CN1382525A - Process for preparing rare-earth type high-silicon gamma-zeolite - Google Patents
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Abstract
A process for preparing rare-earth contained high-Si Y-zeolite incldues drying the rare-earth contained Y-zeolite until its water content is 10 wt.%, introducing SiCl4 gas carrier by dried air in the weight ratio of 0.1-0.9 (SiCl4):1 (Y-zeolite), reaction at 150-600 deg.c for 10 min-6 hr, scavenging with dried air for 5 min-2 hr, and washing in decationic water. Its advantages are simple process, saving energy and no pollution.
Description
The invention relates to a kind of preparation method of y-type zeolite, further say so about a kind of preparation method of rare-earth type high-silicon gamma-zeolite.
In recent years; along with catalytically cracked stock becomes enhancing day by day heavy and the protection Environmental awareness day by day; people require catalytic cracking catalyst should have the hydrothermal stability of higher activity, better hydrogen transfer activity and Geng Gao; to improve heavy oil conversion, preventing from heavy metal pollution ability, again can the voluminous high quality clean gasoline that hangs down alkene, low sulfur content.Y-type zeolite is the active component of cracking catalyst, and therefore the demand for the y-type zeolite with These characteristics also enlarges day by day.
Following several stages has been experienced in the development of y-type zeolite:
The NaY zeolite is not have actively to acid or catalyzed reaction, and people use H
+Exchange substitutes Na
+After making HY type zeolite, just has very high activity.Exchange can have two kinds of methods: the first is handled with diluted acid; It two is to use NH earlier
4+Exchange, NH is removed in thermolysis then
3Stay H
+The HY zeolite has very high activity, but structural stability is relatively poor, and in the dry air more than 500 ℃, its degree of crystallinity is lost, even is positioned in the air in room temperature, also can make its structure deteriorate.
Since the sixties, factory is general is used for oil refining processing for zeolite catalyst, and the stability of zeolite is the major issue of considering in the catalyst preparation process.Industrial cracking catalyst is representative with REY and REHY all based on rare earth Y type zeolite usually.REY zeolite good stability, be with the NaY zeolite in the salts solution of rare earth, under less than 100 ℃ of temperature, stir certain hour, filter then, repeatedly exchange to reach required exchange degree with fresh solution again, and among exchange several times, carry out roasting and make, its content of rare earth is with RE
2O
3Count the heavy % of 10-19.
The REY protonic acid is less.People to increase catalytic activity, introduce an amount of NH in order to introduce more protonic acid in catalyzer when rare earth ion exchanged
4+Obtain REHY, be about to the salts solution and the NH of rare earth
4+Salts solution mix by a certain percentage that the back exchanges with zeolite about 80 ℃ or respectively exchange obtain REHY, its content of rare earth is with RE
2O
3Count the heavy % of 6-14, REHY not only has very high activity, and has solved the problem of HY zeolite poor heat stability.
Deep development along with heavy oil fluid catalytic cracking processing, REHY and REY zeolite as the catalytic cracking catalyst active component, though they have the high and high characteristics of cracking activity of hydrogen transfer activity, be difficult for shrinking but still exist its structure cell, the hydrothermal stability problem of ability higher temperature not, thereby in catalytic cracking unit, easily green coke and easily inactivation.
At USP3,293, reach C.V.MC Darid and P.K.Maher in 192 at " zeolite stability and super steady zeolite " (zeolite chemistry and catalysis, Acs Monograph 171, WashingtonD.C., 1976, disclosed the ultrastable Y (USY) of Hydrothermal Preparation in 285-231).This prepare zeolite process is to use NH under aqueous solution state
4 +Ion-exchange NaY zeolite, the zeolite after the exchange be roasting under 600-825 ℃ and water vapour again, and this process can repeat repeatedly.After the processing of repeatedly exchange, multiple high temp roasting condition, the zeolite structure cell shrinks, and realizes super stabilizing.USY zeolite with this method preparation has good heat and hydrothermal stability, can improve the selectivity of cracking reaction, reduces hydrogen transfer activity, but the limited deficiency of zeolite activity level is also arranged.
The method that adopts earth solution to exchange again is to improve the active a kind of approach of USY, but, because the dealumination complement silicon that in the super stabilizing process, takes place reaction, though the structure cell of zeolite can effectively be shunk, also existing the part lattice but then subsides and stops up the problem in duct, the loading capacity that shows as zeolite is little, gained REUSY zeolite RE
2O
3Content the highest about 3 heavy %, its activity level is still limited, can not satisfy the slags of mixing more, refines the more requirement of heavy crude oil.
A kind of preparation method of rare earth-containing rich silicon ultra stabilization Y-type molecular sieve is disclosed in CN1127161A.This method is the solid RECl with NaY zeolite and porphyrize
3Mix the SiCl that back and dry air carry while hot
4React, a step is realized super stabilizing and the rare earth ion exchanged of NaY, but as the solid RECl of raw material
3Before reaction, need through high-temperature roasting, oven dry; Not only expend the energy, and easily pollute.
The objective of the invention is on the basis of existing technology, a kind of simpler, preparation method of saving the energy and free of contamination rare-earth type high-silicon gamma-zeolite is provided, make the rare-earth type high-silicon gamma-zeolite of preparation have higher content of rare earth and structure cell contraction preferably.
Method provided by the invention is that the y-type zeolite raw material that will contain rare earth carries out drying treatment, make its water-content be lower than 10 heavy %, then according to Y zeolite: the weight ratio of silicon tetrachloride=1: 0.1-0.9, feed the silicon tetrachloride gas that dry air carries, under temperature 150-600 ℃, reacted 10 minutes to 6 hours, and purged 5 minutes to 2 hours with dry air then, remove Na remaining in the zeolite with the decationized Y sieve water washing
+, Cl
-, Al
3+Etc. the solubility by product.
In the method provided by the present invention, the said y-type zeolite raw material that contains rare earth can be the Industrial products of REY or REHY, also can use the product of NaY zeolite gained after rare earth exchanged.
In general, said REY Industrial products, its content of rare earth is with RE
2O
3Count the heavy % of 6-14, Na
2O content is greater than 4 heavy %; Said REHY Industrial products, its content of rare earth is with RE
2O
3Count the heavy % of 10-20, Na
2O content is greater than 2 heavy %.
Said NaY zeolite is as follows through the process of rare earth exchanged: adopt silica alumina ratio greater than 3.5 NaY zeolite and rare earth chloride solution according to NaY: RECl
3: the weight ratio of H2O=1: 0.1-0.25: 5-15, in PH＞3.5, under temperature 80-90 ℃ the condition, carried out rare earth exchanged 30-60 minute, through or not drying obtain.
REY, REHY raw material or the NaY zeolite after the rare earth chloride solution exchange that the present invention is used, they all must pass through drying treatment before reaction, make the heavy % in its water-content＜10, are preferably＜5 heavy %.
The temperature of reaction of the silicon tetrachloride gas that said zeolite and air carry in the zeolite preparation method provided by the invention can be 150-600 ℃, and wherein preferred temperature is 200-500 ℃.
The inventive method has following advantage:
(1), made full use of the silicon tetrachloride gaseous substance and easily spread, be easy to diffuse into the characteristics of zeolite cavity, carry out effective isomorphous substitution reaction, a step realizes aluminium-eliminating and silicon-replenishing and takes off the sodium reaction, do not need repeatedly to exchange and repeatedly roasting.
(2), method provided by the invention compares with the described technology of CN1127161A, raw material sources are extensive, can be industrial REY, REHY zeolite, also can be the NaY zeolites; Particularly when being raw material with the NaY zeolite, rare earth chloride does not need drying to handle, but with the RECl of routine
3The aqueous solution and NaY zeolite exchange, and have made full use of NaY self and have had the characteristics of favourable absorption and desorption performance, obvious like this reduced said among the CN1127161A " with the solid RECl of NaY zeolite and porphyrize
3Mix while hot " the operation uncertainty, preparation condition is no longer harsh.
(3), the inventive method overcome REY effectively, in the REHY preparation process, the rare earth ion exchanged capacity is big, its structure cell is difficult for shrinking and the defective of super stabilizing, makes REY and REHY zeolite after the inventive method is handled, the heat and the hydrothermal stability of zeolite are improved; Also overcome on the other hand in the preparation REUSY zeolite process, after structure cell shrinks, the defective that the rare earth ion exchanged capacity is little.Through the type-Y high silicon zeolite of the inventive method preparation, have higher content of rare earth and structure cell contraction preferably, its RE
2O
3Content is the heavy % of 4-17, and structure cell is contracted in 2.425-2.460nm, Na
2The heavy % of O content＜1, differential heat collapse temperature＞1000 ℃.
To be further described method provided by the invention with example below.
Used NaY, REY, REHY is the Zhou village catalyst plant production of Qilu Petrochemical company in the example.
Example 1-5 explanation the invention provides the preparation process of method.
Example 1
With solid content is 65% NaY zeolite (silica alumina ratio is 4.0, and lattice constant is 2.473nm, and aluminum oxide is 24.8 heavy %, and sodium oxide is 16 heavy %), presses NaY: RECl
3: H
2O=1: 0.21: 15 ratio exchange RECl
3(chemical plant, packet header produces, technical grade, wherein La
2O
3Be 26 heavy %, Ce
2O
3Be 51 heavy %, the content of other rare earth oxide is 23 heavy %) under ℃ condition of PH＞3.5,90, carried out rare earth exchanged 30 minutes, filter then, wash, dry, will dry sample and put into reactor, be dried to the heavy % in water-content＜10.Press zeolite: SiCl
4=1: 0.7 weight ratio is carried SiCl with dry air
4React in (chemical plant, Dagu, Tianjin produce, technical grade), and 200 ℃ of temperature reacts 5 hours, purged 90 minutes with dry air then, with deionized water washing, filtration, in 110 ℃ of baking ovens, dry sample.RE in the sample
2O
3Content is 10.4 heavy % (La wherein
2O
3Be 6.31 heavy %, Ce
2O
3Be 2.08 heavy %, the content of other rare earth oxide is 1.46 heavy %), sodium oxide content is 0.44%, and lattice constant is 2.457nm, and differential heat collapse temperature is 1005 ℃.Sample is designated as G-R-1.
Example 2
With solid content is 75% NaY zeolite (silica alumina ratio is 4.5, and lattice constant is 2.471nm, and aluminum oxide is 2 3.6 heavy %, and sodium oxide is 15.8 heavy %), presses NaY: RECl
3: H
2O=1: 0.1: 15 ratio exchange RECl
3Under ℃ condition of PH＞3.5,95, carried out rare earth exchanged 60 minutes, filter then, washing, oven dry.To dry sample and put into reactor, be dried to water-content＜10%m, press NaY zeolite: SiCl
4=1: 0.1 weight ratio is carried SiCl with dry air
4React, 400 ℃ of temperature were reacted 3 hours, purged 120 minutes with dry air then, and washing and filtering promptly gets sample.RE in the sample
2O
3Content is 4.5 heavy % (La wherein
2O
3Be 2.97 heavy %, Ce
2O
3Be 0.9 heavy %, the content of other rare earth oxide is 0.63 heavy %), sodium oxide content is 0.30 heavy %, and lattice constant is 2.428nm, and differential heat collapse temperature is 1038 ℃.Sample is designated as G-R-2.
Example 3
With solid content is 75% NaY zeolite (silica alumina ratio is 5.05, and lattice constant is 2.466nm, and aluminum oxide is 21.2 heavy %, and sodium oxide is 15.8 heavy %), presses NaY: RECl
3: H
2O=1: 0.25: 15 ratio exchange RECl
3Under ℃ condition of PH＞3.5,85, carried out rare earth exchanged 45 minutes, filter then, wash, dry.To dry sample and put into reactor, be dried to the heavy % in water-content＜6, press NaY zeolite: SiCl
4=1: 0.8 weight ratio is carried SiCl with dry air
4React, 450 ℃ of temperature were reacted 30 minutes, purged 30 minutes with dry air then, and washing and filtering promptly gets sample.RE in the sample
2O
3Content is 8 heavy % (La wherein
2O
3Be 5.35 heavy %, Ce
2O
3Be 1.62 heavy %, the content of other rare earth oxide is the heavy % of 1.13m), sodium oxide content is 0.43 heavy %, and lattice constant is 2.440nm, and differential heat collapse temperature is 1002 ℃.Sample is designated as G-R-3.
Example 4
With solid content is that (silica alumina ratio is 5.05, and lattice constant is 2.469nm, and aluminum oxide is 20 heavy %, and sodium oxide is 4.4 heavy %, RE for 82% REHY zeolite
2O
3Content is 10 heavy %, wherein La
2O
3Be 6.6 heavy %, Ce
2O
3Be 2 heavy %, the content of other rare earth oxide is 1.4 heavy %) put into reactor, be dried to the heavy % in water-content＜7, press REHY: SiCl
4=1: 0.6 ratio is carried SiCl with dry air
4React, 250 ℃ of temperature were reacted 60 minutes, purged 20 minutes with dry air then, and washing and filtering promptly gets sample.RE in the sample
2O
3Content is 9.6 heavy % (La wherein
2O
3Be 5.35 heavy %, Ce
2O
3Be 6.34 heavy %, the content of other rare earth oxide is 1.34 heavy %), sodium oxide content is 0.26 heavy %, and lattice constant is 2.452nm, and differential heat collapse temperature is 1003 ℃.Sample is designated as G-R-4.
Example 5
With solid content is that (silica alumina ratio is 5.1, and lattice constant is 2.465nm, and aluminum oxide 19 heavy %, sodium oxide are 4.5 heavy %, RE for 85% REY zeolite
2O
3Content is 19.4 heavy % (La wherein
2O
3Be 12.8 heavy %, Ce
2O
3Be 3.9 heavy %, the content of other rare earth oxide is 2.7 heavy %) put into reactor, be dried to the heavy % in water-content＜5, press REY: SiCl
4=1: 0.5 ratio is carried SiCl with dry air
4React, 350 ℃ of temperature were reacted 120 minutes, purged 60 minutes with dry air then, and washing and filtering promptly gets sample.RE in the sample
2O
3Content is 13 heavy % (La wherein
2O
3Be 8.6 heavy %, Ce
2O
3Be 2.6 heavy %, the content of other rare earth oxide is 1.8 heavy %), sodium oxide content is 0.35 heavy %, and lattice constant is 2.456nm, and differential heat collapse temperature is 1008 ℃.Sample is designated as G-R-5.
Comparative Examples
Contrast medium is the REHY that the Zhou village catalyst plant is produced, and its preparation process is: the NaY zeolite under the PH=3.5-4.0 condition with RECl
3And NH
4After the exchange of Cl mixing solutions, obtained in 2 hours at 550 ℃ of roasting kiln roastings.The RE of this contrast zeolite
2O
3Content is 13.4m%, wherein La
2O
3Be 12.7m%, Ce
2O
3Be 2.7m%, the content of other rare earth oxide is 1.9m%, and lattice constant is 2.469nm, and sodium oxide content is 4.4m%, and differential heat collapse temperature is 985 ℃.
Example 6
Following example explanation the invention provides the catalytic performance and the hydrogen transfer activity of the type-Y high silicon zeolite of method preparation.
Type-Y high silicon zeolite G-R-1, G-R-3, G-R-5 with contrast medium and the inventive method preparation through 800 ℃/17h, after 100% steam treatment, estimate on heavy oil microreactor.
Appreciation condition is: zeolite loading amount 4g, raw materials used oil are vacuum gas oil, and character is listed in the table 1, and reaction conditions is 520 ℃, and weight hourly space velocity is 16 hours
-1, agent-oil ratio is 3.0.
Each components contents adopts gas chromatography in the reaction.
Evaluation result is listed in the table 2.
In the table 2:
Transformation efficiency=(gas content+gasoline content+coke+loss)/inlet amount * 100%;
Coke selectivity=coke yield/transformation efficiency;
Gasoline selective=gasoline yield/transformation efficiency;
Light oil yield=gasoline yield+gasoline yield;
Hydrogen transfer activity is used ∑ C
4 0/ ∑ C
4 =Expression, ∑ C
4 0/ ∑ C
4 =The numerical value height is the hydrogen transfer activity height then,
Help reducing olefin content in gasoline.
Table 2 is the result show, when transformation efficiency was close with contrast medium REHY, yield of light oil was suitable with the zeolite sample G-R-5 of the inventive method preparation, but gas obviously reduces, particularly ∑ C
4 0/ ∑ C
4 =Apparently higher than REHY1-3 unit, illustrate that supersiliceous zeolite provided by the invention has good hydrogen transfer activity, can effectively reduce alkene in the gasoline.The ∑ C of G-R-3 and G-R-1
4 0/ ∑ C
4 =All greater than REHY, and yield of light oil is suitable, and coke selectivity is better than REHY, and particularly the G-R-3 yield of light oil exceeds nearly 3 percentage points.
This example illustrates that the type-Y high silicon zeolite of method preparation provided by the invention has high activity, and good hydrogen transfer activity is the good active group member of hydro carbons processing catalytic cracking agent.Table 1
Table 2
| The stock oil parameter | Vacuum gas oil |
| Proportion, g/cm 3Viscosity, mm 250 ℃ of 100 ℃ of carbon residues of/s, heavy % | ????).8652 ? ????14.58 ????4.37 ????0.04 |
| Boiling range, ℃ initial boiling point 5% 1.0 20 30% 40 50% 60 70% 80 90% 95% is done | ? ????227 ????274 ????289 ????322 ????347 ????373 ????389 ????401 ????417 ????431 ????446 ????458 ????478 |
| Numbering | ????REHY | ????G-R-1 | ????G-R-2 | ????G-R-3 | ????G-R-5 |
| Product distributes, heavy % gas coke gasoline, diesel＞330 ℃ of transformation efficiencys | ? ????18.3 ????1.2 ????57.2 ????16.2 ????7.1 ????76.7 | ? ????11.7 ????1.0 ????57.0 ????16.3 ????14.0 ????69.7 | ? ????11.4 ????0.7 ????56.2 ????18.1 ????13.6 ????68.3 | ? ????11.1 ????1.0 ????59.9 ????16.7 ????11.3 ????72.0 | ? ????14.7 ????1.2 ????60.1 ????12.4 ????11.6 ????76.0 |
| ????∑C 0 4/∑C ＝ 4 | ????2.1 | ????2.6 | ????2.1 | ????2.6 | ????3.4 |
Claims (7)
1, a kind of preparation method of rare-earth type high-silicon gamma-zeolite, it is characterized in that the y-type zeolite that will contain rare earth carries out drying treatment, after making its water-content be lower than 10 heavy %, according to silicon tetrachloride: Y zeolite=0.1-0.9: 1 weight ratio feeds the silicon tetrachloride gas that dry air carries, under temperature 150-600 ℃, reacted 10 minutes to 6 hours, after the reaction, purged 5 minutes to 2 hours, remove Na remaining in the zeolite with the decationized Y sieve water washing with dry air
+, Cl
-, Al
3+Etc. the solubility by product.
2, according to the said method of claim 1, it is characterized in that the said y-type zeolite that contains rare earth be selected from the Industrial products of REY, REHY or NaY zeolite through rare earth exchanged after or the product of drying gained not.
3, according to the said method of claim 2, the content of rare earth that it is characterized in that said REY Industrial products is with RE
2O
3Count the heavy % of 6-14, Na
2O content is greater than 4 heavy %.
4, according to the said method of claim 2, the content of rare earth that it is characterized in that said REHY Industrial products is with RE
2O
3Count the heavy % of 10-20, Na
2O content is greater than 2 heavy %.
5,, it is characterized in that said NaY zeolite through the process of rare earth exchanged is according to the said method of claim 2: with silica alumina ratio greater than 3.5 NaY zeolite and rare earth chloride solution according to NaY: RECl
3: H
2The weight ratio of O=1: 0.1-0.25: 5-10 in PH＞3.5, under temperature 80-90 ℃ the condition, was carried out rare earth exchanged 30-60 minute.
6,, it is characterized in that saidly containing the water-content that rare earth Y type zeolite carries out after the drying treatment and being lower than 5 heavy % according to the said method of claim 1.
7,, it is characterized in that said temperature of reaction is 200-500 ℃ according to the said method of claim 1.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01115612 CN1121903C (en) | 2001-04-28 | 2001-04-28 | Process for preparing rare-earth type high-silicon gamma-zeolite |
| CA2445597A CA2445597C (en) | 2001-04-28 | 2002-04-24 | A rare earth zeolite y and the preparation process thereof |
| JP2002585092A JP4282059B2 (en) | 2001-04-28 | 2002-04-24 | Method for preparing rare earth zeolite Y |
| DE60236792T DE60236792D1 (en) | 2001-04-28 | 2002-04-24 | RARE METAL Y-ZEOLITE AND METHOD OF MANUFACTURING THEREOF |
| PCT/CN2002/000288 WO2002087758A1 (en) | 2001-04-28 | 2002-04-24 | A rare earth zeolite y and the preparation process thereof |
| EP02726042A EP1390141B1 (en) | 2001-04-28 | 2002-04-24 | A rare earth zeolite y and the preparation process thereof |
| US10/132,911 US6787123B2 (en) | 2001-04-28 | 2002-04-26 | Rare earth zeolite Y and the preparation process thereof |
| US10/811,865 US6991774B2 (en) | 2001-04-28 | 2004-03-30 | Rare earth zeolite Y and the preparation process thereof |
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|---|---|---|---|
| CN 01115612 CN1121903C (en) | 2001-04-28 | 2001-04-28 | Process for preparing rare-earth type high-silicon gamma-zeolite |
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| Publication Number | Publication Date |
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| CN1382525A true CN1382525A (en) | 2002-12-04 |
| CN1121903C CN1121903C (en) | 2003-09-24 |
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|---|---|---|---|
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