CN1330981A - 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 P-contained Y-type zeolite is disclosed, which contains also Si component (1-15 wt.%) which is carried by immersing zeolite in the solution of Si compound and rare-earth component (0.2-15 wt.%). Its advantages are high crystallity 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 rare earth component, 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, with RE
2O
3Meter, described rare earth components contents are the heavy % of 0.2-15.
The preparation method of P-contained Y-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 makes and contains the heavy % of phosphorus component 0.1-10 in the P-contained zeolite that obtains, and described y-type zeolite is the y-type zeolite that contains rare earth, is benchmark with the gross weight of P-contained Y-zeolite, in the oxide of rare earth, the content of described rare earth is the heavy % of 0.2-15.
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 5-15, and the content of described phosphorus component is the heavy % of 0.1-15, is preferably the heavy % of 2-10, and described rare earth components contents is the heavy % of 0.2-15, the heavy % of preferred 1-10.
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 Y-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 Y-zeolite second hole accounts for 15～75% of total pore volume.Described second hole refers to that the bore dia except that molecular sieve intracrystalline micropore is the hole of 20～1000 .Total pore volume adopts low-temperature nitrogen adsorption method to measure, referring to " petrochemical industry analytical method (RIPP test method) ", (volume such as Yang Cuiding, Science Press, 424-426, nineteen ninety publishes).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.
Described rare earth is selected from one or more in the lanthanide series rare-earth elements, as being selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more.Wherein, the mishmetal of preferred lanthanum, cerium or rich lanthanum or rich cerium.Owing to being purchased easily, the mixed rare earth compound of rich lanthanum or rich cerium gets, therefore, and the mishmetal of more preferably rich lanthanum of described rare earth or rich cerium.
Preparation method according to phosphorous rare earth Y type zeolite provided by the invention, though the described y-type zeolite that contains rare earth can be rare earth Y type zeolite REY, among rare earth hydrogen Y zeolite REHY and the hyperastable Y-type RE zeolite REUSY one or more, but, the employing sodium oxide content is that the y-type zeolite that contains rare earth of the heavy % of 3-10 more helps reaching purpose of the present invention, and its reason is discussed hereinafter.Therefore, when the not enough 3-10 of the sodium oxide content in the described y-type zeolite that contains rare earth is heavy, preferably carry out ion-exchange with a kind of sodium salt solution and make the sodium oxide molybdena that contains the heavy % of 3-10 in the y-type zeolite that contains rare earth, the sodium ion switching technology is conventional technology, does not do detailed description at this.With the step of 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 rare earth Y type zeolite that contains phosphorus compound and silicon compound simultaneously.
The described y-type zeolite that contains rare earth can be commercially available, and also can use NaY zeolite, NH
4Y zeolite, HY zeolite, overstable gamma zeolite and the solution that contains rare earth ion carry out ion-exchange, or obtain with the above-mentioned y-type zeolite of the solution impregnation that contains rare earth ion.The described content that contains the y-type zeolite middle rare earth of rare earth should make and contain the heavy % of 0.2-15 in the P-contained zeolite provided by the invention that finally obtains, the rare earth oxide of the heavy % of preferred 1-10.The technology of carrying out ion-exchange with rare earth ion also is that conventional technology is not done detailed description at this.
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.
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 rare earth Y type zeolite of phosphorus and silicon compound, this step comprises, at 550-850 ℃, be preferably under 600-750 ℃ the temperature, described rare earth 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.Here, described inert gas refers in the hydrothermal treatment consists process zeolite not had the gas of destruction, as the gas of group 0 element in air, nitrogen, oxygen, carbon dioxide, the periodic table of elements etc.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 phosphorous rare earth Y type 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 rare earth 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, make skeleton structure of zeolite complete, have the degree of crystallinity higher, overcome the lower shortcoming of prior art P-contained zeolite degree of crystallinity than prior art.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, for example, with phosphorous rare earth Y type zeolite provided by the invention as the catalyst of active component preparation 500 ℃ of reaction temperatures, oil ratio is 6, air speed is 16 hours
-1Condition under carry out the evaluation of small fixed flowing bed, compare with the catalyst that contains the existing phosphorous rare earth Y type zeolite of same amount, conversion ratio, yield of light oil and yield of gasoline obviously improve, coking yield reduces.
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
4)
2SO
4The 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, and 120 ℃ of oven dry obtain NH
4NaY type zeolite.
With 90 the gram (dry basis) above-mentioned preparations NH
4NaY type zeolite is at 2 liters of RECl that contain rare earth oxide 0.8 heavy %
X(Baotou rare earth factory in the Inner Mongol produces, based on lanthanum, in oxide RE
2O
3Content 46 heavy %, wherein, the percentage that each oxide accounts for total oxide weight is La
2O
353.2%, CeO
213.0%, Pr
6O
1113.0%, Nd
2O
320.8%) in the solution, carry out ion-exchange 0.5 hour under 90 ℃, filter, spend the deionised water filter cake to there not being acid group, 120 ℃ of oven dry obtain containing the NH of rare earth
4NaY type zeolite records its Na
2O content is 4.2 heavy %.
3. 80 gram (dry basis) above-mentioned preparations are contained rare earth NH
4(Changhong chemical plant, Beijing commercial product contains 12%SiO for NaY type zeolite and 100 gram Ludox
2) and 28 grams contain P
2O
5Solution behind the ammonium dibasic phosphate solution mixing of 15 heavy % mixes, and 120 ℃ of oven dry obtain P-contained Y-zeolite A provided by the invention.The phosphorus of P-contained Y-zeolite A, silicone content and content of rare earth are as shown in table 1, and dipping silicon wherein and phosphorus content are by calculating, and content of rare earth adopts x-ray fluorescence spectrometry.
Example 2
Phosphorous and rare earth prepare 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 10 heavy % with 2 liters of concentration
4)
2SO
4The 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, and 120 ℃ of oven dry obtain NH
4NaY type zeolite.
With 95 the gram (dry basis) above-mentioned preparations NH
4NaY type zeolite is at 2 liters of RECl that contain rare earth oxide 0.4 heavy %
XIn (with example 1) solution, carry out ion-exchange 0.5 hour under 90 ℃, filter, spend the deionised water filter cake to there not being acid group, 120 ℃ of oven dry obtain containing the NH of rare earth
4NaY type zeolite records its Na
2O content is 3.6 heavy %.
With 90 the gram (dry basis) above-mentioned preparations the NH that contains rare earth
4(Shandong catalyst plant product contains SiO for NaY type zeolite and 90 gram waterglass
215%, modulus 3.3) and 38 grams contain P
2O
59.5 the solution behind the ammonium dibasic phosphate solution mixing of heavy % mixes, 120 ℃ of oven dry obtain the zeolite B of phosphorous and rare earth provided by the invention.The phosphorus of P-contained zeolite B, silicone content and content of rare earth are as shown in table 1, and dipping silicon wherein and phosphorus content are by calculating, and content of rare earth adopts x-ray fluorescence spectrometry.
Comparative Examples 1
The preparation of reference P-contained zeolite.
1. prepare Na by 1 and 2 method in the example 2
2O content is the NH that contains rare earth of 3.6 heavy %
4The NaY zeolite.
2. 6.0 gram diammonium hydrogen phosphates are dissolved in the 120 gram deionized waters, the NH of rare earth is arranged with the exchange of ammonium dibasic phosphate solution dipping 90 gram (dry basis) the above-mentioned preparations that obtain
4NaY type zeolite is after 1 hour, and 120 ℃ of oven dry obtain reference P-contained zeolite B1.Phosphorus content and content of rare earth among the reference zeolite B1 are listed in the table 1.
Example 3
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 3.0 heavy % with 2 liters of concentration
4)
2SO
4The 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.
With 90 the gram (dry basis) above-mentioned preparations NH
4NaY type zeolite is at 2 liters of RECl that contain 1.2 heavy % rare earth oxides
XIn (with example 1) solution, under 90 ℃, carry out ion-exchange 0.5 hour, filter, spend the deionised water filter cake, obtain containing the NH of rare earth after the drying to there not being acid group
4NaY type zeolite records its Na
2O content is 4.3 heavy %.
3. 9.0 gram diammonium hydrogen phosphates are dissolved in the 25 gram water, the ammonium fluosilicate (chemical pure of the ammonium dibasic phosphate solution that obtains and 120 milliliter of 1.0 mol, concentration is greater than 99%, Beijing Chemical Plant's product) solution mixes, with the NH that contains rare earth of mixed solution dipping 80 gram (dry basis) the above-mentioned preparations that obtain
4NaY type zeolite, 120 ℃ of oven dry obtain P-contained zeolite C provided by the invention.Phosphorus among the P-contained zeolite C, rare earth and dipping silicone content are listed in the table 1.
Example 4
The prepare zeolite of phosphorous and rare earth provided by the invention.
1, be extremely steady y-type zeolite of rare earth (REUSY, the Na of 2.448 nanometers with 100 gram (dry basis) lattice constants
2O content is 1.2 heavy %, RE
2O
3Content is 1.5 heavy %, wherein, and La
2O
3Content is 0.8 heavy %, CeO
2Content is 0.2 heavy %, and other rare-earth oxide content are 0.5 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, and 120 ℃ of oven dry obtain containing Na
2The REUSY zeolite of the heavy % of O4.9.
2, with 90 gram (dry basis) above-mentioned Na that contain
2(Changhong chemical plant, Beijing commercial product contains 12%SiO for the REUSY zeolite of O 4.9 heavy % and 100 gram Ludox
2) and 28 grams contain P
2O
5The ammonium dibasic phosphate solution mixed solution of 15 heavy % mixes, and 120 ℃ of oven dry obtain P-contained zeolite D provided by the invention.Table 1 has provided the content of phosphorus, rare earth and dipping silicon among the P-contained zeolite D.
Example 5
The preparation of P-contained zeolite provided by the invention.
With 90 gram (dry basis) lattice constants is the REHY zeolite (Na of 2.465 nanometers
2O content 4.5 heavy %, RE
2O
3Content 3.4 heavy %, wherein, La
2O
3Content is 1.8 heavy %, CeO
2Content is 0.4 heavy %, and other rare-earth oxide content are 1.2 heavy %, and the Shandong catalyst plant is produced) (Changhong chemical plant, Beijing commercial product contains 12%SiO with 80 gram Ludox
2) and 38 grams contain P
2O
56.0 the solution that the ammonium dibasic phosphate solution of heavy % obtains after mixing mixes, 120 ℃ of oven dry obtain P-contained zeolite E provided by the invention.The phosphorus of P-contained zeolite E, silicon and content of rare earth are listed in the table 1.
Comparative Examples 2
Phosphorous and the rare earth prepare zeolite of reference.
Restrain REHY zeolite (with example 5) and 100 grams that (dry basis) lattice constants are 2.465 nanometers with 90 and contain P
2O
52.0 the ammonium dibasic phosphate solution of heavy % mixes, 120 ℃ of oven dry obtain reference P-contained zeolite E1.Phosphorus and content of rare earth among the reference P-contained zeolite E1 are listed in the table 1.
Table 1
| Example number | The zeolite numbering | Phosphorus content, heavy % is (with P 2O 5Meter) | Content of rare earth, heavy % is (with RE 2O 3Meter) | The dipping silicone content, heavy % is (with SiO 2Meter) |
| ????1 | ????A | ????4.4 | ????6.0 | ????12.4 |
| ????2 | ????B | ????3.4 | ????3.1 | ????12.6 |
| Contrast 1 | ????B1 | ????3.4 | ????3.3 | ????- |
| ????3 | ????C | ????5.3 | ????9.6 | ????7.8 |
| ????4 | ????D | ????4.0 | ????1.2 | ????11.3 |
| ????5 | ????E | ????2.2 | ????2.8 | ????9.4 |
| Contrast 2 | ????E1 | ????2.2 | ????3.0 | ????- |
Example 6-10
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 1-5 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 3
This Comparative Examples illustrates after hydrothermal treatment step, the character of reference P-contained zeolite.
Method by example 7 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.
Comparative Examples 4
This Comparative Examples illustrates after hydrothermal treatment step, the character of reference P-contained zeolite.Method by example 10 is carried out hydrothermal treatment consists to zeolite, be used zeolite be the reference P-contained zeolite E1 of Comparative Examples 2 preparation, the results are shown in Table 2.
Table 2
| Example number | 6 | ?7 | Comparative Examples 3 | ??8 | ???9 | ??10 | Comparative Examples 4 |
| The zeolite numbering | A | ?B | ??B1 | ??C | ??D | ??E | ??E1 |
| The hydrothermal treatment consists temperature, ℃ | 600 | ?650 | ??650 | ??700 | ??750 | ??700 | ??700 |
| The hydrothermal treatment consists time, minute | 30 | ?60 | ??60 | ??90 | ??120 | ??120 | ??120 |
| Steam atmosphere | 100% steam | 100% steam | 100% steam | 50% steam | 100% steam | 100% steam | 100% steam |
| Relative crystallinity, % | 75 | ?72 | ??58 | ??72 | ??70 | ??73 | ??60 |
| Lattice constant, dust | 24.62 | ?24.58 | ??24.58 | ??24.56 | ??24.48 | ??24.52 | ??24.52 |
| Specific surface, rice 2/ gram | 625 | ?598 | ??559 | ??582 | ??576 | ??592 | ??555 |
| Total pore volume, milliliter/gram | 0.358 | ?0.352 | ??0.360 | ??0.348 | ??0.342 | ??0.353 | ??0.350 |
| The second hole volume, milliliter/gram | 0.093 | ?0.109 | ??0.113 | ??0.116 | ??0.135 | ??0.128 | ??0.125 |
| Second hole accounts for total pore volume percentage | 26.0 | ?31.0 | ??31.4 | ??33.3 | ??39.5 | ??36.3 | ??35.7 |
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 the scope of 600-750 ℃ of hydrothermal treatment consists temperature, its relative crystallinity all is not less than 70%, 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 72%, and the identical reference P-contained zeolite B1 of phosphorus content of employing prior art for preparing, after under similarity condition, handling, its relative crystallinity has only 58%, and zeolite relative crystallinity provided by the invention has improved 24.1% than reference zeolite.Again for example, with P-contained zeolite E provided by the invention roasting after 120 minutes in 700 ℃ of 100% steam, relative crystallinity is 73%, and the identical reference P-contained zeolite E1 of phosphorus content of employing prior art for preparing, after handling under similarity condition, its relative crystallinity has only 60%, and zeolite relative crystallinity provided by the invention has improved 21.7% than reference zeolite, this means that compared with prior art the present invention has lost 24.1% and 21.7% zeolite respectively less.
Example 11
This example illustrates the catalytic performance of P-contained Y-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 Y-zeolite B of 50 gram (dry basis) examples, 2 preparations is carried out hydrothermal treatment consists with the method for example 7, (contain Al with 30 gram aluminium colloidal sols then
2O
321 heavy %, the Shandong catalyst plant is produced), 60 gram kaolin (solid content 85 heavy %, kaolin company in Suzhou produces) 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, reaction condition and reaction result are listed in the table 4.
Comparative Examples 5
The catalytic performance of the phosphorous rare earth zeolite of this Comparative Examples explanation reference.
Method by example 11 prepares catalyst, and the different reference P-contained zeolite B1 that just prepare with Comparative Examples 3 replace P-contained zeolite B provided by the invention, obtain reference catalyst DC.
The method of pressing example 11 is estimated the catalytic performance of reference catalyst DC, and appreciation condition is with the results are shown in Table 4.
Table 3 feedstock oil character
| Density (20 ℃), g/cm 3 | ????0.9044 |
| Kinematic viscosity, mm 2/s 50℃ 100℃ | ????57.69 ????9.96 |
| Freezing point, ℃ | ????40.0 |
| Carbon residue, m% | ????2.97 |
| Molecular weight (actual measurement) | ????390 |
| C 7Insoluble matter | ????0.37 |
| C，m％ | ????85.98 |
| H，m％ | ????12.86 |
| S，m％ | ????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 evaluating catalyst condition and result
| Example number | ????11 | Comparative Examples 5 |
| Catalyst | ????ZC | ????DC |
| Reaction temperature, ℃ | ????500 | ????500 |
| Oil ratio | ????6 | ????6 |
| Air speed, hour -1 | ????16 | ????16 |
| Conversion ratio, heavy % | ????73.6 | ????71.0 |
| Yield of light oil, heavy % | ????77.4 | ????72.2 |
| Product is formed, heavy % H 2-C 2Liquefied gas gasoline, diesel heavy oil coke | ????1.4 ????11.9 ????55.8 ????21.6 ????4.8 ????4.5 | ????1.8 ????12.2 ????51.2 ????21.0 ????8.0 ????5.8 |
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 73.6 heavy %, yield of light oil is up to 77.4 heavy %, yield of gasoline is up to 55.8 heavy %, coking yield is 4.5 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 71.0 heavy % respectively, 72.2 heavy %, 51.2 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 5.8 heavy %, yield of light oil, yield of gasoline has improved 3.66% respectively, 7.20% and 8.98%, coking yield has then reduced by 22.41%.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.
In the table 4, conversion ratio=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield; Yield of light oil=yield of gasoline+diesel yield.
Claims (20)
1. a P-contained Y-zeolite contains phosphorus, it is characterized in that, this zeolite also contains a kind of silicon components and rare earth component, 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, and in rare earth oxide, described rare earth components contents is the heavy % of 0.2-15.
2. zeolite according to claim 1 is characterized in that, the content of described silicon components is the heavy % of 5-15, and the content of described phosphorus component is the heavy % of 2-10, and described rare earth components contents is the heavy % of 1-10.
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. zeolite according to claim 1 and 2 is characterized in that, described rare earth is selected from the mishmetal of lanthanum, cerium or rich lanthanum or rich cerium.
10. zeolite according to claim 9 is characterized in that described rare earth is selected from the mishmetal of rich lanthanum or rich cerium.
11. the preparation method of the described P-contained Y-zeolite of claim 1 comprises that drying is characterized in that with a kind of raw material y-type zeolite of a kind of solution impregnation of phosphorus compound, this method also comprises the solution impregnation y-type zeolite with silicon compound, with SiO
2Meter, the consumption of described silicon compound solution make the P-contained zeolite that obtains contain the heavy % of silicon components 1-15, with P
2O
5Meter, the consumption of described phosphorus-containing compound solution makes and contains the heavy % of phosphorus component 0.1-10 in the P-contained zeolite that obtains, and described y-type zeolite is the y-type zeolite that contains rare earth, is benchmark with the gross weight of P-contained Y-zeolite, in the oxide of rare earth, the content of described rare earth is the heavy % of 0.2-15.
12. method according to claim 11 is characterized in that, the described y-type zeolite that contains rare earth is selected from rare earth Y type zeolite REY, one or more among rare earth hydrogen Y zeolite REHY and the hyperastable Y-type RE zeolite REUSY.
13. method according to claim 12 is characterized in that, the described y-type zeolite that contains rare earth is selected from the rare earth Y type zeolite REY of the sodium oxide molybdena that contains the heavy % of 3-10, one or more among rare earth hydrogen Y zeolite REHY and the hyperastable Y-type RE zeolite REUSY.
14. method according to claim 11 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.
15., it is characterized in that described silicon compound solution is selected from one or more in Ludox, waterglass and the ammonium fluosilicate aqueous solution according to claim 11 or 14 described methods.
16., it 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 according to claim 11 or 14 described methods.
17. method according to claim 11, 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.
18. method according to claim 17 is characterized in that described sintering temperature is 600-750 ℃, roasting time 15 minutes to 5 hours.
19. method according to claim 17 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.
20. method according to claim 17 is characterized in that described steam atmosphere is meant steam and the Air mixing gas of 100% steam or water vapour content at least 10 body %.
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|---|---|---|---|
| CNB001097458A CN1142023C (en) | 2000-07-05 | 2000-07-05 | P-contained Y-zeolite and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001097458A CN1142023C (en) | 2000-07-05 | 2000-07-05 | P-contained Y-zeolite and its preparing process |
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| CN1330981A true CN1330981A (en) | 2002-01-16 |
| CN1142023C CN1142023C (en) | 2004-03-17 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332758C (en) * | 2004-02-27 | 2007-08-22 | 中国石油化工股份有限公司 | REY molecular sieve containing phosphor and amorphous silica, preparation method and application |
| 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 |
| 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 |
| US10888848B2 (en) | 2017-02-22 | 2021-01-12 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst and preparation thereof |
| US11052381B2 (en) | 2017-02-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
-
2000
- 2000-07-05 CN CNB001097458A patent/CN1142023C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332758C (en) * | 2004-02-27 | 2007-08-22 | 中国石油化工股份有限公司 | REY molecular sieve containing phosphor and amorphous silica, preparation method and application |
| 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 |
| US9968915B2 (en) | 2012-06-01 | 2018-05-15 | Petrochina Company Limited | Phosphorus-containing ultrastable Y-type rare earth molecular sieve 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 |
| US11052381B2 (en) | 2017-02-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
| US10888848B2 (en) | 2017-02-22 | 2021-01-12 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst and preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1142023C (en) | 2004-03-17 |
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