CN1168658C - Y zeolite preparation - Google Patents
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- CN1168658C CN1168658C CNB011309814A CN01130981A CN1168658C CN 1168658 C CN1168658 C CN 1168658C CN B011309814 A CNB011309814 A CN B011309814A CN 01130981 A CN01130981 A CN 01130981A CN 1168658 C CN1168658 C CN 1168658C
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Abstract
The present invention relates to a method for preparing a Y type zeolite. In the method, a raw material Y type zeolite contacts with the atmosphere containing water steam, wherein the atmosphere containing water steam contains a gas mixture, and the gas mixture is formed from ammonia components and chlorine and/or fluorine components which exist in the forms of water vapor or a mixture of ammonia, hydrogen chlorides and/or hydrogen fluorides and ammonium chlorides and/or ammonium fluorides; by taking the gas mixture as a reference, the contents of the ammonia are from 50 ppm to 30 wt%, and the contents of the chlorine and/or the fluorine are from 50 ppm to 15 wt%; the contact temperature is from 450 to 700 DEG C, and the contact time is from 1 to 10 hours.
Description
Technical field
The invention relates to a kind of method of modifying of faujusite, more specifically say so about a kind of method of modifying of y-type zeolite.
Background technology
Y-type zeolite can be used as sorbent material and various catalyzer, as cracking catalyst, and the active ingredient of hydrocracking catalyst.Because the y-type zeolite silica alumina ratio of lattice constant big (lattice constant is greater than 24.60 dusts) is lower, has more acid site, thereby, be especially suitable for use as the active ingredient of hydrocracking catalyst.Yet the outstanding shortcoming of this y-type zeolite is that thermostability is not high, and its degree of crystallinity is lower after roasting.For improving the stability of y-type zeolite, usually, be prepared into overstable gamma zeolite with the y-type zeolite super stabilizing.The method that the y-type zeolite super stabilizing is the most frequently used is a hydrothermal method, is about to y-type zeolite and at high temperature contacts with the atmosphere of moisture vapor.
US4,036,739 discloses a kind of method of catalytically crack hydrocarbons raw material production low boiling point hydrocarbon, discloses a kind of preparation method of y-type zeolite in this method, comprises a kind of NH that contains the heavy % of sodium 0.6-5 of (1) roasting
4NaY zeolite, described roasting under the temperature of 600-1650 (315.6-898.9 ℃), and with the water vapor of 0.5Psi contacts at least condition under carry out, the time of contact is to the 24.40-24.64 dust with the structure cell that reduces described zeolite; (2) zeolite after the roasting is carried out the ammonium exchange, the condition of exchange makes at least 25% of remaining sodium ion be replaced by ammonium ion, obtain the product that sodium content obtains in (2) step of roasting temperature of 600-1500 (315.6-898.9 ℃) less than 1 product (3) that weighs %, ammonium in enough effective elimination zeolites basically of the time of roasting does not make the lattice constant of zeolite be contracted to below 24.40 dusts.
Though the y-type zeolite stability that adopts aforesaid method to obtain is improved, but, along with silica alumina ratio reduces (contraction of lattice constant), reduce in the acid site of zeolite, degree of crystallinity descends, and generate a large amount of non-framework aluminums in zeolite, the existence of non-framework aluminum also directly influences the catalytic performance of zeolite in the zeolite.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming of prior art, a kind of thermostability that can improve y-type zeolite is provided, significantly do not reduce the lattice constant of y-type zeolite again, the y-type zeolite that obtains has the method for modifying of the y-type zeolite of higher crystallinity and less non-framework aluminum.
The method of modifying of y-type zeolite provided by the invention comprises a kind of raw material y-type zeolite is contacted with a kind of atmosphere of moisture vapor, resulting product is carried out the ammonium exchange, washing is also dry, wherein, described raw material y-type zeolite is that a kind of sodium oxide content is not higher than 5 heavy %, lattice constant is the y-type zeolite of 24.6-24.75 dust, the atmosphere of described moisture vapor contains a kind of gaseous mixture, this gaseous mixture is by water vapor, ammonia components and chlorine and/or fluorine component are formed, described ammonia components and chlorine and/or fluorine component are with ammonia, the form of hydrogenchloride and/or hydrogen fluoride and ammonium chloride and/or Neutral ammonium fluoride mixture exists, with described gaseous mixture is benchmark, in ammonia, the content of described ammonia components is the heavy % of 50ppm to 30, in chlorine and/or fluorine, the content of described chlorine and/or fluorine component is the heavy % of 50ppm to 15, and the temperature of described contact is 450-700 ℃, and be 1-10 hour duration of contact
Method provided by the invention has following advantage:
Y-type zeolite with method preparation provided by the invention has higher thermostability, and lattice constant does not significantly reduce.For example, adopt method provided by the invention to prepare y-type zeolite, the y-type zeolite of preparing does not significantly reduce than lattice constant with initial raw material zeolite facies, and after 550 ℃ of roastings, relative crystallinity is all more than 60%.And the y-type zeolite of employing prior art for preparing, after 550 ℃ of roastings, relative crystallinity is the highest to have only 58%.
Y-type zeolite with method preparation provided by the invention does not have non-framework aluminum.
The above-mentioned physico-chemical property of the y-type zeolite of method preparation provided by the invention has determined this y-type zeolite to have better catalytic performance.For example, the hydrocracking catalyst that contains the y-type zeolite of method provided by the invention preparation has hydrogenation cracking activity and the activity stability higher than prior art.
Embodiment
According to method provided by the invention, be benchmark with described gaseous mixture, in ammonia, the content of described ammonia components is the heavy % of 50ppm to 30, the heavy % of preferred 1-30, in chlorine and or fluorine, described fluorine and/or chlorine components contents are the heavy % of 50ppm-15, are preferably the heavy % of 1-15.The preferred chlorine component of described chlorine and/or fluorine component.
The gaseous mixture that the atmosphere of described moisture vapor can just be made up of water vapor, ammonia components and chlorine and/or fluorine component also can be the gas mixture of this gaseous mixture and rare gas element.In the described gas mixture, the content of the described gaseous mixture of being made up of water vapor, ammonia components and chlorine and/or fluorine component is not less than 10 body %, preferably is not less than 40 body %.Described rare gas element refers to not destroy one or more in the zeolite structured arbitrary gas, as in the zero group gas in air, oxygen, nitrogen, the periodic table of elements one or more, because air and nitrogen cheaply are easy to get, therefore, preferred air of described rare gas element or nitrogen.
Ammonia components in the described moisture vapor atmosphere and chlorine and/or fluorine component adopt following method to mix with water vapor: by each component ratio in the gas phase, with ammoniacal liquor and ammonium chloride and/or Neutral ammonium fluoride and water mixing, all evaporate the mixing solutionss that obtain then.At described contact conditions, promptly under 450-700 ℃ the temperature, described ammonia components and chlorine and/or fluorine component exist with ammonia, hydrogenchloride and/or hydrogen fluoride and ammonium chloride and/or Neutral ammonium fluoride form of mixtures, and are in chemical equilibrium.
Described moisture vapor atmosphere contacts with described raw material y-type zeolite, can carry out Static Contact in encloses container, and the bed that also the atmosphere continuous flow of described moisture vapor can be crossed a described raw material y-type zeolite dynamically contacts.
When described moisture vapor atmosphere and described raw material zeolite carried out Static Contact in encloses container, the consumption of described moisture vapor atmosphere should make the water vapor in the moisture vapor atmosphere and the weight ratio of described raw material y-type zeolite be not less than 0.1, is preferably 0.1-4.When described moisture vapor atmosphere dynamically contacted with described raw material y-type zeolite, the flow of described moisture vapor atmosphere should make the amount of the water vapor that every gram catalyzer per minute passes through be at least 0.1 gram, is preferably the 0.1-4 gram.
The temperature of described contact is 450-700 ℃, is preferably 500-650 ℃, and the time of contact is 1-10 hour, is preferably 1-3 hour.
Described ammonium exchange can be adopted conventional ammonium ion exchange method, be about to contact with a kind of aqueous solution that contains ammonium ion with zeolite after moisture vapor atmosphere contacts, the condition of contact is: the contact temperature is 60-120 ℃, is preferably 80-100 ℃, and be 1-10 hour duration of contact, be preferably 1-3 hour, solvent and solute weight ratio is 3-50, is preferably 5-20, contains in the aqueous solution of ammonium ion, the concentration of ammonium ion is the 0.5-4 mole, is preferably the 0.8-3 mol.The number of times of contact is reduced to below the 1 heavy % sodium oxide content in the zeolite.
According to embodiment preferred of the present invention, the aqueous solution that contains ammonium ion that adopt described ammonium clearing house is the aqueous solution that contains ammonium ion of pH value for 3-6, adopts such aqueous solution that contains ammonium ion can remove the non-framework aluminum of the minute quantity that generates in the zeolite.Adjusting contains the acid of the pH value of aqueous solution of ammonium ion can be with in mineral acid and the organic acid one or more, example hydrochloric acid, nitric acid, formic acid, acetate, tartrate, EDTA etc.
Described raw material y-type zeolite is that a kind of sodium oxide content is not higher than 5 heavy %, and lattice constant is the y-type zeolite of 24.60-24.75 dust, and this zeolite can be purchased and get, and also can prepare with the NaY zeolite with the ammonium ion exchange method.The ammonium ion exchange method is conventionally known to one of skill in the art, and the present invention also is described in front.
The following examples will the present invention will be further described.
Example 1
Following example illustrates method provided by the invention.
(1) (lattice constant is 24.72 dusts, silica alumina ratio SiO with the NaY zeolite
2/ Al
2O
3Be 5.2, sodium oxide content is 12 heavy %, Chang Ling refinery catalyst plant is produced) be that the aqueous ammonium chloride solution of 2.3 mol mixes with concentration, solvent and solute weight ratio is 10, is warming up to 95 ℃, under agitation carries out ion-exchange 1 hour, filter, spend the ion-cleaning solid product and be not detected to there being chlorion, 120 ℃ of oven dry, obtaining sodium oxide content is the y-type zeolite of 4.8 heavy %.
(2) take by weighing y-type zeolite 60 grams that the sodium oxide content that obtains is 4.8 heavy %, with 40 gram deionized waters, 5 gram ammonium chlorides and 10 gram concentration are that the ammonia soln of 25 heavy % mixes, and mixture is placed an encloses container, and with the suction filtration machine air is wherein extracted out, be warming up to 600 ℃ then, under 600 ℃ temperature, liquid phase part all evaporates, and the ammonia 11.9 that consists of of gas phase weighs %, chlorine 5.8 heavy %, all the other are water.Contact and stop heating after 3 hours.
(3) will be that 4.0 concentration is that the aqueous ammonium chloride solution of 2.3 mol mixes (the pH value of aqueous ammonium chloride solution is regulated with acetate) with zeolite after moisture vapor atmosphere contacts and pH value, solvent and solute weight ratio is 10, under 95 ℃ temperature, carry out ion-exchange 1 hour, filter, with deionized water wash to not having acid ion, 120 ℃ of oven dry.With the zeolite after the oven dry and pH value is that 3.0 concentration is that the aqueous ammonium chloride solution of 2.3 mol mixes (the pH value of aqueous ammonium chloride solution is regulated with acetate), solvent and solute weight ratio is 10, under 95 ℃ of temperature, carried out ion-exchange 1 hour, filter, the washing solid product is to there not being acid ion, 120 ℃ of oven dry obtain the y-type zeolite Z1 that method provided by the invention prepares.Table 1 has provided the physico-chemical property of Z1.
Wherein, lattice constant, degree of crystallinity adopt X-ray diffraction method to measure.Specific surface adopts cryogenic nitrogen absorption BET method to measure.Sodium oxide content adopts the X-fluorescence spectrum method for measuring.Non-framework aluminum characterizes with infrared spectroscopy, and wave number is 3740cm in the infrared spectra
-1Characteristic peak be the characteristic peak of non-framework aluminum in the zeolite, if there is non-framework aluminum in the zeolite, in the infrared spectrum this characteristic peak can appear, otherwise, this characteristic peak does not then appear.Wherein, described degree of crystallinity is relative crystallinity, and the degree of crystallinity of NaY zeolite described in (1) is decided to be 100%, and the degree of crystallinity of the zeolite of method provided by the invention (or control methods) preparation promptly is the degree of crystallinity with respect to described NaY zeolite.
Comparative Examples 1
The preparation method of this Comparative Examples explanation reference y-type zeolite.
Method by example 1 prepares y-type zeolite, and the step that different is does not contact with y-type zeolite in encloses container with moisture vapor atmosphere obtains reference zeolite B
1B
1Physico-chemical property list in the table 1.
Comparative Examples 2
The preparation method of this Comparative Examples explanation reference y-type zeolite.
Method by example 1 prepares y-type zeolite, and different is not add ammonium chloride and ammoniacal liquor, obtains reference y-type zeolite B
2B
2Physico-chemical property list in the table 1.
Example 2
This example illustrates method provided by the invention.
Method by example 1 prepares y-type zeolite, different is the air of not extracting out in the described encloses container, under described contact conditions, regulate the content of air, the content that makes the gaseous mixture of being made up of water vapor and ammonia components and chlorine component in the gas phase is 50 body %, air content is 50 body %, obtains the y-type zeolite Z of method preparation provided by the invention
2Z
2Physico-chemical property list in the table 1.
Comparative Examples 3
The preparation method of this Comparative Examples explanation reference y-type zeolite.
Method by example 2 prepares y-type zeolite, and different is not add ammoniacal liquor and ammonium chloride, obtains reference y-type zeolite B
3B
3Physico-chemical property list in the table 1.
Example 3-4
Following example illustrates method provided by the invention.
Method by example 1 prepares y-type zeolite, the consumption that contact temperature that different is is respectively 650 ℃ and 500 ℃ water is respectively 21 grams and 200 and restrains, the consumption of ammoniacal liquor is respectively 15 grams and 1 gram, the consumption of ammonium chloride is respectively 10 grams and 4 grams, gas phase is formed the ammonia be respectively 20.1 heavy %, the chlorine of 13.6 heavy %, all the other be ammonia, the 1.3 weight % of water and 2.1 heavy % chlorine, all the other are water, be respectively duration of contact 1 hour and 2 hours, and obtained the y-type zeolite Z of method preparation provided by the invention
3And Z
4Z
3And Z
4Physico-chemical property list in the table 1.
Example 5
This example illustrates method provided by the invention.
With nitrogen carry by water vapor, (ammonia content is 20 heavy % to the gaseous mixture that ammonia components and chlorine component are formed, cl content is 10 heavy %, all the other are water), the y-type zeolite bed (y-type zeolite by example 1 (1) preparation) of flow with per 100 mol sieve, the 200 gram water of per minute by placing tube furnace, the consumption of y-type zeolite is 100 grams, a nitrogen content is 50 body % in the gas phase, by water vapor, the content of the gaseous mixture that ammonia components and chlorine component are formed is 50 body %, the temperature that gas contacts with y-type zeolite is 550 ℃, ventilates to stop ventilation and cooling after 3 hours.
To carry out ammonium exchange and oven dry with the y-type zeolite after moisture vapor gas contacts by the method for (3) in the example 1, obtain y-type zeolite Z provided by the invention
5Z
5Physico-chemical property list in the table 1.
Table 1
| Example number | The y-type zeolite numbering | Lattice constant (A) | Specific surface (rice 2/ gram) | Na 2O (heavy %) | Degree of crystallinity (%) | Degree of crystallinity * (％) | The non-framework aluminum characteristic peak |
| 1 | Z 1 | 24.65 | 682 | 0.78 | 70.4 | 64.3 | Do not have |
| Comparative Examples 1 | B 1 | 24.66 | 671 | 0.74 | 66.8 | 56.2 | Do not have |
| Comparative Examples 2 | B 2 | 24.56 | 667 | 0.75 | 65.4 | 58.2 | Have |
| 2 | Z 2 | 24.65 | 656 | 0.85 | 63.5 | 60.5 | Do not have |
| Comparative Examples 3 | B 3 | 24.55 | 676 | 0.83 | 57.0 | 54.5 | Have |
| 3 | Z 3 | 24.68 | 667 | 0.88 | 68.7 | 61.3 | Do not have |
| 4 | Z 4 | 24.65 | 662 | 0.98 | 66.3 | 62.4 | Do not have |
| 5 | Z 5 | 24.65 | 689 | 0.70 | 61.8 | 63.4 | Do not have |
* degree of crystallinity is the degree of crystallinity of 550 ℃ of roastings after 2 hours
The result of table 1 shows: (1) is compared with the y-type zeolite without steam-treated, the y-type zeolite of method preparation provided by the invention is greatly improved through the degree of crystallinity of 550 ℃ of roastings after 2 hours, and the degree that lattice constant dwindles is very little, improved 14.4% as degree of crystallinity, and lattice constant there is not difference substantially.This explanation is compared with the y-type zeolite that does not carry out steam treatment, when the y-type zeolite that adopts method provided by the invention to prepare does not have obviously to reduce lattice constant, has higher thermostability.(2) with through steam-treated, do not compare with the y-type zeolite that the chlorine component obtains but do not contain ammonia components in the gas phase, the zeolite of method provided by the invention preparation has higher degree of crystallinity, and also is like this after 2 hours through 550 ℃ of roastings.Simultaneously, adopt the y-type zeolite of method provided by the invention preparation not contain non-framework aluminum, and through steam-treated but do not contain the y-type zeolite that ammonia components and chlorine component obtain in the gas phase tangible non-framework aluminum infrared signature peak is arranged.Therefore, the y-type zeolite of method preparation provided by the invention has the thermostability higher than prior art, does not have significantly to reduce the lattice constant of zeolite again, has higher crystallization reservation degree, has less non-framework aluminum simultaneously again.
Example 6-10
Following example illustrates the catalytic performance of the y-type zeolite of method preparation provided by the invention.
Take by weighing the y-type zeolite Z of example 1-5 preparation respectively
1-Z
5Mix with pseudo-boehmite (solid content is 75 heavy %, and trade name is the SB powder, and German CONDEA company produces), add entry again and mix and to pinch, be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, at different roasting temperatures, obtain carrier of hydrocracking catalyst S
1-S
5Table 2 has provided y-type zeolite Z in the preparation process
1-Z
5Consumption, maturing temperature and the roasting time of (dry basis), pseudo-boehmite (dry basis), water, table 3 has provided support of the catalyst S
1-S
5Composition, this composition is got by calculating.
Take by weighing support of the catalyst S respectively
2-S
5100 grams (dry basis) flooded 1 hour with the ammonium fluoride aqueous solution of 100 milliliters of different concns, and be filtered to no obvious water droplet with B and drip, 120 ℃ of oven dry, under different temperature, the time that roasting is different.Take by weighing S respectively
1S with the last fluorine of dipping
2-S
5100 grams (dry basis), ammonium metawolframate and nickelous nitrate mixing solutions with 250 milliliters of different concns flooded 1 hour respectively, being filtered to no obvious drop with B drips, 120 ℃ of oven dry, the different time of roasting under differing temps, obtain containing the hydrocracking catalyst C of the y-type zeolite of method preparation provided by the invention
1-C
5Table 4 has provided in the preparation process content and the roasting condition of Tungsten oxide 99.999, nickel oxide in the concentration of used ammonium fluoride solution, ammonium metawolframate and the nickelous nitrate mixing solutions.Table 5 has provided catalyzer C
1-C
5The content and the vector contg of middle Tungsten oxide 99.999, nickel oxide, fluorine.Wherein, Tungsten oxide 99.999, nickel oxide content measuring method are referring to " petrochemical complex analytical procedure " (RIPP test method(s)), P360～361, Science Press (1990).The measuring method of fluorine is referring to the P185 that ibidems～187 page.Vector contg=100%-tungsten oxide content-nickel oxide content-fluorine content.
With the decane is raw material, evaluate catalysts C on the small fixed hydroeracking unit
1-C
5Hydrogenation cracking activity, 0.2 milliliter of catalyzer loading amount, the granules of catalyst diameter is the 0.3-0.45 millimeter, temperature of reaction is 370 ℃, reaction pressure is 4.0 MPas, hydrogen to oil volume ratio is 25, liquid hourly space velocity is 60 hours
-1The transformation efficiency of n-decane is as shown in table 6.
Comparative Examples 4-5
The catalytic performance of following Comparative Examples explanation reference zeolite.
Method by example 6 prepares support of the catalyst and catalyzer, and different is to use reference y-type zeolite B respectively
1And B
2Replace Z
1, obtain reference catalyst carrier S B
1And SB
2And reference catalyst CB
1And CB
2Method by example 6 is estimated catalyzer.Table 2 has provided B in the preparation process
1, B
2, pseudo-boehmite, water consumption, maturing temperature and roasting time.Table 3 has provided SB
1And SB
2Composition.Table 4 has provided Tungsten oxide 99.999 and the nickel oxide content and the roasting condition of used ammonium metawolframate and nickelous nitrate mixing solutions in the preparation process.Table 5 has provided CB
1And CB
2Composition.Table 6 has provided evaluation result.
Comparative Examples 6
The catalytic performance of this Comparative Examples explanation reference zeolite.
Method by example 7 prepares support of the catalyst and catalyzer, and different is with reference y-type zeolite B
3Replace Z
2, obtain reference catalyst carrier S B
3With reference catalyst CB
3The method of pressing example 7 is to catalyzer CB
3Carry out activity rating.Table 2 has provided B in the preparation process
3, pseudo-boehmite, water consumption and maturing temperature and roasting time.Table 3 has provided SB
3Composition.Table 4 has provided Tungsten oxide 99.999 and the nickel oxide content and the roasting condition of used ammonium metawolframate and nickelous nitrate mixing solutions in the preparation process.Table 5 has provided CB
3The content and the vector contg of middle Tungsten oxide 99.999 and nickel oxide.Table 6 has provided evaluation result.
Table 2
| Example number | Zeolite | Pseudo-boehmite consumption (gram) | Water (gram) | Maturing temperature (℃) | Roasting time (hour) | |
| Kind | Consumption (gram) | |||||
| 6 | Z 1 | 60 | 40 | 80 | 550 | 4 |
| Comparative Examples 4 | B 1 | 60 | 40 | 80 | 550 | 4 |
| Comparative Examples 5 | B 2 | 60 | 40 | 80 | 550 | 4 |
| 7 | Z 2 | 25 | 75 | 93 | 600 | 4 |
| Comparative Examples 6 | B 3 | 25 | 75 | 93 | 600 | 4 |
| 8 | Z 3 | 10 | 90 | 93 | 650 | 2 |
| 9 | Z 4 | 30 | 70 | 66 | 500 | 8 |
| 10 | Z 5 | 60 | 40 | 66 | 500 | 6 |
Table 3
| Example number | Bearer number | Carrier is formed | ||
| Zeolite type | Zeolite content, heavy % | Alumina content, heavy % | ||
| 6 | S 1 | Z 1 | 60.0 | 40.0 |
| Comparative Examples 4 | SB 1 | B 1 | 60.0 | 40.0 |
| Comparative Examples 5 | SB 2 | B 2 | 60.0 | 40.0 |
| 7 | S 2 | Z 2 | 25.0 | 75.0 |
| Comparative Examples 6 | SB 3 | B 3 | 25.0 | 75.0 |
| 8 | S 3 | Z 3 | 10.0 | 90.0 |
| 9 | S 4 | Z 4 | 30.0 | 70.0 |
| 10 | S 5 | Z 5 | 60.0 | 40.0 |
Table 4
| Example number | 6 | Comparative Examples 4 | Comparative Examples 5 | 7 | Comparative Examples 6 | 8 | 9 | 10 | |
| Bearer number | S 1 | SB 1 | SB 2 | S 2 | SB 3 | S 3 | S 4 | S 5 | |
| The dipping of fluorine | Ammonium fluoride aqueous solution concentration, heavy % | - | - | - | 2.6 | 2.6 | 6.5 | 2.2 | 3.8 |
| Maturing temperature, ℃ | - | - | - | 450 | 450 | 300 | 500 | 380 | |
| Roasting time, hour | - | - | - | 4 | 4 | 8 | 2 | 3 | |
| The dipping of nickel tungsten | Tungsten oxide content in the solution restrains/100 milliliters | 31.20 | 31.20 | 31.20 | 35.50 | 35.50 | 24.60 | 49.05 | 34.88 |
| Nickel oxide content in the solution restrains/100 milliliters | 7.88 | 7.88 | 7.88 | 7.57 | 7.57 | 3.22 | 11.74 | 9.32 | |
| Maturing temperature, ℃ | 500 | 500 | 500 | 450 | 450 | 550 | 350 | 400 | |
| Roasting time, hour | 2 | 2 | 2 | 4 | 4 | 2 | 8 | 6 | |
Table 5
| Example number | The catalyzer numbering | Bearer number | Vector contg (heavy %) | WO 3(heavy %) | NiO (heavy %) | Fluorine content (heavy %) |
| 6 | C 1 | S 1 | 75.7 | 19.4 | 4.9 | - |
| Comparative Examples 4 | CB 1 | SB 1 | 75.8 | 19.3 | 4.9 | - |
| Comparative Examples 5 | CB 2 | SB 2 | 75.7 | 19.3 | 5.0 | - |
| 7 | C 2 | S 2 | 71.7 | 22.1 | 4.7 | 1.5 |
| Comparative Examples 6 | CB 3 | SB 3 | 71.8 | 22.0 | 4.6 | 1.6 |
| 8 | C 3 | S 3 | 76.9 | 15.3 | 2.0 | 5.8 |
| 9 | C 4 | S 4 | 61.0 | 30.5 | 7.3 | 1.2 |
| 10 | C 5 | S 5 | 70.0 | 21.7 | 5.8 | 2.5 |
Table 6
| Example number | The catalyzer numbering | The n-decane transformation efficiency, heavy % |
| 6 | C 1 | 72.6 |
| Comparative Examples 4 | CB 1 | 63.8 |
| Comparative Examples 5 | CB 2 | 64.1 |
| 7 | C 2 | 68.2 |
| Comparative Examples 6 | CB 3 | 62.3 |
| 8 | C 3 | 40.5 |
| 9 | C 4 | 75.2 |
| 10 | C 5 | 67.8 |
The result of table 6 shows, under the close situation of zeolite, Tungsten oxide 99.999 and nickel oxide content, compares with the catalyzer that contains the reference zeolite, and the catalyzer that contains the y-type zeolite of method preparation provided by the invention has higher hydrogenation cracking activity.The transformation efficiency of n-decane has improved 9.5-13.8% than the catalyzer that contains the reference zeolite.
Example 11-12
Following example illustrates the catalytic performance of the y-type zeolite of method preparation provided by the invention.
The surperficial carbon deposit of the inactivation of catalyzer and catalyzer is closely related, and organic basic nitrogenous compound (as pyridine) easily and the generation of the cracking activity center of catalyzer is strong adsorbs, thereby the condensation side reaction easily takes place, and finally causes catalyst carbon deposit.In addition, the speed of catalyst surface carbon deposit is also closely related with reaction conditions, and when low and/or air speed when higher, catalyst surface carbon deposit speed can be accelerated as hydrogen-oil ratio.Following example just is based on above-mentioned principle, adopts the heptane that contains pyridine as raw material, in higher temperature, under lower hydrogen-oil ratio and the higher air speed, catalyzer is accelerated inactivation, investigates activity of such catalysts stability.Being reaction raw materials with the n-decane carries out activity rating to the catalyzer of accelerating behind the inactivation, and it is high more to accelerate behind the inactivation transformation efficiency of n-decane, illustrates that this activity of such catalysts stability is high more.
The catalyzer C that to be respectively charged into 2 milliliters of particle diameters in the reactor of small stationary bed apparatus be the 0.3-0.45 millimeter
1And C
2, be 25 in 4.0 MPas, 370 ℃, hydrogen to oil volume ratio, liquid hourly space velocity is 60 hours
-1Condition under decane is carried out hydrocracking, react after 10 hours, replace n-decane with accelerating inactivation reaction raw material (normal heptane that promptly contains the heavy % of pyridine 1), simultaneously, temperature is increased to 400 ℃, hydrogen to oil volume ratio is reduced to 5, liquid hourly space velocity was increased to 300 hours
-1, react and accelerate the inactivation end after 100 hours.Again replace the normal heptane that contains pyridine 1 heavy % with n-decane, temperature of reaction is reduced to 370 ℃ simultaneously, hydrogen to oil volume ratio is increased to 25, and liquid hourly space velocity was reduced to 60 hours
-1, the composition that continues 4 hours post analysis products of reaction calculates the transformation efficiency of n-decane, and the results are shown in Table 7.
Comparative Examples 7-9
The catalytic performance of following Comparative Examples explanation reference zeolite.
Press the method evaluate catalysts of example 11-12, the different reference catalyst CB that just use respectively
1, CB
2Replace catalyzer C
1, use reference catalyst CB
3Replace catalyzer C
2, the results are shown in Table 7.
Table 7
| Example number | Catalyzer | The n-decane transformation efficiency, heavy % |
| 11 | C 1 | 35.5 |
| Comparative Examples 7 | CB 1 | 23.8 |
| Comparative Examples 8 | CB 2 | 24.5 |
| 12 | C 2 | 31.5 |
| Comparative Examples 9 | CB 3 | 21.6 |
The result of table 7 shows, after accelerating inactivation, the hydrocracking catalyst that contains the y-type zeolite of method provided by the invention preparation has the high activity that manys than the hydrocracking catalyst of the zeolite that contains prior art for preparing, this explanation, the hydrocracking catalyst of the y-type zeolite of method preparation provided by the invention has higher activity stability.Because the difference of two kinds of catalyzer only is that employed zeolite is different, therefore, illustrates that zeolite provided by the invention has higher activity stability.
Claims (12)
1. the method for modifying of a y-type zeolite, this method comprises a kind of raw material y-type zeolite is contacted with a kind of atmosphere of moisture vapor, resulting product is carried out the ammonium exchange, washing is also dry, it is characterized in that, described raw material y-type zeolite is that a kind of sodium oxide content is not higher than 5 heavy %, lattice constant is the y-type zeolite of 24.6-24.75 dust, the atmosphere of described moisture vapor contains a kind of gaseous mixture, this gaseous mixture is by water vapor, ammonia components and chlorine and/or fluorine component are formed, described ammonia components and chlorine and/or fluorine component are with ammonia, the form of hydrogenchloride and/or hydrogen fluoride and ammonium chloride and/or Neutral ammonium fluoride mixture exists, with described gaseous mixture is benchmark, in ammonia, the content of described ammonia components is the heavy % of 50ppm to 30, and in chlorine and/or fluorine, the content of described chlorine and/or fluorine component is the heavy % of 50ppm to 15, the temperature of described contact is 450-700 ℃, and be 1-10 hour duration of contact.
2. method according to claim 1 is characterized in that, the content of ammonia components is the heavy % of 1-30 in the atmosphere of described moisture vapor, and the content of chlorine and/or fluorine component is the heavy % of 1-15.
3. method according to claim 1 and 2 is characterized in that described chlorine and/or fluorine component refer to the chlorine component.
4. method according to claim 1, it is characterized in that, the gaseous mixture that the atmosphere of described moisture vapor is made up of water vapor, ammonia components and chlorine and/or fluorine component, or the gas mixture of this gaseous mixture and rare gas element, in this gas mixture, the content of the described gaseous mixture of being made up of water vapor, ammonia components and chlorine and/or fluorine component is not less than 10 body %.
5. method according to claim 4 is characterized in that, the content of the described gaseous mixture of being made up of water vapor, ammonia components and chlorine and/or fluorine component is not less than 40 body %.
6. method according to claim 4 is characterized in that described rare gas element refers to air or nitrogen.
7. method according to claim 1 is characterized in that, described contact temperature is 500-650 ℃, and be 1-3 hour duration of contact.
8. method according to claim 1, it is characterized in that, the atmosphere of described moisture vapor is carried out with contacting in encloses container of described raw material y-type zeolite, and the consumption of the atmosphere of described moisture vapor makes the water vapor in the moisture vapor atmosphere and the weight ratio of described raw material y-type zeolite be not less than 0.1.
9. method according to claim 8 is characterized in that, the weight ratio of described water and described raw material y-type zeolite is 0.1-4.
10. method according to claim 1, it is characterized in that, the way of contact of the atmosphere of described moisture vapor and described raw material y-type zeolite is: the atmosphere of moisture vapor flows through the bed of a described raw material y-type zeolite constantly, and the flow of the atmosphere of described moisture vapor makes the amount of the water vapor that every gram zeolite per minute passes through be at least 0.1 gram.
11. method according to claim 10 is characterized in that, it is the 0.1-4 gram that the flow of the atmosphere of described moisture vapor makes the amount of the water vapor that every gram zeolite per minute passes through.
12. method according to claim 1, it is characterized in that, the exchange of described ammonium comprises and will contact with a kind of aqueous solution that contains ammonium ion with zeolite after described moisture vapor atmosphere contacts, the condition of contact is: the contact temperature is 60-120 ℃, be 1-10 hour duration of contact, solvent and solute weight ratio is 3-50, contain in the aqueous solution of ammonium ion, the concentration of ammonium ion is the 0.5-4 mol, the number of times of contact is reduced to below the 1 heavy % sodium oxide content in the zeolite, and the described pH value of aqueous solution that contains ammonium ion is 3-6.
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| CNB011309814A CN1168658C (en) | 2001-08-29 | 2001-08-29 | Y zeolite preparation |
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| CNB011309814A CN1168658C (en) | 2001-08-29 | 2001-08-29 | Y zeolite preparation |
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| CN1168658C true CN1168658C (en) | 2004-09-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102625779B (en) * | 2009-07-29 | 2014-09-24 | 南非核能源有限公司 | Treatment of zirconia-based material with ammonium bi-fluoride |
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2001
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102625779B (en) * | 2009-07-29 | 2014-09-24 | 南非核能源有限公司 | Treatment of zirconia-based material with ammonium bi-fluoride |
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