CN1330982A - P-contained Y-zeolite and its preparing process - Google Patents
P-contained Y-zeolite and its preparing process Download PDFInfo
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Abstract
A Y-type zeolite is disclosed, which contains P component (0.1-15 wt.%) and Si component (1-15 wt.%) which is carried by immersing zeolite in the solution of Si compound. Its advantages are high crystallinity and higher catalytic performance in heavy oil transfer.
Description
The invention relates to a kind of faujasite and preparation method thereof.More particularly, be about a kind of P-contained Y-zeolite and preparation method thereof.
Phosphorus is introduced the catalytic performance that molecular sieve can improve catalyst.
EP252,761A2 disclose a kind of hydrocarbon cracking catalyzer, and this catalyst contains (a) a kind of nonzeolite inorganic oxide matrix and (b) a kind of superstable gamma-type crystalline zeolite.Described zeolite has carried out preliminary treatment, and pretreated method is that described zeolite is contacted the sufficiently long time with a kind of phosphorus-containing compound, makes the described zeolite-loaded phosphorus of going up effective dose.
EP397 discloses a kind of composition in 183, and said composition contains Na
2O content is the ion-exchange NaY zeolite of the heavy % of 2-5 and with P
2O
5Meter, the phosphorus of the heavy % of 0.1-4.0.The preparation method of said composition comprises that (a) carries out ion-exchange and washing with a kind of NaY zeolite, obtaining a kind of NaO content is the exchange y-type zeolite of the heavy % of 1-5, (b) will exchange y-type zeolite and a kind of phosphorus compound solution hybrid reaction, described phosphorus compound is selected from one group that is made up of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), sodium dihydrogen phosphate, (c) reclaims with P
2O
5The meter phosphorus content is the P-contained Y-zeolite product of the heavy % of 0.1-4.
In the phosphorus modifying method of molecular sieve, with phosphorus-containing compound solution separately with molecular sieve, especially behind the Y zeolite dipping, obtaining phosphorus containing molecular sieve through hydrothermal treatment consists is common zeolite phosphorus main methods of modification, general by such processing, can remove the aluminium in the part zeolite lattice and the structure cell of zeolite is dwindled, the hydrothermal stability of raising molecular sieve, phosphorus is combined with molecular sieve more effectively, make the selection of catalysts that contains this kind P-contained zeolite also obtain to a certain degree improvement.But molecular sieve is after the phosphorus modification, and its degree of crystallinity but has obvious decline, and this not only causes a large amount of losses of zeolite, and influential to the stability and the activity of molecular sieve, and will further have influence on the performance of catalyst.
The objective of the invention is to overcome the lower shortcoming of hydrothermal treatment consists post crystallization degree in the prior art P-contained Y-zeolite preparation process, provide a kind of new through the higher P-contained zeolite of hydrothermal treatment step post crystallization degree.Another object of the present invention provides the preparation method of this P-contained zeolite.
Zeolite provided by the invention contains phosphorus, and wherein, this zeolite also contains a kind of silicon components, and described silicon components is to get on the method load of silicon compound solution dipping zeolite, with SiO
2Meter, the content of described silicon components are the heavy % of 1-15, with P
2O
5Meter, the content of described phosphorus component are the heavy % of 0.1-15.
The preparation method of P-contained zeolite provided by the invention comprises with a kind of raw material y-type zeolite of a kind of solution impregnation of phosphorus compound, and drying wherein, also comprises the solution impregnation y-type zeolite with silicon compound, with SiO
2Meter, the consumption of described silicon compound solution make and contain the heavy % of silicon components 1-15 in the P-contained zeolite that obtains, with P
2O
5Meter, the consumption of described phosphorus-containing compound solution make and contain the heavy % of phosphorus component 0.1-15 in the P-contained zeolite that obtains.
According to P-contained zeolite provided by the invention, the content of described silicon components is the heavy % of 1-15, is preferably the heavy % of 5-12, and the content of described phosphorus component is the heavy % of 0.1-15, is preferably the heavy % of 2-10.
Described silicon components is to get on the method load of silicon compound solution dipping zeolite, the solution of described silicon compound is selected from the aqueous solution or organic solution and this silicon compound as liquid of silicon compound, as Ludox, waterglass, the fluosilicate aqueous solution, organo-silicon compound and their solution etc., preferred silicon compound solution is selected from Ludox, waterglass, the fluosilicate aqueous solution, dimethicone, in the polymethylphenyl siloxane fluid one or more, more preferred silicon compound solution is selected from Ludox, waterglass, the ammonium fluosilicate aqueous solution, polymethylphenyl siloxane fluid 255, polymethylphenyl siloxane fluid 250, polymethylphenyl siloxane fluid 274, in the dimethicone one or more.Particularly preferred silicon compound solution is selected from one or more in Ludox, waterglass and the ammonium fluosilicate aqueous solution.
According to P-contained Y-zeolite provided by the invention, after 550～850 ℃ of hydrothermal treatment consists, its relative crystallinity is not less than 70%, said relative crystallinity is the percent value of the degree of crystallinity of P-contained Y-zeolite provided by the invention and the degree of crystallinity of NaY raw material (defining its degree of crystallinity is 100%) among the present invention, the assay method of this relative crystallinity is referring to " petrochemical industry analytical method (RIPP test method) " (volume such as Yang Cuiding, Science Press, 414-415, nineteen ninety publishes).
P-contained zeolite provided by the invention has following pore size distribution, and after 550-850 ℃ of hydrothermal treatment consists, the pore volume of this P-contained zeolite second hole accounts for 15～75% of total pore volume, is preferably 20-60%.Described second hole refers to that the bore dia except that molecular sieve intracrystalline micropore is the hole of 20～1000 dusts.Total pore volume adopts low-temperature nitrogen adsorption method to measure, referring to " petrochemical industry analytical method (RIPP test method) " (424-426, nineteen ninety publishes for volume such as Yang Cuiding, Science Press).Determine the micro pore volume of molecular sieve from adsorption isotherm according to the T graphing method, total pore volume is deducted micro pore volume obtain the second hole volume.
Preparation method according to P-contained zeolite provided by the invention, described step with silicon-containing compound dipping y-type zeolite can be before soaking the phosphorus step, carry out afterwards or simultaneously, in order to reduce operating procedure, preferably, promptly flood synthetic step of step of phosphorus and silicon compound with a kind of solution impregnation y-type zeolite that contains phosphorus compound and silicon compound simultaneously.
Described phosphorus-containing compound is selected from this area various phosphorus compounds commonly used, as phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate etc.Described silicon-containing compound is described in front.The concentration of phosphorus-containing compound and silicon compound solution is unimportant, as long as phosphorus compound and silicon compound can be immersed on the y-type zeolite equably,, can also repeatedly flood if solution concentration is lower, but preferred single-steeping.
Described raw material y-type zeolite can be selected various y-type zeolites, as NaY, NH
4In Y, HY zeolite, the overstable gamma zeolite one or more, wherein, preferred sodium oxide content is the y-type zeolite of the heavy % of 3-10, is the NaY of the heavy % of 3-10 as sodium oxide content.Adopt the y-type zeolite of high oxidation sodium content more to help reaching purpose of the present invention, its reason will be discussed hereinafter.Therefore, when using NH
4When one or more in Y zeolite, HY, the zeolite overstable gamma zeolite are raw material, if the not enough 3-10 of sodium content is heavy %, though can be directly as raw material of the present invention, but, under the preferable case, carry out ion-exchange with solution that contains sodium ion and described zeolite, make the sodium oxide molybdena that contains the heavy % of 3-10 on the zeolite.
According to method provided by the invention, after dipping phosphorus and silicon compound, all right, and preferably have the step that hydrothermal treatment consists dipping is gone up the y-type zeolite of phosphorus and silicon compound, this step comprises, at 550-850 ℃, be preferably under 600-750 ℃ the temperature, described y-type zeolite is contacted with a kind of steam-laden atmosphere, be at least time of contact 10 minutes, preferred 15 minutes to 5 hours, described steam-laden atmosphere can be 100% steam, also can be to contain the steam of at least 10 body % steam and the gaseous mixture of inert gas, described inert gas refers in the hydrothermal treatment consists process zeolite not had the gas of destruction, as air, nitrogen, oxygen, carbon dioxide, gas of group 0 element etc. in the periodic table of elements.Wherein, one or more in preferred air, nitrogen and the carbon dioxide.In the hydrothermal treatment consists process, zeolite generation dealuminzation phenomenon, owing to contain silicon components in the P-contained zeolite provided by the invention, wherein the part silicon atom can migrate in the room of y-type zeolite dealuminzation formation, zeolite is mended silicon, though the zeolite that sodium oxide content is lower also can use, but in the zeolite of high oxidation sodium content, the existence of sodium oxide molybdena can slow down the dealuminzation speed of zeolite, the speed that makes silicon atom enter the dealuminzation room is accelerated relatively, thereby sodium oxide content is that the y-type zeolite of the heavy % of 3-10 is preferred.Mending the silicon effect is maintained skeleton structure of zeolite, therefore, hydrothermal treatment consists not only makes zeolite produce many second holes, and phosphorus and zeolite are combined better, and owing to the benefit silicon effect of silicon components to zeolite, skeleton structure of zeolite can be complete, has the degree of crystallinity higher than prior art, overcome the prior art P-contained zeolite through the lower shortcoming of hydrothermal treatment consists post crystallization degree.The raising of relative crystallinity means that zeolite changes the minimizing of amorphous silicon aluminum portions into, i.e. the minimizing of wastage of material.
P-contained zeolite provided by the invention also has than the better catalytic performance of prior art, and for example, 500 ℃ of reaction temperatures, oil ratio is 6, and air speed is 16 hours
-1Condition under, with a kind of pipe oil transportation is raw material, at small fixed flowing bed P-contained zeolite provided by the invention is estimated as the catalyst of active component preparation, conversion ratio is up to 74.0 heavy %, yield of light oil is up to 77.9 heavy %, the C5+ yield of gasoline is up to 57.0 heavy %, coking yield is 4.2 heavy %, and under identical condition, when adopting the catalyst of the existing P-contained zeolite of same amount, conversion ratio, yield of light oil, yield of gasoline has only 71.8 heavy % respectively, 72.1 heavy %, 51.4 heavy %, coking yield are then up to 5.4 heavy %, employing contains the catalyst of P-contained zeolite provided by the invention and compares with the catalyst that employing contains existing P-contained zeolite, conversion ratio, yield of light oil, yield of gasoline have improved 3.06% respectively, 8.04% and 10.89%, coking yield has then reduced by 22.22%.
The following examples will the present invention is described further, but not thereby limiting the invention.
Example 1
The preparation of P-contained zeolite provided by the invention.
1. with 100 grams (dry basis), lattice constant is that the NaY type zeolite (sodium oxide content 14 heavy %, the Shandong catalyst plant is produced) of 2.473 nanometers is the NH of 5 heavy % with 2 liters of concentration
4The Cl aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and spent the deionised water filter cake to there not being acid group, obtained NH after the drying
4NaY type zeolite records its Na
2O content is 4.9 heavy %.
2. the diammonium hydrogen phosphates (Beijing Chemical Plant produce, analyzes pure) of 8.22 grams are dissolved in the 20 gram decationized Y sieve water and stir evenly, (Changhong chemical plant, Beijing commercial product contains 12 and weighs %SiO to join 80 gram Ludox then
2) in mix, obtain the solution of phosphorus-containing compound and silicon compound, with the NH of the above-mentioned preparation of the solution impregnation that obtains 90 grams
4NaY type zeolite then 120 ℃ of oven dry, obtains P-contained Y-zeolite A provided by the invention, and phosphorus and the silicone content of P-contained Y-zeolite A are as shown in table 1.Dipping silicon wherein and phosphorus content are by calculating.
Example 2
The preparation of P-contained zeolite provided by the invention.
1. by the method for example 1 identical NaY zeolite is carried out ion-exchange, that different is NH
4The concentration of aqueous solution of Cl is 10 heavy %, and must contain sodium oxide content is the NH of 3.8 heavy %
4The NaY zeolite.
2. the method by example 1 prepares P-contained zeolite, and the consumption of different is diammonium hydrogen phosphate is 4.11 grams, and the deionized water consumption is 15 grams, obtains P-contained zeolite B provided by the invention.Phosphorus among the P-contained zeolite B and dipping silicone content are listed in the table 1.
Comparative Examples 1
The preparation of reference P-contained zeolite.
1. prepare Na by 1 method in the example 2
2O content is the NH of 3.8 heavy %
4The NaY zeolite.
2. 4.11 gram diammonium hydrogen phosphates are dissolved in the 100 gram deionized waters, restrain the NH that steps 1 obtain with the ammonium dibasic phosphate solution dipping 90 that obtains
4The NaY zeolite, 120 ℃ of oven dry obtain reference P-contained zeolite B1.Phosphorus content among the reference zeolite B1 is listed in the table 1.
Example 3
The preparation of P-contained zeolite provided by the invention.
1. by the method for example 1 identical NaY zeolite is carried out ion-exchange, getting sodium oxide content is the NH of 4.9 heavy %
4The NaY zeolite.
2. 12.33 gram diammonium hydrogen phosphates are dissolved in the 25 gram water, the ammonium fluosilicate of the ammonium dibasic phosphate solution that obtains and 190 milliliter of 1 mol (chemical pure, the Beijing Chemical Plant produces) solution is mixed, with the NH that obtains in the mixed solution dipping 90 gram steps 1 that obtain
4The NaY zeolite, 120 ℃ of oven dry obtain P-contained zeolite C provided by the invention.Phosphorus among the P-contained zeolite C and dipping silicone content are listed in the table 1.
Example 4
The preparation of P-contained zeolite provided by the invention.
1. be the overstable gamma zeolite (Na of 2.446 nanometers with 100 gram (dry basis) lattice constants
2O content is 0.8 heavy %, and the Shandong catalyst plant is produced) and 2 liters of Na that concentration are 5 heavy %
2SO
4Aqueous solution was carried out ion-exchange 0.5 hour in 60 ℃, filtered, and spent the deionised water filter cake to there not being acid group, drying, and obtaining sodium oxide content is the overstable gamma zeolite of 4.6 heavy %.
2. 8.22 gram diammonium hydrogen phosphates are dissolved in the 20 gram deionized waters, the ammonium dibasic phosphate solution that obtains is mixed with the ammonium fluosilicate solution of 120 milliliter of 0.5 mol, with the ultrastable that obtains in the mixed solution dipping 90 gram steps 1 that obtain, drying obtains P-contained zeolite D provided by the invention.Table 1 has provided the phosphorus among the P-contained zeolite D and has flooded the content of silicon.
Table 1
| Example number | The zeolite numbering | Phosphorus content, heavy % is (with P 2O 5Meter) | The dipping silicone content, heavy % is (with SiO 2Meter) |
| ????1 | ????A | ????4.2 | ????9.2 |
| ????2 | ????B | ????2.2 | ????9.4 |
| Contrast 1 | ????B1 | ????2.4 | ????- |
| ????3 | ????C | ????6.1 | ????10.6 |
| ????4 | ????D | ????4.4 | ????7.0 |
Example 5-8
Below example explanation, through the character of the P-contained zeolite provided by the invention of hydrothermal treatment consists.
The P-contained zeolite that example 1-4 is prepared the different time of roasting in steam atmosphere, with x-ray diffraction method mensuration their relative crystallinity and lattice constant, is measured their specific surface, pore volume with cryogenic nitrogen absorption BET method under different temperature respectively.The results are shown in Table 2.
Comparative Examples 2
The explanation of this Comparative Examples is through the character of the reference P-contained zeolite of hydrothermal treatment consists.
Method by example 6 is carried out hydrothermal treatment consists to zeolite, be used zeolite be the reference P-contained zeolite B1 of Comparative Examples 1 preparation, the results are shown in Table 2.
The measurement result of P-contained zeolite in table 2 example and the Comparative Examples
| Example number | ????5 | ????6 | Comparative Examples 2 | ????7 | ????8 |
| The zeolite numbering | ????A | ????B | ????B1 | ????C | ????D |
| The hydrothermal treatment consists temperature, ℃ | ????600 | ????650 | ????650 | ????700 | ????750 |
| The hydrothermal treatment consists time, minute | ????20 | ????60 | ????60 | ????90 | ????120 |
| Steam atmosphere | ????100％ | ????100％ | ????100％ | ????50％* | ????100％ |
| Relative crystallinity, % | ????80 | ????75 | ????60 | ????73 | ????70 |
| Lattice constant, dust | ????24.59 | ????24.52 | ????24.50 | ????24.50 | ????24.42 |
| Specific surface, rice 2/ gram | ????628 | ????602 | ????558 | ????588 | ????582 |
| Total pore volume, milliliter/gram | ????0.369 | ????0.362 | ????0.349 | ????0.344 | ????0.340 |
| The second hole volume, milliliter/gram | ????0.088 | ????0.100 | ????0.095 | ????0.107 | ????0.137 |
| Second hole accounts for total pore volume percentage | ????23.8 | ????27.6 | ????27.2 | ????31.1 | ????40.3 |
* the steam and the Air mixing gas that contain 50 body % steam
From the result of table 2 as can be seen, after high-temperature water heat treatment, compare with existing P-contained zeolite, the relative crystallinity of zeolite provided by the invention is greatly enhanced, in sintering temperature 600-750 ℃ scope, its relative crystallinity all is not less than 75%, and other physico-chemical property does not then have difference substantially.For example, with P-contained zeolite B provided by the invention roasting after 60 minutes in 650 ℃ of 100% steam, relative crystallinity is 75%, and the reference P-contained zeolite B1 of employing prior art for preparing, after handling under similarity condition, its relative crystallinity has only 60% respectively, and zeolite relative crystallinity provided by the invention has improved 25% than reference zeolite, this means that compared with prior art the present invention has lost 25% zeolite less.
Example 9
This example illustrates the catalytic performance of P-contained zeolite provided by the invention.
70 gram boehmites (are contained Al
2O
334.8 heavy %, Shandong Aluminum Plant produces) and 70 gram deionized waters mixing making beating, adding 20 gram concentration again is the hydrochloric acid of 37 heavy %, stirs, and is warming up to 70 ℃, aging 1.5 hours, and the boehmite slurries that obtain wearing out.
The P-contained zeolite B of 50 gram (dry basis) examples, 2 preparations is carried out hydrothermal treatment consists by the condition of example 6, (contain Al with 30 gram aluminium colloidal sols then
2O
321 heavy %, the Shandong catalyst plant is produced), 60 grams (solid content 85 heavy %) kaolin (Suzhou kaolin company product) and above-mentioned aging boehmite mix.500 ℃ of roastings weighed % and NH with 20 times of weight in the HCl 0.84 that contains of butt sample respectively after 2 hours
3.H
2The solution of O 0.62 heavy %, concentration are that ammonia spirit and the deionized water of 0.17 heavy % mixes making beating, washing, filters, and obtain containing the catalyst of P-contained zeolite provided by the invention after the drying, are designated as ZC.Through 800 ℃ in 100% steam, after aging 4 hours, be raw material with the pipe oil transportation shown in the table 3, the catalytic performance of evaluate catalysts ZC on small fixed flowing bed-tion reacting device, with gas chromatographic analysis product composition, reaction condition and reaction result are listed in the table 4.
Wherein, conversion ratio=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield
Yield of light oil=yield of gasoline+diesel yield.
Comparative Examples 4
The catalytic performance of this Comparative Examples explanation reference P-contained zeolite.
Method by example 9 prepares catalyst, and the different reference P-contained zeolite B1 that just prepare with Comparative Examples 2 replace P-contained zeolite B provided by the invention, obtain reference catalyst DC1.
The method of pressing example 9 is estimated the catalytic performance of reference catalyst DC1, and appreciation condition is with the results are shown in Table 4.
Table 3
| Density (20 ℃), g/cm 3 | ????0.9044 |
| Kinematic viscosity, mm 2/s 50℃ 100℃ | ????57.69 ????9.96 |
| Freezing point, ℃ | ????40.0 |
| Carbon residue, heavy % | ????2.97 |
| Molecular weight (actual measurement) | ????390 |
| C 7Insoluble matter | ????0.37 |
| C, heavy % | ????85.98 |
| H, heavy % | ????12.86 |
| S, heavy % | ????0.55 |
| Alkali nitrogen, ppm | ????1000 |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% 70% 90% | ????243 ????294 ????316 ????395 ????429 ????473 ????530 |
Table 4
| Example number | ????9 | Comparative Examples 4 |
| Catalyst | ????ZC | ????DC1 |
| Reaction temperature, ℃ | ????500 | ????500 |
| Oil ratio | ????6 | ????6 |
| Air speed, hour -1 | ????16 | ????16 |
| Conversion ratio, heavy % | ????74.0 | ????71.8 |
| Yield of light oil, heavy % | ????77.9 | ????72.1 |
| Product is formed, heavy % H 2-C 2Liquefied gas gasoline, diesel heavy oil coke | ????1.3 ????11.5 ????57.0 ????20.9 ????5.1 ????4.2 | ????1.8 ????13.2 ????51.4 ????20.7 ????7.5 ????5.4 |
Result from table 4 as can be seen, when adopting P-contained zeolite provided by the invention as the catalyst of active component preparation, conversion ratio is up to 74.0 heavy %, yield of light oil is up to 77.9 heavy %, the C5+ yield of gasoline is up to 57.0 heavy %, coking yield is 4.2 heavy %, and under identical condition, when adopting the catalyst of the existing P-contained zeolite of same amount, conversion ratio, yield of light oil, yield of gasoline have only 71.8 heavy % respectively, 72.1 heavy %, 51.4 heavy %, coking yield adopts the catalyst that contains P-contained zeolite provided by the invention to compare conversion ratio with the catalyst that employing contains existing P-contained zeolite then up to 5.4 heavy %, yield of light oil, yield of gasoline has improved 3.06% respectively, 8.04% and 10.89%, coking yield has then reduced by 22.22%.This explanation, compare with reference catalyst, the catalyst that contains zeolite provided by the invention has higher activity, higher yield of light oil, higher gasoline selective and lower coke selectivity, this explanation the present invention has not only improved the degree of crystallinity of P-contained zeolite, reduced the loss of zeolite, the prepared P-contained zeolite that goes out also has than the better catalytic performance of prior art.
Claims (18)
1. a P-contained Y-zeolite contains a kind of phosphorus component, it is characterized in that, this zeolite also contains a kind of silicon components, and described silicon components is with in the method load of silicon compound solution dipping zeolite, with SiO
2Meter, the content of described silicon components are the heavy % of 1-15, with P
2O
5Meter, the content of described phosphorus component are the heavy % of 0.1-15.
2. zeolite according to claim 1, the content that it is characterized in that described silicon components are the heavy % of 5-12, and the content of phosphorus component is the heavy % of 2-10.
3. zeolite according to claim 1 is characterized in that, described silicon compound solution is selected from one or more in Ludox, waterglass, the fluosilicate aqueous solution, the organo-silicon compound solution.
4. zeolite according to claim 3 is characterized in that, described silicon compound solution is selected from one or more in Ludox, waterglass, the fluosilicate aqueous solution, dimethicone, the polymethylphenyl siloxane fluid.
5. zeolite according to claim 4 is characterized in that, described silicon compound solution is selected from one or more in Ludox, waterglass and the ammonium fluosilicate aqueous solution.
6. zeolite according to claim 1 is characterized in that, after 550～850 ℃ of hydrothermal treatment consists, the relative crystallinity of described P-contained zeolite is not less than 70%.
7. zeolite according to claim 1 is characterized in that, after 550～850 ℃ of hydrothermal treatment consists, the pore volume of described P-contained zeolite second hole accounts for the 15-75% of total pore volume.
8. zeolite according to claim 1 is characterized in that, the pore volume of described second hole accounts for the 20-60% of total pore volume.
9. the preparation method of the described P-contained zeolite of claim 1, this method comprises that drying is characterized in that with a kind of raw material y-type zeolite of a kind of solution impregnation of phosphorus-containing compound, this method also comprises with silicon compound solution floods described y-type zeolite, with SiO
2Meter, the consumption of described silicon compound solution make and contain the heavy % of silicon components 1-15 in the P-contained zeolite that obtains, with P
2O
5Meter, the consumption of described phosphorus compound solution make and contain the heavy % of phosphorus component 0.1-15 in the P-contained zeolite that obtains.
10. method according to claim 9 is characterized in that, described with silicon compound solution dipping y-type zeolite with carry out simultaneously with phosphorus compound solution impregnation y-type zeolite.
11. the method according to claim 9 or 10 is characterized in that, described silicon compound solution is selected from one or more in Ludox, waterglass and the ammonium fluosilicate aqueous solution.
12. the method according to claim 9 or 10 is characterized in that, described phosphorus compound is selected from a kind of or a kind of in phosphoric acid, phosphorous acid, phosphoric anhydride, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate, ammonium phosphite, dihydrogen phosphite ammonium, the aluminum phosphate.
13. method according to claim 9 is characterized in that, described raw material y-type zeolite is selected from NaY, NH
4In Y, HY, the overstable gamma zeolite one or more.
14. method according to claim 13 is characterized in that, described raw material y-type zeolite is selected from Na
2O content is NaY, the NH of 3～10 heavy %
4In Y, HY, the overstable gamma zeolite one or more.
15. method according to claim 9, it is characterized in that, after with silicon compound solution and phosphorus compound solution impregnation y-type zeolite, also has a hydrothermal treatment step, this hydrothermal treatment step is included under 500～850 ℃ the temperature, with the roasting in steam atmosphere of described y-type zeolite, roasting time at least 10 minutes.
16. method according to claim 9 is characterized in that described sintering temperature is 600-750 ℃, roasting time 15 minutes to 5 hours.
17. method according to claim 15 is characterized in that described steam atmosphere is meant 100% steam or the steam of water vapour content at least 10 body % and the gaseous mixture of inert gas.
18. method according to claim 17 is characterized in that described steam atmosphere is meant steam and the Air mixing gas of 100% steam or containing water vapor content at least 10 body %.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172536A (en) * | 2011-03-16 | 2011-09-07 | 天津工业大学 | Method for preparing loaded phosphide catalyst by taking red phosphorus as phosphorus source |
| WO2013177727A1 (en) | 2012-06-01 | 2013-12-05 | 中国石油天然气股份有限公司 | Phosphorus-containing ultrastable y-type rare earth molecular sieve and preparation method therefor |
-
2000
- 2000-07-05 CN CN 00109746 patent/CN1121902C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172536A (en) * | 2011-03-16 | 2011-09-07 | 天津工业大学 | Method for preparing loaded phosphide catalyst by taking red phosphorus as phosphorus source |
| WO2013177727A1 (en) | 2012-06-01 | 2013-12-05 | 中国石油天然气股份有限公司 | Phosphorus-containing ultrastable y-type rare earth molecular sieve and preparation method therefor |
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| Publication number | Publication date |
|---|---|
| CN1121902C (en) | 2003-09-24 |
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