CN1121903C - Process for preparing rare-earth type high-silicon gamma-zeolite - Google Patents

Process for preparing rare-earth type high-silicon gamma-zeolite Download PDF

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Publication number
CN1121903C
CN1121903C CN 01115612 CN01115612A CN1121903C CN 1121903 C CN1121903 C CN 1121903C CN 01115612 CN01115612 CN 01115612 CN 01115612 A CN01115612 A CN 01115612A CN 1121903 C CN1121903 C CN 1121903C
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zeolite
heavy
rare earth
content
nay
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CN1382525A (en
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杜军
李峥
王鹏
达志坚
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to JP2002585092A priority patent/JP4282059B2/en
Priority to CA2445597A priority patent/CA2445597C/en
Priority to DE60236792T priority patent/DE60236792D1/en
Priority to PCT/CN2002/000288 priority patent/WO2002087758A1/en
Priority to EP02726042A priority patent/EP1390141B1/en
Priority to US10/132,911 priority patent/US6787123B2/en
Publication of CN1382525A publication Critical patent/CN1382525A/en
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Publication of CN1121903C publication Critical patent/CN1121903C/en
Priority to US10/811,865 priority patent/US6991774B2/en
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Abstract

The present invention relates to a process for preparing rare-earth type high-silicon Y-zeolite, which comprises the steps: drying the rare-earth contained Y-zeolite until the water content is less than 10 wt. %, introducing SiCl4 gas carried by dried air in the weight ratio of 0.1-0.9 (SiCl4): 1 (Y-zeolite), reacting for 10 minutes to 6 hours at 150 to 600 DEG C, scavenging with dried air for 5 minutes to 2 hours after the reaction, and washing and removing residual Na+, Cl-, Al3+ and other soluble by-products with decationic water. Compared with the prior art, the process has the advantages of simpler process, energy saving and no pollution.

Description

A kind of preparation method of rare-earth type high-silicon gamma-zeolite
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 consciousness 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 transformation, 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 does not have activity to acid or catalytic 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 thermal decomposition 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 structural deterioration.
Since the sixties, zeolite catalyst has been widely used in the oil refining processing, 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 salting liquid 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 Bronsted acid is less.People to increase catalytic activity, introduce an amount of NH in order to introduce more Bronsted acid in catalyst when rare earth ion exchanged 4+Obtain REHY, be about to the salting liquid and the NH of rare earth 4+Salting liquid 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 RFCC 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 (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 steam 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 a kind of approach of USY activity, 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 ion exchange 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 not only to expend the energy, and easily pollute through high-temperature roasting, oven dry.
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 the drying processing, make its water content be lower than 10 heavy %, then according to the 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 accessory substance.
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: H 2The weight ratio of O=1: 0.1-0.25: 5-15 in PH＞3.5, under temperature 80-90 ℃ the condition, was 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 be handled through super-dry before reaction, make the heavy % in its water content＜10, are preferably＜5 heavy %.
The reaction temperature of the silicon tetrachloride gas that the said name of boiling is carried with air in the zeolite preparation method provided by the invention can be 150-600 ℃, and wherein preferably temperature is 200-500 ℃.
The inventive method has following advantage:
(1), made full use of the silicon tetrachloride gaseous material 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 good adsorption 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 Y-type high-Si 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 aluminium oxide is 24.8 heavy %, and sodium oxide molybdena 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 aluminium oxide is 23.6 heavy %, and sodium oxide molybdena 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 weight %, 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 aluminium oxide is 21.2 heavy %, and sodium oxide molybdena 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 aluminium oxide is 20 heavy %, and sodium oxide molybdena 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 aluminium oxide 19 heavy %, sodium oxide molybdena are 4.5 heavy %, RE for 85% REY zeolite 2O 3Content is 194 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 mixed solution, 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 Y-type high-Si zeolite of method preparation.
Y-type high-Si 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 (VGO), and character is listed in the table 1, and reaction condition is 520 ℃, and weight (hourly) space velocity (WHSV) is 16 hours-1, and 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:
Conversion ratio=(gas content+gasoline content+coke+loss)/inlet amount * 100%;
Coke selectivity=coke yield/conversion ratio;
Gasoline selective=gasoline yield/conversion ratio;
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 conversion ratio 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 silica-rich 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 Y-type high-Si 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
The feedstock oil parameter Vacuum gas oil (VGO)
Proportion, g/cm 3Viscosity, mm 250 ℃ of 100 ℃ of carbon residues of/s, heavy % 0.8652 14.58 4.37 0.04
Boiling range; ℃ initial boiling point 5% 10 20 30% 40 50% 60 70% 80 90% 95% is done 227 274 289 322 347 373 389 401 417 431 446 458 478
Table 2
Numbering REHY G-R-1 G-R-2 G-R-3 G-R-5
Product distributes, heavy % gas coke gasoline, diesel＞330 ℃ of conversion ratios 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 the drying processing, 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+The solubility accessory substance.
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 dry the processing and being lower than 5 heavy % according to the said method of claim 1.
7,, it is characterized in that said reaction temperature is 200-500 ℃ according to the said method of claim 1.
CN 01115612 2001-04-28 2001-04-28 Process for preparing rare-earth type high-silicon gamma-zeolite Expired - Fee Related CN1121903C (en)

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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
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
JP2002585092A JP4282059B2 (en) 2001-04-28 2002-04-24 Method for preparing rare earth zeolite Y
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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