CN1233790C - Nitrogenous zeolite cracking catalyst and preparing method thereof - Google Patents
Nitrogenous zeolite cracking catalyst and preparing method thereof Download PDFInfo
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- CN1233790C CN1233790C CN 02158177 CN02158177A CN1233790C CN 1233790 C CN1233790 C CN 1233790C CN 02158177 CN02158177 CN 02158177 CN 02158177 A CN02158177 A CN 02158177A CN 1233790 C CN1233790 C CN 1233790C
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Abstract
The present invention relates to a nitrogenous zeolite cracking catalyst containing nitrogenous zeolite and a substrate material, wherein the nitrogenous zeolite is crystal silicon aluminate containing 0.01 to 5 wt% of nitrogen measured by an element. The preparation method of the nitrogenous zeolite cracking catalyst comprises: the nitrogenous zeolite and the substrate material are mixed, pulped and dried in a spray mode, and an obtained product is washed and dried, wherein the nitrogenous zeolite is prepared by directly mixing ammonium nitrate and zeolite according to the weight ratio of 0.1 to 30:1 and by heating the mixture at the temperature of 50 to 600DEG C for 0.1 to 15 hours. The catalyst has the advantages of high activity, high light oil yield and preferable water thermal stability.
Description
Technical field
The invention relates to a kind of cracking catalyst that contains zeolite and preparation method thereof, more particularly, is about a kind of nitrogenous zeolitic cracking catalyst and preparation method thereof.
Background technology
Because world economy ground development is increasing to the demand of lightweight oil, more and more higher requirement has been proposed the catalytic cracking catalyst of processing normal slag or subtracting mink cell focus such as slag.The activity of cracking catalyst comes from zeolite and matrix, so the research of current cracking catalyst, having is some performance that changes cracking catalyst by the modification to zeolite or matrix greatly, to satisfy the requirement of processing heavy oil.
USP5545784 has disclosed a kind of method of zeolite being carried out modification by the solid ionic exchange process.This method is that the zeolite behind the calcination activation is mixed with the metallic compound of capacity, and in the presence of rare gas element heating this solid mixture to 400～600 ℃, then it is cooled to room temperature, again under hydrogen atmosphere in 280～350 ℃ of reduction 10～14 hours.This method can make metallic element be distributed in zeolite inside equably, and the zeolite after the modification is applicable to hydrogenation of olefins.
Nitrogen compound, particularly organic basic nitrogen compound can directly occupy the activity of such catalysts center with electronics and chemical action, and making it can not the absorption reaction species, thereby makes catalyst activity reduction.This is a general knowledge well known to those of ordinary skill in the art.Therefore, adopt nitrogen compound that the report that zeolite carries out modification is not seen so far as yet.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of nitrogenous zeolitic cracking catalyst, this Preparation of catalysts method is provided simultaneously.
Nitrogenous zeolitic cracking catalyst provided by the invention contains nitrogenous zeolite and substrate material, and described nitrogenous zeolite is the crystal aluminosilicate that contains in the heavy % nitrogen of element 0.01-5, and described nitrogen is with its maxivalence attitude N
+ 5Form exist.
The preparation method of nitrogenous zeolitic cracking catalyst provided by the invention is as follows: nitrogenous zeolite is mixed making beating with substrate material, and spraying drying, the product that washing obtains is also dry; Wherein, described nitrogenous prepare zeolite be with ammonium nitrate and zeolite by 0.1-30: 1 weight ratio is directly mixed, and in 50-600 ℃ of heating 0.1-15 hour down, reclaims the gained zeolite.
Compared with prior art, catalyzer provided by the invention has higher activity, comparatively ideal yield of light oil and hydrothermal stability preferably.For example, the catalyzer that the HY type zeolite 30 heavy % by nitrogenous 0.20 heavy % provided by the invention, silicon oxide 30 heavy %, kaolin 40 heavy % are formed is through 800 ℃, 100% water vapour after aging 4 hours, 482 ℃ of temperature of reaction, and weight hourly space velocity 16 hours
-1, under the condition of agent-oil ratio 4, be that 227-475 ℃ decompressed wax oil is a raw material with the boiling range, carry out the catalytic cracking small-scale test, its transformation efficiency is 69 heavy %, and gasoline yield is 50.6 heavy %, and diesel yield is 26.1 heavy %.And contain the conventional H Y zeolite and form identical catalyzer after same burin-in process, under similarity condition, carrying out FCC tests, it is 45.0 heavy % that its transformation efficiency has only 62.8 heavy %, gasoline yield, diesel yield is 23.3 heavy %.
Nitrogenous zeolite of the present invention has higher thermostability.For example, the lattice avalanche temperature of the y-type zeolite of nitrogenous 0.20 heavy % provided by the invention is 1045 ℃, and the lattice avalanche temperature of corresponding unazotized y-type zeolite has only 1033 ℃.
Description of drawings
Fig. 1 is the x-ray photoelectron energy spectrogram of nitrogen element on the nitrogenous HY zeolite provided by the present invention, and spectral line 1 wherein is etching 0 minute, and spectral line 2 is etching 5 minutes, and spectral line 3 is etching 13 minutes.
Fig. 2 is that the x-ray photoelectron of aluminium element on the nitrogenous HY zeolite provided by the present invention can spectrogram.
Among Fig. 1, Fig. 2, X represents bound energy, and ev represents electron-volt.
Embodiment
According to catalyzer provided by the invention, described nitrogenous zeolite is the crystal aluminosilicate that contains in the heavy % nitrogen of element 0.01-5, preferably contains the crystal aluminosilicate in the heavy % nitrogen of element 0.01-3.
According to catalyzer provided by the invention, described crystal aluminosilicate is selected from faujusite, mordenite or has in the zeolite of ZSM-5 structure one or more, one or more in preferred HY zeolite, REY zeolite, REHY zeolite, USY zeolite, REUSY zeolite, the ZSM-5 zeolite.
Utilize the X-ray photoelectron spectroscopic analysis method that the distribution situation of nitrogen element on zeolite on the nitrogenous zeolite investigated, concrete grammar is as follows: choose Ar
+The different time points of etching is made x-ray photoelectron can spectrogram.As shown in Figure 1, N has all appearred in three curves
1sThe bound energy peak, and peak area is roughly the same.The distribution uniform of this explanation nitrogen on zeolite, promptly the nitrogen element is at the outside surface of zeolite and the concentration basically identical in the duct.N
1sBound energy is that 405.7ev (the bound energy peak in the curve 2 has drift slightly) shows that nitrogen is with its maxivalence attitude N
+ 5Form exists.
Utilize the X-ray photoelectron spectroscopic analysis method again the distribution situation of aluminium element on zeolite to be investigated.The result as shown in Figure 2, the Al in the zeolite
2pBound energy is 74.4ev, with the Al of Al-N in the bibliographical information
2pBound energy 74.4ev is consistent, has confirmed to have in the zeolite generation of Al-N key.
The content of described nitrogenous zeolite in catalyzer is zeolite content commonly used in the general cracking catalyst, is generally the heavy % of 10-40.
According to catalyzer provided by the invention, described substrate material is selected from one or more in the cracking catalyst substrate material commonly used, in preferred silicon oxide, aluminum oxide, silica-alumina, silico-aluminate, the clay one or more, one or more in more preferred aluminum oxide, silicon oxide, the clay.Described clay is the clay that cracking catalyst matrix is commonly used, as in kaolin, halloysite, polynite, the wilkinite one or more, and preferred kaolin.The content of described matrix in catalyzer is matrix content commonly used in the general cracking catalyst.
Can also contain rare earth element in the catalyzer provided by the invention, rare earth element may reside in the nitrogenous zeolite, also may reside in the substrate material, can also be present among the said two devices simultaneously.The total content of described rare earth element (in rare earth oxide) can be the heavy % of the 0-20 of total catalyst weight, the heavy % of preferred 0-15.Described rare earth element is selected from: the mixture of one or more in lanthanum, cerium, praseodymium, the neodymium.
Preparation of catalysts method provided by the invention comprises mixes making beating, spraying drying with nitrogenous zeolite with substrate material.Wherein, described nitrogenous prepare zeolite method comprises: with ammonium nitrate and zeolite according to 0.1-30: 1 weight ratio is directly mixed, and under 50-600 ℃, heated 0.1-15 hour, preferably heated 0.5-10 hour down in 80-550 ℃ in confined conditions, reclaim the gained zeolite.
According to Preparation of catalysts method provided by the invention, the described raw material zeolite that is used for preparing nitrogenous zeolite can be one or more of existing aluminosilicate zeolite, it can be zeolite with macropore, as faujusite, Beta zeolite, omega zeolite, it also can be zeolite with mesopore, as zeolites such as mordenite, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, can also be zeolite, as erionite, ZSM-34 zeolite with aperture.The preferred faujusite of described raw material zeolite, mordenite, have in the zeolite of ZSM-5 structure one or more.Most preferred raw material zeolite is: one or more in HY zeolite, REY zeolite, REHY zeolite, USY zeolite, REUSY zeolite, the ZSM-5 zeolite.
The weight ratio of described ammonium nitrate and raw material zeolite is 0.1-30: 1, and preferred 0.1-20: 1, more preferred 0.1-15: 1.
According to Preparation of catalysts method provided by the invention, described substrate material is selected from cracking catalyst substrate material commonly used or in its precursor one or more, in preferred silicon oxide or its precursor, aluminum oxide or its precursor, silica-alumina, silico-aluminate, the clay one or more, one or more in more preferred silicon oxide or its precursor, aluminum oxide or its precursor, the clay.The precursor of described silicon oxide can be various silicon oxide precursor as the catalyst substrates material, as silicon sol, and silicon gel, water glass etc.The precursor of described aluminum oxide can be various aluminum oxide precursor as the catalyst substrates material, as aluminium colloidal sol, various hydrated aluminum oxide (as pseudo-boehmite, gibbsite etc.).Described clay is selected from cracking catalyst matrix clay commonly used, as in kaolin, halloysite, polynite, the wilkinite one or more, and preferred kaolin.
When catalyzer contained rare earth element, Preparation of catalysts method provided by the invention can also comprise the step of introducing rare earth element.The introducing of described rare earth element can be adopted usual method, carries out in the arbitrary steps of Preparation of catalysts process.For example, can adopt the raw material zeolite that contains rare earth to prepare the zeolite of nitrogenous (containing rare earth simultaneously) of the present invention, also can adopt pickling process to flood nitrogenous zeolite with the aqueous solution of compounds containing rare earth.The zeolite of nitrogenous (containing rare earth simultaneously) mixes making beating, spraying drying with substrate materials such as aluminum oxide and/or clay or its precursor after drying.Again for example, the available aqueous solution that contains rare earth compound mixes making beating with substrate materials such as all or part of aluminum oxide, silicon oxide and/or clay or its precursor, dry then, again it is mixed making beating, spraying drying with nitrogenous zeolite (and another part substrate material or its precursor).
Above-mentioned roasting, washing, drying process all adopt conventional method and condition.
The following examples will give further instruction to nitrogenous zeolitic cracking catalyst provided by the present invention and preparation method thereof, but therefore the present invention is not subjected to any restriction.
Used zeolite is Sinopec Qilu Petrochemical company catalyst plant Industrial products among the embodiment.Nitrogen in the zeolite (in element) content is by chemiluminescence determination; Rare earth and sodium are (with Na
2The O meter) content adopts x-ray fluorescence spectrometry.
Embodiment 1
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
(1) takes by weighing the 200 NaY zeolite (Na that restrain
2O 12 heavy %, lattice constant 2.468 nanometers) be that ammonium sulfate and the vitriolic mixing solutions of 0.5 mol, PH4-5 mixes with 2 liters, ammonium sulfate concentrations, carried out ion-exchange 1 hour at 80 ℃, filter, with the deionized water wash solid product to there not being the free acid radical ion.Ion exchange process carries out twice.Dry resulting zeolite (abbreviating B as).
(2) take by weighing the above-mentioned zeolite B of 150 grams, make it to mix,, can make the y-type zeolite A1 of nitrogenous (in element, down together) provided by the invention 0.77 heavy % in confined conditions in 300 ℃ of roastings 1 hour with 750 gram ammonium nitrate.
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Adopt step substantially the same manner as Example 1 to be prepared, different is that the ammonium nitrate consumption is 1500 grams in the step (2), and maturing temperature is 500 ℃, and roasting time is 0.5 hour, obtains the y-type zeolite A2 of nitrogenous 1.43 heavy %.
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Adopt step substantially the same manner as Example 1 to be prepared, different is that the ammonium nitrate consumption is 150 grams in the step (2), and maturing temperature is 150 ℃, and roasting time is 2 hours, obtains the y-type zeolite A3 of nitrogenous 0.15 heavy %.
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Prepare modified zeolite of Y-type by the described method of step (2) among the embodiment 1, different is with HY zeolite (Na
2The heavy % of O 0.65, lattice constant is 2.466 nanometers, silica alumina ratio is 5.1) to replace zeolite B, the consumption of ammonium nitrate be 300 grams, 200 ℃ of maturing temperatures, roasting time 1.5 hours obtains the y-type zeolite A4 of nitrogenous 0.20 heavy %.
Embodiment 5-7
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Prepare modified zeolite of Y-type by the described method of step (2) among the embodiment 1, different is with USY zeolite (Na
2O 0.82 heavy %, lattice constant is 2.440 nanometers, silica alumina ratio is 7.0) replacement zeolite B, the consumption of ammonium nitrate is respectively 150 grams, 900 grams and 1500 grams, maturing temperature is respectively 150 ℃, 500 ℃ and 200 ℃, roasting time was respectively 2 hours, 1 hour and 2 hours, obtained nitrogenous USY zeolite A5, A6 and A7, and its nitrogen content is respectively 0.18 heavy %, 0.94 heavy %, 1.36 heavy %.
Embodiment 8-9
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Prepare modified zeolite of Y-type by the described method of step (2) among the embodiment 1, different is with REY zeolite (Na
2O 1.4 heavy %, lattice constant is 2.452 nanometers, silica alumina ratio is 5.4, RE
2O
319.8 heavy %, La in the rare earth
2O
3With CeO
2Weight ratio be 4.0) replace zeolite B, the consumption of ammonium nitrate to be respectively 300 grams and 1500 grams, maturing temperature is respectively 150 ℃, roasting time is 2 hours, obtains nitrogenous REY zeolite A8 and A9, its nitrogen content is respectively 0.17 heavy %, 1.30 weight %.
Embodiment 10-11
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Prepare modified zeolite of Y-type by the described method of step (2) among the embodiment 1, different is with REUSY zeolite (Na
2O 1.0 heavy %, lattice constant is 2.443 nanometers, silica alumina ratio is 6.8, RE
2O
31.8 heavy %, La in the rare earth
2O
3With CeO
2Weight ratio be 4.1) replace zeolite B, ammonium nitrate consumption to be respectively 1200 grams and 450 grams, obtain nitrogenous REUSY zeolite A10 and A11, its nitrogen content is respectively 1.12 heavy %, 0.28 weight %.
Embodiment 12
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Prepare modified zeolite of Y-type by the described method of step (2) among the embodiment 1, different is with REHY zeolite (Na
2O 3.8 heavy %, lattice constant is 2.446 nanometers, silica alumina ratio is 5.4, RE
2O
33.8 heavy %, La in the rare earth
2O
3With CeO
2Weight ratio be 4.1) to replace zeolite B, ammonium nitrate consumption be 300 grams, obtains the REHY zeolite A12 of nitrogenous 0.22 heavy %.
Embodiment 13
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Prepare nitrogenous zeolite by the described method of step (2) among the embodiment 1, different is with mordenite (Na
2The heavy % of O＜0.1, silica alumina ratio is 15.9) to replace zeolite B, ammonium nitrate consumption be 600 grams, 200 ℃ of maturing temperatures, roasting time 2 hours obtains the mordenite A13 of nitrogenous 0.35 heavy %.
Embodiment 14
The used nitrogenous prepare zeolite of catalyzer provided by the invention.
Prepare nitrogenous zeolite by the described method of step (2) among the embodiment 1, different is with ZSM-5 zeolite (Na
2The heavy % of O＜0.1, silica alumina ratio is 88) to replace zeolite B, ammonium nitrate consumption be 600 grams, 200 ℃ of maturing temperatures, roasting time 2 hours obtains the ZSM-5 zeolite A14 of nitrogenous 0.37 heavy %.
Embodiment 15
Present embodiment explanation: the preparation of nitrogenous zeolitic cracking catalyst provided by the present invention and catalytic cracking reaction performance thereof.
Nitrogenous 0.15 of 1 kilogram of (dry basis) embodiment, 4 preparations are weighed the HY type zeolite A4 of %, 4 kilograms of solid contents are the silicon sol (Zhou village catalyst plant product) of 25 heavy %, 2 kilograms of kaolin (dry basises, Suzhou mining company produces) and be equivalent to spraying drying behind the deionized water thorough mixing of aforementioned substances gross weight 50%, and then under 90 ℃, carry out ion-exchange 1 hour with the ammonium sulfate solution that 60 liters of concentration are 5 heavy %, filter, washing leaching cake is to there not being free acid group, in 120 ℃ of dryings 1 hour, and in 800 ℃ with 100% water vapour aging 4 hours, obtain containing nitrogenous zeolite 30 heavy % provided by the invention, silicon oxide 30 heavy %, the catalyzer C1 of kaolin 40 heavy %.
With boiling range is 227-475 ℃ decompressed wax oil, estimates its catalytic performance on the small stationary bed bioreactor, 482 ℃ of temperature of reaction, and weight hourly space velocity 16 hours-1, agent-oil ratio 4, stock oil character is listed in table 1, and evaluation result is listed in table 2.Wherein, distribution of reaction products adopts gas chromatographic analysis.
Comparative Examples 1
This Comparative Examples explanation: the cracking reaction performance that contains the catalyzer of conventional H y-type zeolite.
Prepare catalyzer by embodiment 15 described methods, just general nitrogenous zeolite A4 wherein changes the raw material HY zeolite among the embodiment 4 into, makes reference catalyst D1.Estimate the reactivity worth of D1 with the method identical with embodiment 15, evaluation result is listed in table 2.
By the evaluation result in the table 2 as can be seen, compare with the evaluation result of contrast medium D1, the transformation efficiency of catalyzer C1 has improved 4.8 percentage points, gasoline yield has improved 5.6 percentage points, diesel yield has improved 2.8 percentage points, the heavy oil productive rate has reduced by 6.8 percentage points, and dry gas and coke yield all have apparent in view reduction.Therefore, catalyzer C1 not only has higher transformation efficiency, good heavy oil cracking ability, and has more satisfactory product distribution.
Table 1
| Proportion d 4 20Gram per centimeter 3 | 0.8652 |
| Viscosity, millimeter 2/ second | |
| 50℃ | 14.58 |
| 100℃ | 4.37 |
| Carbon residue, heavy % | 0.04 |
| Boiling range, ℃ | |
| Initial boiling point | 227 |
| 10％ | 289 |
| 30％ | 347 |
| 50％ | 389 |
| 70％ | 417 |
| 90％ | 446 |
| Do | 475 |
Table 2
| The embodiment numbering | 15 | Comparative Examples |
| The catalyzer numbering | C1 | D1 |
| Transformation efficiency, heavy % | 67.6 | 62.8 |
| Productive rate, heavy % | ||
| Dry gas | 1.4 | 1.8 |
| Liquefied gas | 13.6 | 14.4 |
| Gasoline | 50.6 | 45.0 |
| Diesel oil | 26.1 | 23.3 |
| Heavy oil | 6.2 | 13.0 |
| Coke | 2.1 | 2.5 |
Embodiment 16-17
Present embodiment explanation: Preparation of catalysts provided by the present invention and catalytic perfomance thereof.
Step (1): (Shandong Aluminum Plant produces with 72 gram pseudo-boehmites, alumina content is 35.0 heavy %) and 100 restrain deionized waters and mix after, progressively drip 25ml concentrated hydrochloric acid (chemical pure, contain the heavy % of HCl 36-38, the Beijing Chemical Plant produces) stir, be warming up to 70 ℃, aging 1.5 hours, get the aged pseudo-boehmite.Prepare two parts of aged pseudo-boehmites.
Step (2): get nitrogenous REY zeolite A8 and each 100 gram of A9 of embodiment 8-9 preparation, mix with the kaolin of 120 grams, the aluminium colloidal sol (Zhou village catalyst plant product) and a aged pseudo-boehmite of 80 grams respectively after the pulverizing, in 500 ℃ of roastings 2 hours.
Step (3): the product that step (2) obtains is pulverized, the aqueous hydrochloric acid that is 5 heavy % with 20 times of concentration to stem-based catalyst successively under 60 ℃, concentration are aqueous sodium hydroxide solution and the deionized water wash of 5 heavy % respectively, after the filtration, with filter cake 120 ℃ dry 2 hours down, both catalyzer C2 provided by the invention, C3.
Adopt the evaluation method identical, identical stock oil evaluate catalysts C2, C3, the results are shown in table 3 with embodiment 15.
Comparative Examples 2
This Comparative Examples explanation: the cracking reaction performance that contains the catalyzer of conventional REY type zeolite.
With replacing nitrogenous zeolite A8, A9 in the embodiment 16-17 step (2) as the REY zeolite of raw material among the embodiment 8-9, other preparation process is all identical with embodiment 16-17, obtains reference catalyst D2.Adopt evaluation method identical and identical stock oil evaluate catalysts D2, the results are shown in table 3 with embodiment 15.
Table 3
| The embodiment numbering | 16 | 17 | Comparative Examples 2 |
| The catalyzer numbering | C2 | C3 | D2 |
| Transformation efficiency, heavy % | 68.8 | 68.2 | 63.5 |
| Productive rate, heavy % | |||
| Dry gas | 1.5 | 1.8 | 1.9 |
| Liquefied gas | 16.1 | 16.0 | 15.7 |
| Gasoline | 48.5 | 47.8 | 42.4 |
| Diesel oil | 25.6 | 25.3 | 24.1 |
| Heavy oil | 6.4 | 6.9 | 13.8 |
| Coke | 1.9 | 2.2 | 2.1 |
Claims (10)
1, a kind of zeolitic cracking catalyst is characterized in that this catalyzer contains nitrogenous zeolite and substrate material, and described nitrogenous zeolite is the crystal aluminosilicate that contains in the heavy % nitrogen of element 0.01-5, and described nitrogen is with its maxivalence attitude N
+ 5Form exist.
2,, it is characterized in that described nitrogenous zeolite is the crystal aluminosilicate that contains in the heavy % nitrogen of element 0.01-3 according to the catalyzer of claim 1.
3,, it is characterized in that described crystal aluminosilicate is selected from faujusite, mordenite or has in the zeolite of ZSM-5 structure one or more according to the catalyzer of claim 1 or 2.
4,, it is characterized in that described crystal aluminosilicate is selected from one or more in HY zeolite, REY zeolite, REHY zeolite, USY zeolite, REUSY zeolite, the ZSM-5 zeolite according to the catalyzer of claim 3.
5,, it is characterized in that this catalyzer contains the nitrogenous zeolite of the heavy % of 10-40 and the substrate material of surplus according to the catalyzer of claim 1.
6, the preparation method of the described zeolitic cracking catalyst of claim 1 is characterized in that this method is that nitrogenous zeolite is mixed making beating with substrate material, spraying drying, and the product that washing obtains is also dry; Wherein said nitrogenous zeolite with ammonium nitrate and zeolite by 0.1-30: 1 weight ratio directly mixes, in 50-600 ℃ down heating made in 0.1-15 hour.
7, according to the method for claim 6, it is characterized in that described zeolite as nitrogenous zeolite raw material is selected from: faujusite, mordenite, have in the zeolite of ZSM-5 structure one or more.
8,, it is characterized in that described zeolite as raw material is selected from: one or more in HY zeolite, REY zeolite, REHY zeolite, USY zeolite, REUSY zeolite, the ZSM-5 zeolite according to the method for claim 7.
9, according to the method for claim 6, the weight ratio that it is characterized in that described ammonium nitrate and raw material zeolite is 0.1-20: 1.
10, according to the method for claim 6, the mixture that it is characterized in that described ammonium nitrate and zeolite is in confined conditions in 80-550 ℃ of heating 0.5-10 hour.
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Granted publication date: 20051228 |