465C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085722C (en) * | 1998-08-14 | 2002-05-29 | 中国石油化工集团公司 | Cracking catalyst of P-contained zeolite and its preparing process |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072030C (en) * | 1997-11-11 | 2001-10-03 | 中国石油化工总公司 | Phosphorus-contained octahedro zeolite hydrocarbons cracking catalyst and preparation method therefor |
| ES2282488T3 (en) | 2001-07-02 | 2007-10-16 | Exxonmobil Chemical Patents Inc. | INHIBITION OF THE COKE FORMATION IN A CATALYST IN THE MANUFACTURE OF AN OLEFINA. |
| US6872680B2 (en) | 2002-03-20 | 2005-03-29 | Exxonmobil Chemical Patents Inc. | Molecular sieve catalyst composition, its making and use in conversion processes |
| US7271123B2 (en) | 2002-03-20 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Molecular sieve catalyst composition, its making and use in conversion process |
| US7375048B2 (en) * | 2004-04-29 | 2008-05-20 | Basf Catalysts Llc | ZSM-5 additive |
| CN111686791B (en) * | 2019-03-12 | 2023-04-25 | 中国石油天然气股份有限公司 | Catalytic cracking gasoline octane number auxiliary agent and preparation method thereof |
| CN113842844A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Dechlorination method and application of microsphere solid |
-
1990
- 1990-09-27 CN CN 90107910 patent/CN1022465C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085722C (en) * | 1998-08-14 | 2002-05-29 | 中国石油化工集团公司 | Cracking catalyst of P-contained zeolite and its preparing process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1060304A (en) | 1992-04-15 |
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