CN1075466C - Method for preparing superstable Y type zeolite - Google Patents
Method for preparing superstable Y type zeolite Download PDFInfo
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Abstract
The present invention relates to a method for preparing superstable Y type zeolite, which comprises the steps: Y type zeolite is in contact with an acid solution and a solution containing ammonium ions and is treated in water steam at high temperature, the dosage of acid is 1.5 to 6 moles of hydrogen ions in each mole of framework aluminum, the concentration of the acid solution is from 0.1 to 5 Eq/L, the contact temperature of the Y type zeolite and the acid solution is from 5 to 100 DEG C, the contact time is from 0.5 to 72 hours, and the weight ratio of the Y type zeolite to the ammonium ions is 2 to 20. The superstable Y zeolite prepared by the method has the advantages of abundant secondary pore and high relative crystallinity, and the Y type zeolite used in the method can be NaY zeolite whose lattice constant is greater than 24.50 cupola and sodium oxide content is greater than 1 wt% and even 5 wt%.
Description
The invention relates to the preparation method of faujusite, more specifically say so about a kind of preparation method of overstable gamma zeolite.
Overstable gamma zeolite generally is prepared from by the y-type zeolite dealuminzation.Though carry out the liquid phase dealuminzation and carry out gas phase with four silicon oxide and take out the method for aluminium and can be prepared into the higher overstable gamma zeolite of relative crystallinity with ammonium silicofluoride, the overstable gamma zeolite that obtains lacks the indispensable topology secondary pore of heavy oil fluid catalytic cracking structure.
C.V.Dvid and P.K.Maher (Zeolite Chemistry and Catalysis, ACS Monograph171, P285～331, Washington D.C., 1976) the hydrothermal dealumination method of Ti Chuing is one of most widely used method, and this method is earlier with the aqueous solution exchange of NaY zeolite with ammonium ion, to reduce the sodium ions content in the zeolite, in 600～825 ℃ of zeolites after roasting ammonium ion exchange under the water vapour atmosphere, make its super stabilizing then.This method cost is lower and be easy to large-scale industrialization production, and the ultrastable Y that obtains also has more rich secondary pore, but the loss of overstable gamma zeolite degree of crystallinity is serious, sometimes can be with a toll of 40%.
US 5,139, and 984 disclose a kind of preparation method of faujusite silico-aluminate, and this method comprises the acid treatment faujusite with 2～20 moles of/kilogram zeolites, and the silica alumina ratio of described faujusite is 15～25, at least 500 meters of specific surfaces
2/ gram, and lattice constant is 24.36～24.50 dusts.
EP 0,569,626A1 discloses a kind of preparation method of acidifying sealumination modified Y zeolite, this method comprises a kind of y-type zeolite is contacted 0.5～6 hour with a kind of acidic medium at 24～60 ℃, described y-type zeolite is selected from the dealuminium Y type beta stone of ammonium, hydrogen or metal exchange, the silica alumina ratio of this dealuminium Y type beta stone is 10～120 lattice constants, 24.30～24.50 dusts, and has the secondary pore of bore dia 100～600 dusts.
Prior art shows that lattice constant is very poor greater than the faujusite of 24.50 dusts, particularly na-pretreated zeolite (as the NaY zeolite) acid resistance, and the crystalline structure of zeolite is easy to be destroyed by acid.Moreover when the steam treatment y-type zeolite, the sodium content in the zeolite shrinks its structure cell and has a significant impact, if sodium content is higher in the zeolite, the structure cell of y-type zeolite is difficult to be contracted to super steady level.Thereby, generally need not acid directly handle the sodium type faujusite of lattice constant in the prior art greater than 24.50 dusts, US 5,139,984 and EP 0,569, the used raw material zeolite of 626A1 all is lattice constant zeolites less than 24.50 dusts, with this zeolite of acid treatment only is the secondary pore structure of modulation zeolite, and structure cell shrinks less.Usually at first adopt the sodium content in the ammonium ion exchange method reduction zeolite when y-type zeolite is carried out steam treatment, this ion-exchange must repeat just can make more than twice the sodium content in the zeolite to be reduced to below the 1 heavy % usually.Therefore, the not high shortcoming of the overstable gamma zeolite degree of crystallinity that existing hydrothermal dealumination method obtains except that existence, also there is the shortcoming of complicated operation.
CN 1,042,523A discloses a kind of chemical dealuminization and water-heat process and has combined and be used alternatingly the method for preparing high-silicon Y-Zeolite, it comprises that the solution that will contain ammonium ion and mineral acid mixes with a kind of y-type zeolite, at 25～100 ℃, best 50～95 ℃ of dealuminzations 0.5～3 hour, best 1～2 hour, wherein Suan consumption was 0.1～1.2 mole of H of every mole of zeolite aluminium
+, best 0.5～1.0 mole of H
+, acid concentration is 0.5～5N, best 2～4N carries out ion-exchange simultaneously in the dealumination process, with the sodium ion in the ammonium ion replacement zeolite.And then with the NH that obtains
4Y zeolite carries out dealuminzation with mineral acid or other dealumination agents, carries out steam-treated subsequently, repeats successively once to several times with the process of sour dealuminzation and steam dealumination.Y zeolite raw material wherein can be the NaY zeolite that contains the crystallization NaY zeolite of mother liquor or do not contain mother liquor.Though this method can directly be used the NaY zeolite to do raw material zeolite is taken out aluminium, the y-type zeolite product that obtains also has more rich secondary pore structure and higher degree of crystallinity, but still fail to break through traditional thought, its the first step mainly is with the sodium ion in ammonium ion and the hydrogen ion exchanging zeolite with containing ammonium ion and acid with the effect of zeolite blended, because the consumption of acid is less, has only 0.1～1.2 mole of H of every mole of zeolite aluminium
+To zeolite framework aluminium to remove effect very little, if used NaY zeolite raw material is the NaY zeolite slurry that contains crystallization mother liquor, because of mother liquor is a kind of basic solution, the part acid that adds will neutralize with alkaline mother liquor, thereby acid will be littler to the effect that removes of zeolite framework aluminium.Thereby adopt this method to be difficult to disposable the NaY zeolite to be prepared into high silicon overstable gamma zeolite, and must be through the process of chemical dealuminization and steam dealumination repeatedly, this process is equally too complicated, in industrial very difficult realization.
The objective of the invention is to overcome the shortcoming that the product zeolite crystallinity is not high or dealumination process is too complicated in the existing method, provide a kind of more simple and resulting zeolite product both to have higher crystallinity, have the preparation method of the overstable gamma zeolite of more rich secondary pore again.
The preparation method of overstable gamma zeolite provided by the invention comprises a kind of y-type zeolite is contacted with a kind of solution that contains ammonium ion with a kind of acid solution, and the product that obtains carried out steam-treated, wherein, the consumption of described acid be the concentration of every mole of zeolite framework aluminium 1.5～6 moles of hydrogen ions, acid solution be 0.1～5 equivalent/liter, the temperature that y-type zeolite contacts with acid solution is 5～100 ℃, and be 0.5～72 hour duration of contact; The described solution that contains ammonium ion contacts with y-type zeolite with acid solution, perhaps earlier y-type zeolite is contacted with acid solution, contact with the solution that contains ammonium ion again, the weight ratio of y-type zeolite and ammonium ion is 2～20, the temperature of described steam-treated is 5 00～850 ℃, 0.5～8 hour treatment time.
According to method provided by the invention, its concrete steps are as follows:
(1) y-type zeolite is contacted 0.5～72 hour with a kind of solution that contains ammonium ion at 5～100 ℃ with a kind of acid solution, or earlier y-type zeolite is contacted 0.5～72 hour with a kind of acid solution at 5～100 ℃, contact with a kind of solution that contains ammonium ion, filtration, washing are not detected to there being acid ion again.The consumption of wherein said acid is every mole of zeolite aluminium 1.5～6 moles of hydrogen ions, the concentration of acid solution be 0.1～5 equivalent/liter, the weight ratio of y-type zeolite and ammonium ion is 2～20.
(2) solid product that (1) is obtained is dry or moist, carries out pyroprocessing under the atmosphere of moisture vapor, promptly gets a kind of overstable gamma zeolite.
Wherein, described y-type zeolite is any one y-type zeolite, and for example it can be the higher NaY zeolite of direct synthetic sodium content, also can be lower zeolite of sodium content such as HY zeolite, NH
4Y zeolite and exchanged the y-type zeolite of other metal ions is as the rare-earth type y-type zeolite.The lattice constant of y-type zeolite can be greater than 24.50 dusts also can be smaller or equal to 24.50 dusts.The zeolite of method particularly suitable provided by the invention is direct synthetic NaY zeolite, and promptly lattice constant is worked energetically 24.50 dusts, and in sodium oxide, sodium content is greater than the NaY zeolite of 1 heavy %, particularly sodium content greater than 5 heavy %.
Acid in the described acid solution can be selected from one or more in solubility mineral acid and the organic acid, and described mineral acid is as being in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, hydrofluoric acid, Hydrogen bromide, the perchloric acid one or more; Described organic acid is as can being that in formic acid, acetate, benzene toluene, the oxalic acid one or more also can be that water dissolvable contains one or more in the organic acid of a plurality of carboxyls; In the preferred hydrochloric acid of acid in the described acid solution, sulfuric acid, nitric acid and the phosphoric acid one or more.
Preferred every mole of zeolite framework aluminium 1.5～4.5 moles of hydrogen ions of the consumption of described acid, preferred 0.1～3 equivalent of the concentration of acid solution/liter.
Preferred 50～95 ℃ of the temperature that y-type zeolite contacts with acid solution, preferred 5～48 hours of duration of contact.
The described solution that contains ammonium ion can contact with y-type zeolite with acid solution, also can be earlier with y-type zeolite with after a kind of acid solution contacts, contact with the solution that contains ammonium ion again, more preferred earlier with y-type zeolite and the mode that contacts with the solution that contains ammonium ion again after a kind of acid solution contacts.In this case, y-type zeolite and acid solution 5～100 ℃ contact 0.5～72 hour after, the solution that contains ammonium ion can directly join in the mixture of y-type zeolite and acid solution; The solution that contains ammonium ion also can with mix through acid treatment and filtering acid solution, drying or without the exsiccant y-type zeolite, the solution that contains ammonium ion is contacted with y-type zeolite; The solution that contains ammonium ion with can also in the process of steam-treated y-type zeolite, carry out through contacting of acid-treated y-type zeolite, at this moment, the available solution that contains ammonium ion will be wetting or nonwetting through acid-treated y-type zeolite, then, feed the solution that contains ammonium ion continuously, and heat up simultaneously, at high temperature to carrying out steam-treated through acid-treated y-type zeolite.
In the described solution that contains ammonium ion, the precursor of ammonium ion is solubility ammonium salt or alkali, can be selected from ammonium chloride, ammonium sulfate as it, one or more in ammonium nitrate, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, the ammoniacal liquor.
When the solution that contains ammonium ion with when contacting of acid-treated y-type zeolite carried out in the process of steam treatment y-type zeolite, contain the preferred ammonia soln of solution of ammonium ion.
The weight ratio of y-type zeolite and ammonium ion preferred 2～15.When the solution that contains ammonium ion with when contacting of acid-treated y-type zeolite carried out in steam-treated y-type zeolite zeolite process, can be by the consumption of above-mentioned ammonium ion, the solution that will contain ammonium ion is carried equably, makes it to contact with zeolite.The temperature that y-type zeolite contacts with ammonium ion can in very large range change, and can change in 5～850 ℃ of scopes as it, and duration of contact is generally greater than 0.5 hour.When the contact temperature was higher than the decomposition temperature of ammonium ion precursor, precursor was decomposed the generation ammonia, and ammonia is contacted with y-type zeolite, and this can obtain effect same.
When y-type zeolite contacts with the solution that contains ammonium ion or afterwards, can adopt the mode of ion-exchange in y-type zeolite, to introduce other metal ion, as rare earth ion.
Described high-temperature water vapor is handled and can be carried out according to a conventional method.Y-type zeolite and acid solution be with after the solution that contains ammonium ion contacts, and after filtration, washing is not to there being acid group, directly roasting at high temperature of the wet cake that obtains is carried out dealuminzation with spontaneous water vapor to zeolite.The wet cake that obtains also can drying or non-drying, carries out high-temperature roasting in the presence of the atmosphere of moisture vapor, makes the zeolite dealuminzation.Y-type zeolite with can be after filtration after acid contact, washing is not to there being acid group, through or drying not, directly under the atmosphere of moisture vapor and ammonia, carry out high-temperature roasting.The atmosphere of described moisture vapor can be 100% water vapor, also can be to contain other not participate in the inert gas atmosphere of reacting.Described rare gas element is as being air, nitrogen, helium, neon, argon gas etc.
The temperature that described high-temperature water vapor is handled is conventional temperature range, and it can be 500～850 ℃, preferred 550～750 ℃; The time of handling is conventional time range, and it can be 0.5～8 hour, preferred 1～5 hour.
As previously mentioned, in the prior art, before y-type zeolite carried out hydrothermal dealumination, sodium oxide content is reduced to below the 1 heavy %, otherwise structure cell is difficult to shrink and reaches super steady level, and is except that the restriction to sodium oxide content, also restricted usually to the lattice constant of y-type zeolite, be that lattice constant can not be greater than 24.50 dusts, otherwise the structure of y-type zeolite is very easily destroyed by acid.
Method provided by the invention has but broken through this idea, adopt earlier and y-type zeolite is carried out dealuminzation with a large amount of acid, simultaneously or thereafter again with contain ammonium ion solution and contact, carry out the method for steam-treated at last, not only sodium oxide content and the lattice constant to the raw material y-type zeolite do not have any restriction, the content of sodium oxide in y-type zeolite can be greater than 1 heavy %, even can be greater than 5 heavy %, lattice constant can be greater than 24.50 dusts, and the product zeolite that obtains is when having significantly structure cell contraction and more rich secondary pore, also have very high degree of crystallinity, its degree of crystallinity is near 100%.This is that prior art is incomparable.
Method provided by the invention is owing to the method that has adopted a chemical dealuminization and a steam roasting, thereby its operation is very simple, very big facility is provided for industrial scale operation, thereby has wide prospect in industrial application.
The overstable gamma zeolite of method provided by the invention preparation is owing to have abundant secondary pore and near 100% relative crystallinity, thereby has advantages of high catalytic activity.It can be used as the active ingredient of various hydrocarbon conversion catalysts, be especially suitable for use as the active ingredient of catalytic cracking catalyst, hydrocracking catalyst, hydrotreating catalyst, when as the active ingredient of catalytic cracking catalyst, have stronger heavy oil conversion performance and higher yield of light oil, this from following example as can be seen.
The following examples will the present invention will be further described, but do not limit the present invention in any form.
Example 1
Prepare overstable gamma zeolite according to method provided by the invention.
(relative crystallinity is decided to be 100% to take by weighing 500 gram (dry basis) NaY zeolites, lattice constant 24.69 dusts, silica alumina ratio 4.9, sodium oxide content 13.5 heavy %, the Zhou village catalyst plant is produced) 5 liters of deionized waters of adding, under agitation be warming up to 80 ℃, add 2 equivalents/liter 2 liters of hydrochloric acid solns, constant temperature 8 hours adds 200 gram solid ammonium chlorides, stirred 1 hour, filtration, washing are not detected to there being chlorion, and in 600 ℃, roasting is 2 hours under spontaneous water vapour atmosphere for gained wet cake (water-content is 47 heavy %), promptly get the overstable gamma zeolite of the inventive method preparation, be designated as A.Table 1 has provided sodium oxide content, chloride ion content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and the secondary porosity of A.
Wherein sodium oxide content adopts aas determination, and chloride ion content adopts the standard electrode method to measure, and relative crystallinity is a benchmark with 533 crystal face diffraction peak peak areas, adopts unimodal method to measure, and lattice constant is calculated and got by following formula:
A wherein
oBe lattice constant, θ is the 2 θ angles that provide of 533 crystal face diffraction peaks half.Specific surface, pore volume, secondary pore volume are measured with cryogenic nitrogen absorption BET method, and the secondary porosity is the ratio of secondary pore volume and pore volume.The avalanche temperature adopts differential thermal analyzer to measure.
Comparative Examples 1
If this Comparative Examples explanation in preparation process y-type zeolite not with contain NH
4 +Solution contact then can not reach the object of the invention.
Prepare overstable gamma zeolite according to example 1 described method, but the NaY zeolite does not add ammonium chloride after acid treatment, the contrast overstable gamma zeolite note that makes is made B.Table 1 has provided sodium oxide and chloride ion content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and the secondary porosity of contrast overstable gamma zeolite B.
Comparative Examples 2
The explanation of this Comparative Examples is only carried out a chemical dealuminization and a steam-treated as consumption sour in the method that adopts CN 1042523A, can not reach the object of the invention.
Take by weighing NaY zeolite slurry 250 grams (containing NaY butt 75 grams) that contain crystallization mother liquor, add 100 gram ammonium sulfate, add the making beating of 1000 ml deionized water again, add concentration and be 140 milliliters of the sulphuric acid solns of 1 mol, handled 1 hour heat temperature raising to 95～100 ℃, filters, washs to the sulfate radical-free ion to be detected, and gained wet cake (water content is 47 heavy %) is in 600 ℃, roasting is 2 hours under spontaneous water vapour atmosphere, must contrast zeolite C.Table 1 has provided sodium oxide content and chloride ion content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and the secondary porosity of C.
Comparative Examples 3
This Comparative Examples illustrates the situation of Hydrothermal Preparation overstable gamma zeolite routinely.
With example 1 described NaY zeolite 500 grams (dry basis) and 5000 grams, 10 heavy % (NH
4)
2SO
4Aqueous solution under agitation is warming up to 90 ℃ and carried out ion-exchange 1 hour, filters, washs to there not being SO
4 2-, handled filter cake 2 hours with 100% water vapor down at 600 ℃, the zeolite after the steam-treated is weighed % (NH with 5000 grams 10 again
4)
2SO
4Aqueous solution under agitation is warming up to 90 ℃ and carried out ion-exchange 1 hour, filters, washs to there not being SO
4 2-Ion was handled 4 hours with 100% water vapor down at 600 ℃ again, made the contrast overstable gamma zeolite, and note is made D.Table 1 provides sodium oxide content, chloride ion content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and the secondary porosity of D.
Table 1
| Example number | 1 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Product zeolite numbering | A | B | C | D |
| Sodium oxide content, heavy % | 4.3 | 4.2 | 4.5 | 1.2 |
| Chloride ion content, heavy % | 0.01 | 0.03 | - | - |
| Relative crystallinity, % | 101 | 65 | 100 | 70 |
| Lattice constant, dust | 24.48 | 24.47 | 24.62 | 24.49 |
| The avalanche temperature, ℃ | 1032 | 1020 | 890 | 1010 |
| Specific surface, rice 2/ gram | 776 | 660 | 750 | 675 |
| Pore volume, milliliter/gram | 0.360 | 0.321 | 0.324 | 0.325 |
| The secondary pore volume, milliliter/gram | 0.105 | 0.045 | 0.025 | 0.085 |
| The secondary porosity, % | 29.2 | 14.0 | 7.72 | 26.2 |
The result of table 1 shows, adopt method provided by the invention, just can make the lattice constant of NaY zeolite be contracted to 24.48 dusts through a chemical dealuminization and a hydrothermal treatment consists from 24.69 dusts, reach super steady level, simultaneously, make the relative crystallinity of overstable gamma zeolite can keep 100%, and have 29.2% secondary porosity, up to 776 meters
2The specific surface of/gram and 1032 ℃ avalanche temperature.And if the NaY zeolite does not contact with the solution that contains ammonium ion, though also can make lattice constant be contracted to 24.47 dusts, its relative crystallinity, secondary porosity, specific surface are much lower.Adopt the method for CN 1042523A, but without repeating to take out the aluminium process, only carry out once chemistry and take out aluminium and a hydrothermal dealumination, though can keep higher relative crystallinity, but it is less that structure cell shrinks, do not reach super steady level, thereby its avalanche temperature is much lower, and has low-down secondary porosity.Though adopt conventional hydrothermal dealumination method through the secondary ions exchange, the secondary hydrothermal treatment consists of longer time, structure cell shrinks and also only reaches the level that the present invention adopts method, its relative crystallinity and specific surface are very low.The above results illustrates that method provided by the invention is not only simple to operate, and the quality of the zeolite product that obtains also is better than prior art greatly.
Example 2
Prepare overstable gamma zeolite according to method provided by the invention.
Prepare overstable gamma zeolite according to example 1 described method, just with 2 liter of 2 equivalent/liter hydrochloric acid change into 3.5 liter of 1.5 equivalent/liter phosphoric acid, the time that the NaY zeolite contacts with phosphoric acid solution is 18 hours, restrains solid NH with 200
4Cl changes 100 gram solid phosphoric acid ammoniums into, filter, washing is not to having the filter cake that obtains behind the acid ion at 650 ℃, with 100% steam-treated 2 hours, the overstable gamma zeolite of method preparation provided by the invention, remember and make E.Table 2 has provided sodium oxide content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and the secondary porosity of E.
Example 3
Prepare overstable gamma zeolite according to method provided by the invention.
Prepare overstable gamma zeolite according to example 1 described method, but with 2 liter of 2 equivalent/liter hydrochloric acid soln change into 2 liter of 2 equivalent/liter salpeter solution, the time that the NaY zeolite contacts with salpeter solution is 24 hours, with 200 gram solid NH
4Cl changes 400 gram solid ammonium nitrate into, filter cake behind the filtration washing is in 600 ℃, roasting is 3 hours under 100% water vapour atmosphere, promptly get the overstable gamma zeolite F of the inventive method preparation, table 2 has provided sodium oxide content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and the secondary porosity of F.
Example 4
Prepare overstable gamma zeolite according to method provided by the invention.
Prepare overstable gamma zeolite according to example 1 described method, different is not add solid ammonium chloride, directly will be with the zeolite filtration of acid treatment, washing is to there not being acid ion, and with filter cake under ammonia that contains ammonia 10 heavy % and water vapor mixture atmosphere in 700 ℃ of roastings 2 hours, to contain the ammonia soln of 10 heavy % ammonia, flow velocity is 5 ml/min, promptly gets overstable gamma zeolite provided by the invention.Note is made G.Table 2 has provided sodium oxide content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and the secondary porosity of G.
Example 5
Prepare overstable gamma zeolite according to method provided by the invention.
Prepare overstable gamma zeolite according to example 1 described method, different is with the 200 gram solid ammonium chlorides rare earth chloride solution that to change 120 milliliters of rare earth oxide content into be 207 mg/ml and 200 gram solid ammonium chlorides (wherein in the rare earth chloride solution in oxide compound, contain lanthanum 54 mg/ml, antimony 102 mg/ml, other rare earth is 51 mg/ml), the overstable gamma zeolite that makes is designated as H.Table 2 has provided sodium oxide content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and the secondary porosity of H.
Example 6
Prepare overstable gamma zeolite according to method provided by the invention.
Prepare overstable gamma zeolite according to example 5 described methods, different is that the re chloride consumption is 250 milliliters, and the overstable gamma zeolite that makes is designated as J.Table 2 has provided the sodium oxide content of J, rare earth oxide content, relative crystallinity, lattice constant, avalanche temperature, specific surface, pore volume, secondary pore volume and secondary porosity.
Table 2
| Example number | 2 | 3 | 4 | 5 | 6 |
| The overstable gamma zeolite numbering | E | F | G | H | J |
| Sodium oxide content, heavy % | 4.5 | 4.0 | 5.0 | 4.2 | 4.0 |
| Rare earth oxide content, heavy % | - | - | - | 2.2 | 5.0 |
| Relative crystallinity, % | 98 | 95 | 90 | 98 | 92 |
| Lattice constant, dust | 24.47 | 24.48 | 24.47 | 24.49 | 24.50 |
| The avalanche temperature, ℃ | 1030 | 1020 | 1015 | 1032 | 1040 |
| Specific surface, rice 2/ gram | 785 | 760 | 750 | 780 | 745 |
| Pore volume, milliliter/gram | 0.353 | 0.347 | 0.320 | 0.342 | 0.350 |
| The secondary pore volume, milliliter/gram | 0.098 | 0.086 | 0.072 | 0.100 | 0.082 |
| The secondary porosity, % | 27.8 | 24.5 | 22.5 | 29.2 | 23.4 |
Example 7
This example explanation is with the overstable gamma zeolite that the adopts method preparation provided by the invention catalytic performance as the cracking catalyst of active ingredient.
With 2 kilograms of kaolin (butts, Suzhou china clay company produces), 0.12 kilogram of technical hydrochloric acid and 20 kilograms of deionized waters mix making beating, add 1.25 kilograms of pseudo-boehmites, stir after 1 hour 0.35 kilogram of the overstable gamma zeolite A that adds example 1 preparation, behind the homogeneous at 600 ℃ of following spray drying formings.With the sample after the moulding with 20 times to the butt sample, concentration is that the ammonium dihydrogen phosphate aqueous solution of 0.016 heavy % mixes, 80 ℃ were stirred 30 minutes down, filter, 120 ℃ of oven dry, and 800 ℃ down with 100% steam aging 4 hours, get the catalyzer I.
With boiling range is that 235～337 ℃ straight distillation light diesel oil is that raw material is estimated its light oil microactivity on the small stationary bed bioreactor, 460 ℃ of temperature of reaction, catalyzer loading amount 5 grams, weight hourly space velocity 16 hours
-1, agent weight of oil ratio is 3.2.
Vacuum gas oil with 227～475 ℃ of boiling ranges is a reaction raw materials, the micro-activity of heavy oil of evaluate catalysts I on the small stationary bed bioreactor, and 482 ℃ of temperature of reaction, catalyzer loading amount 5 grams, weight hourly space velocity 16 hours-1, agent weight of oil ratio is 4.Table 3 has provided the character of vacuum gas oil, and table 4 has provided zeolite content, sodium oxide content, phosphorus content, specific surface and the pore volume of catalyzer I, and table 5 has provided the light oil microactivity of catalyzer I, heavy oil conversion rate and products distribution.Wherein phosphorus content adopts the analysis of x-ray fluorescence spectrometry method in the catalyzer, and crackate is formed the employing gas chromatographic analysis.
Comparative Examples 4
The explanation of this Comparative Examples is the catalytic performance of the cracking catalyst of active ingredient with the overstable gamma zeolite of conventional Hydrothermal Preparation.
Method by example 7 prepares catalyzer, and that different is the overstable gamma zeolite D that the overstable gamma zeolite A of example 1 preparation is changed into Comparative Examples 3 preparations, and the catalyzer of preparing note is made II.
Under the condition identical with example 7 with the light oil microactivity and the micro-activity of heavy oil of same stock oil evaluate catalysts II.Table 4 has provided zeolite content, sodium oxide content, phosphorus content, specific surface and the pore volume of catalyst II, and table 5 has provided light oil microactivity and the heavy oil conversion rate and the products distribution of catalyst II.
Example 8
This example explanation is with the overstable gamma zeolite that the adopts method preparation provided by the invention catalytic performance as the cracking catalyst of active ingredient.
Get SiO
2Content is 25 liters of the water glass of 58 grams per liters, under agitation adding 8.75 liters is the alum liquor of 75 grams per liters in aluminum oxide content, wore out 20 minutes in 45 ℃, the ammoniacal liquor that adds 0.95 liter of 16 heavy %, filter, obtaining alumina content is the silicate gel carrier of 31 heavy %, 20 kilograms of 0.35 kilogram of the overstable gamma zeolite H of adding example 5 preparations and deionized waters, stir, behind the homogeneous in 600 ℃ of spray drying formings.To the sample butt, phosphorus concentration is the (NH of 0.005 heavy % with the sample after the moulding and 20 times
4)
3PO
4Aqueous solution, 60 ℃ of constant temperature 15 minutes, the filter cake after the filtration repeat the (NH with same amount
4)
3PO
4The aqueous solution handles twice, filter, 120 ℃ of dryings, the sample that obtains 800 ℃ down with 100% steam aging 4 hours, make the catalyzer III.
Under the condition identical, with the light oil microactivity and the micro-activity of heavy oil of identical stock oil evaluate catalysts III with example 7.Table 4 has provided zeolite content, sodium oxide content, phosphorus content, rare earth oxide content, specific surface and the pore volume of catalyzer III.Table 5 has provided light oil microactivity and the heavy oil conversion rate and the product distribution of catalyzer III.
Example 9
The explanation of this example is the catalytic performance of the cracking catalyst of active ingredient with the overstable gamma zeolite that adopts method preparation provided by the invention.
The overstable gamma zeolite J that takes by weighing 0.3 kilogram of example 6 preparation pulls an oar with 1.1 kilograms of kaolin (butt), 0.4 kilogram of (butt) aluminium colloidal sol (salic 22 heavy %, Zhou village, Shandong catalyst plant product), behind the homogeneous in 600 ℃ of spray drying formings.With the sample after the moulding and 10 times to sample butt weight, phosphorus concentration is the (NH of 0.064 heavy %
4)
3PO
4Solution mixes, and 20 ℃ were stirred 60 minutes down, filtration, drying, and the sample that obtains wore out 4 hours at 800 ℃ with 100% water vapor, made the catalyzer IV.
Under the condition identical, with the light oil microactivity and the micro-activity of heavy oil of identical stock oil evaluate catalysts IV with example 7.Table 4 has provided zeolite content, sodium oxide content, phosphorus content, rare earth oxide content, specific surface and the pore volume of catalyzer IV.Table 5 has provided light oil microactivity and the heavy oil conversion rate and the product distribution of catalyzer IV.
Table 3
| Density (20 ℃), gram per centimeter 3 | 0.8652 |
| Viscosity (50 ℃), millimeter 2/ second | 14.58 |
| Viscosity (100 ℃), millimeter 2/ second | 4.37 |
| Bituminous matter, heavy % C 5Insolubles C 7Insolubles | 0.60 0.026 |
| Carbon residue, heavy % | 0.04 |
| Sulphur content, heavy % | 0.42 |
| Boiling range, the heavy % 5 10 20 30 40 60 80 95 of ℃ initial boiling point does | 227 274 289 322 347 373 401 431 458 475 |
Table 4
| Example number | 7 | Comparative Examples 4 | 8 | 9 |
| The catalyzer numbering | Ⅰ | Ⅱ | Ⅲ | Ⅳ |
| Zeolite content, heavy % | 15 | 15 | 15 | 25 |
| Sodium oxide content, heavy % | 0.13 | 0.12 | 0.07 | 0.12 |
| Phosphorus content, heavy % | 0.52 | 0.60 | 0.55 | 0.63 |
| Rare earth oxide content, heavy % | 0 | 0 | 0.35 | 1.3 |
| Specific surface, rice 2/ gram | 190 | 200 | 290 | 225 |
| Pore volume, milliliter/gram | 0.19 | 0.20 | 0.39 | 0.26 |
Table 5
| Example number | 7 | Comparative Examples 4 | 8 | 9 |
| The catalyzer numbering | Ⅰ | Ⅱ | Ⅲ | Ⅳ |
| Light oil microactivity, heavy % | 60 | 55 | 67 | 69 |
| Transformation efficiency, heavy % | 63.17 | 60.41 | 68.90 | 70.99 |
| Product distributes, and heavy % natural gas liquid solar oil is greater than 330 ℃ of cut coke | 10.95 50.21 15.07 22.76 2.01 | 11.01 47.25 13.10 26.49 2.15 | 12.98 53.62 16.23 14.87 2.30 | 13.44 55.10 16.25 12.76 2.45 |
The result of table 5 shows, with compare as the catalyzer of active ingredient with the overstable gamma zeolite of conventional hydrothermal dealumination method preparation, be that the catalyzer of active ingredient has high activity, high yield of light oil and stronger mink cell focus conversion capability with the overstable gamma zeolite that adopts method preparation provided by the invention.
Claims (10)
1. the preparation method of an overstable gamma zeolite comprises a kind of y-type zeolite is contacted with a kind of solution that contains ammonium ion with a kind of acid solution, and the product that obtains carried out steam-treated, it is characterized in that, the consumption of described acid be the concentration of every mole of zeolite framework aluminium 1.5～6 moles of hydrogen ions, acid solution be 0.1～5 equivalent/liter, the temperature that y-type zeolite contacts with acid solution is 5～100 ℃, and be 0.5～72 hour duration of contact; The described solution that contains ammonium ion contacts with y-type zeolite with acid solution, perhaps earlier y-type zeolite is contacted with acid solution, contact with the solution that contains ammonium ion, the weight ratio of y-type zeolite and ammonium ion is 2～20, the temperature of described steam-treated is 500～850 ℃, 0.5～8 hour treatment time.
2. according to the described method of claim 1, it is characterized in that described y-type zeolite is that lattice constant is worked energetically 24.50 dusts, the sodium oxide content NaY zeolite greater than 1 heavy %.
3. according to the described method of claim 1, it is characterized in that the described solution that contains ammonium ion and y-type zeolite contact acid solution with carry out after y-type zeolite contacts.
4. according to the described method of claim 3, it is characterized in that the described solution that contains ammonium ion carries out with contacting in the process of steam treatment y-type zeolite of y-type zeolite, the described solution that contains ammonium ion refers to ammonia soln.
5. according to the described method of claim 1, the consumption that it is characterized in that described acid is every mole of zeolite framework aluminium 1.5～4.5 moles of hydrogen ions, the concentration of acid solution be 0.1～3 equivalent/liter.
6. according to the described method of claim 1, it is characterized in that the temperature that y-type zeolite contacts with acid solution is 50～95 ℃, 5～48 hours duration of contact.
7. according to claim 1,3,5 or 6 described methods, it is characterized in that acid in the described acid solution is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
8. according to the described method of claim 1, the weight ratio that it is characterized in that described y-type zeolite and ammonium ion is 2～15.
9. according to claim 1,3 or 8 described methods, the precursor that it is characterized in that described ammonium ion is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, the ammoniacal liquor, and the perhaps described solution that contains ammonium ion replaces with the atmosphere that contains ammonia.
10. according to the described method of claim 1, the temperature that it is characterized in that described steam-treated is 550～750 ℃, 1～5 hour treatment time.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9789475B2 (en) | 2011-12-15 | 2017-10-17 | Petrochina Company Limited | Ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9840422B2 (en) | 2011-12-15 | 2017-12-12 | Petrochina Company Limited | Magnesium modified ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9844772B2 (en) | 2011-12-15 | 2017-12-19 | Petrochina Company Limited | Heavy oil catalytic cracking catalyst and preparation method therefor |
| US9889439B2 (en) | 2011-12-15 | 2018-02-13 | Petrochina Company Limited | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
| US9968918B2 (en) | 2012-06-01 | 2018-05-15 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
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| CN101410182A (en) * | 2006-03-30 | 2009-04-15 | 新日本石油株式会社 | Hydrocracking catalyst, and method for production of fuel base material |
| CN103359760A (en) * | 2012-04-06 | 2013-10-23 | 华东理工大学 | Method for removing sodium from sodium zeolite molecular sieve through ion exchange |
| CN103964463B (en) * | 2013-01-30 | 2016-11-23 | 中国石油天然气股份有限公司 | A kind of preparation method of Y type molecular sieve |
| CN108452834B (en) * | 2017-02-22 | 2020-03-24 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
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|---|---|---|---|---|
| US4503023A (en) * | 1979-08-14 | 1985-03-05 | Union Carbide Corporation | Silicon substituted zeolite compositions and process for preparing same |
| CN1042523A (en) * | 1989-06-15 | 1990-05-30 | 中国石油化工总公司兰州炼油化工总厂 | A kind of method for preparing high-silicon Y-Zeolite |
| US5139984A (en) * | 1989-10-04 | 1992-08-18 | Research Association For Residual Oil Processing | Faujasite-type aluminosilicates, a method of producing the same, and hydrocracking catalysts for heavy hydrocarbon oils |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4503023A (en) * | 1979-08-14 | 1985-03-05 | Union Carbide Corporation | Silicon substituted zeolite compositions and process for preparing same |
| CN1042523A (en) * | 1989-06-15 | 1990-05-30 | 中国石油化工总公司兰州炼油化工总厂 | A kind of method for preparing high-silicon Y-Zeolite |
| US5139984A (en) * | 1989-10-04 | 1992-08-18 | Research Association For Residual Oil Processing | Faujasite-type aluminosilicates, a method of producing the same, and hydrocracking catalysts for heavy hydrocarbon oils |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9789475B2 (en) | 2011-12-15 | 2017-10-17 | Petrochina Company Limited | Ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9840422B2 (en) | 2011-12-15 | 2017-12-12 | Petrochina Company Limited | Magnesium modified ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9844772B2 (en) | 2011-12-15 | 2017-12-19 | Petrochina Company Limited | Heavy oil catalytic cracking catalyst and preparation method therefor |
| US9889439B2 (en) | 2011-12-15 | 2018-02-13 | Petrochina Company Limited | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
| US9968918B2 (en) | 2012-06-01 | 2018-05-15 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
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| CN1220238A (en) | 1999-06-23 |
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