CN1636633A - Prepn process of cracking catalyst - Google Patents
Prepn process of cracking catalyst Download PDFInfo
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- CN1636633A CN1636633A CN 200410096001 CN200410096001A CN1636633A CN 1636633 A CN1636633 A CN 1636633A CN 200410096001 CN200410096001 CN 200410096001 CN 200410096001 A CN200410096001 A CN 200410096001A CN 1636633 A CN1636633 A CN 1636633A
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- molecular sieve
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Abstract
The cracking catalyst preparing process includes twice or more times of contact mixing between NaY molecular sieve and 6-94 % concentration ammonium salt aqua in the weight ratio of 1 to 0.1-24 at normal pressure and at temperature higher than 90 deg.c and lower than the boiling point of the ammonium salt aqua to lower the Na2O content inside the molecular sieve to below 1.5 wt%, mixing with carrier, and drying. The preparation process has short process, low power consumption and high dispersivity of the molecular sieve, and the catalyst has activity higher that in available technology.
Description
Technical field
The invention relates to a kind of method for preparing cracking catalyst, further say so and contain the method for the cracking catalyst of super-stable Y molecular sieves about a kind of preparation.
Background technology
The step of prior art for preparing cracking catalyst is: (1) NaY molecular sieve after filtration, the exchange of ammonium, dry, step such as water roasting, the exchange of secondary ammonium, drying and the roasting of secondary water make ultra-steady Y molecular sieve; (2) ultra-steady Y molecular sieve mixes with carrier through making beating, after grinding, and spray-dried again, washing and drying and other steps obtain product.For example, disclosed method is to adopt 3%～5% ammonium salt solution repeatedly to exchange the sodium content that reduces in the molecular sieve among the USP4415439, adopting once or twice, roasting prepares super stable molecular sieve, again will be super steady Y become glue to spray drying one-tenth catalyzer through grinding the making beating back with carrier, exist long flow path, energy consumption big, lose deficiency many, molecular sieve poor dispersion in carrier.
Disclosed catalyzer among the USP4085069, wherein the ammonium exchange process of the NaY molecular sieve that discloses among the embodiment 1 is to be approximately the ammonium nitrate solution of 77 heavy % under 350 °F with concentration, in the autoclave, boost and carry out under the power (being about 16atm) certainly, and when adopting autoclave, equipment cost and running cost are all higher, also are not easy to operate continuously (other operation all is an atmospheric operation).
Summary of the invention
Purpose of the present invention is exactly at the deficiencies in the prior art, provides that a kind of flow process is short, energy consumption is low, is convenient to the method for preparing cracking catalyst of operate continuously.
The method for preparing cracking catalyst provided by the invention, it is characterized in that with the ammonium salt aqueous solution of NaY molecular sieve and concentration 6～94 heavy % normal pressure, greater than 90 ℃ be that 0.1～24 weight ratio contacts more than twice or twice to the condition that is not more than the ammonium salt aqueous solution boiling temperature according to ammonium salt and molecular sieve, make Na in the molecular sieve
2O content is reduced to below the 1.5 heavy %, mixes with carrier, drying again.
Among the preparation method provided by the invention, said NaY molecular sieve can adopt degree of crystallinity greater than 80%, SiO
2/ Al
2O
3Be 3～6, Na
2O content is 8～12% NaY molecular sieve; Also can adopt through conventional ammonium exchange step Na
2O content is lower than 4.5 heavy %NaY molecular sieves, and wherein said conventional ammonium exchange step is well known to those of ordinary skill in the art, i.e. the processes that contacting with molecular sieve for 70 ℃～90 ℃ times with the ammonium salt aqueous solution of 2～5 heavy %.
Among the preparation method provided by the invention, said ammonium salt is used always by the present technique field, generally is selected from ammonium nitrate, ammonium chloride or ammonium sulfate.In the said treatment condition, temperature preferred 100 ℃ to the boiling temperature that is not more than ammonium salt aqueous solution.
The ammonium salt aqueous solution of different sorts and concentration, the boiling spread under normal pressure is also different, so service temperature also has difference.For example, concentration is the aqueous ammonium nitrate solution of 9.09 heavy % because its boiling point is 101 ℃, so service temperature greater than 90 ℃ to being not more than 101 ℃; Concentration is the aqueous ammonium nitrate solution (160 ℃ of boiling points) of 93.20 heavy %, service temperature greater than 90 ℃ to being not more than 160 ℃; Concentration is the aqueous ammonium chloride solution (115 ℃ of boiling points) of 46.94 heavy %, service temperature greater than 90 ℃ to being not more than 115 ℃; Concentration is the ammonium sulfate solution (115 ℃ of boiling points) of 53.55 heavy %, service temperature greater than 90 ℃ to being not more than 115 ℃.
For aqueous ammonium nitrate solution, concentration preferred 15.0～90.0 heavy %, more preferably 60.0～90.0 heavy %; For aqueous ammonium chloride solution, concentration preferred 10.0～36.0 heavy %, more preferably 16.0～30.0 heavy %; For ammonium sulfate solution, concentration preferred 10.0～55.0 heavy %, more preferably 30.0～40.0 heavy %.
Among the preparation method provided by the invention, the weight ratio of said ammonium salt and molecular sieve be preferably greater than or equal 0.8, more preferably greater than or equal 1.
Among the preparation method provided by the invention, in NaY molecular sieve and ammonium salt aqueous solution operating of contacts, according to Na in the used NaY molecular sieve
2The difference of amounts of ammonium salt and duration of contact and temperature in O content, the ammonium salt aqueous solution, usually operation will be carried out more than twice or twice, certainly, the number of times that such operation is carried out the more, Na in the molecular sieve
2O content then can more lack.Gained molecular sieve, Na are handled in contact through ammonium salt aqueous solution
2O content weighs below the % 1.0, and prepared catalyzer has better light oil microactivity, therefore, and Na
2O content is preferably below 1.0 heavy %.But, consider the factor that simplifies the operation and reduce cost, preferably carry out the operating of contacts of twice molecular sieve and ammonium salt aqueous solution, each time is 10 minutes～10 hours, usually after carrying out the first time, Na in the molecular sieve
2O content can be reduced to below the 2 heavy %, again after, generally can make Na
2O content reaches below the 1.5 heavy %, better effects if be below 1.0 heavy %.In repeating step, in the ammonium salt aqueous solution operating parameterss such as amounts of ammonium salt, duration of contact and temperature with last time can be identical or different.
In the method provided by the invention, said cracking catalyst is made up of Y zeolite and carrier, and wherein said carrier is binding agent and clay.
Said binding agent can be selected from a kind of in aluminium colloidal sol, pseudo-boehmite, silicon sol, the phosphorus aluminium glue or two or more mixture wherein, the double aluminium binder that wherein preferred aluminium colloidal sol and pseudo-boehmite are formed.
Said clay is the cracking catalyst common clay, as kaolin, the intercalation soil of Peng, sepiolite etc.
Adopt the method for preparing cracking catalyst provided by the invention, have the following advantages:
(1) preparation method provided by the invention, under normal pressure, carry out, solve prior art NaY molecular sieve and fallen sodium in autoclave, the equipment cost of being brought and the running cost that carry out the ammonium swap operation under the power of boosting are all higher, are not easy to the problem of operate continuously (other operation all is an atmospheric operation).
(2) preparation method provided by the invention by two steps or the above exchange of two steps, drops to the sodium content of molecular sieve below the 1.5 heavy %, and filter cake directly mixes with carrier, directly obtains catalyzer through super-dry.Without any calcination steps, energy consumption is reduced greatly in molecular sieve and the catalyst preparation process; In addition, molecular sieve is not assembled, and dispersity is better than conventional cracking catalyst, has overcome the deficiency of molecular sieve poor dispersion in carrier in the prior art.For example, adopt in the catalyzer of prior art for preparing the granularity V (0 of molecular sieve, 0.5)=4.2 μ m, V (0,0.9)=13.3 μ m (laser particle analyzer mensuration), promptly 50% granularity is less than 4.2 μ m, 90% granularity must make V (0,0.9)≤10.0 μ m through grinding less than 13.3 μ m; And the catalyzer that adopts the inventive method to prepare, the molecular sieve granularity is V (0,0.5)=3.7 μ m, V (0,0.9)=9.8 μ m, illustrates that its granularity is little, is convenient to disperse.
(3) cracking catalyst of employing method preparation provided by the invention has higher light oil microactivity than the catalyzer of prior art for preparing.For example, the catalyzer of examples preparation, its light oil microactivity are all more than 77, and the light oil microactivity of the catalyzer of Comparative Examples preparation has only 75.
Embodiment
Following example will the invention will be further described.
Reagent used in the example is except that special mark, and its specification is chemical pure.
Example 1
With (NH
4)
2SO
4, water and NaY according to 10: 10: 1 weight ratio with (NH
4)
2SO
4Mix with water stir after, add NaY molecular sieve (its Na
2O content is 3.5%, and degree of crystallinity is 85.9, and structure cell is 24.71 ), be warming up to 106 ℃, constant temperature stirred 1 hour, Na behind the filtration washing
2O content is 1.1%, repeats above step more once, Na behind the filtration washing
2O content is 0.6%.The molecular sieve granularity is V (0,0.5)=3.7 μ m, V (0,0.9)=9.8 μ m.
350 grams through above-mentioned steps handle the molecular sieve filter cake, (contain Al with 200 gram pseudo-boehmites (solid content 34.8 heavy %, Shandong Aluminum Plant's product), 100 gram aluminium colloidal sols
2O
321 heavy %, Qilu Petrochemical company catalyst plant product) and 350 gram kaolin (solid content 85.0%, China Kaolin Co., Ltd's Industrial products) mix stirring 30 minutes, after 180 ℃ of dryings, make catalyzer again.
This catalyzer molecular sieve lattice constant behind 800 ℃ of 4 hours hydrothermal agings is 24.34 , and light oil microactivity is 80.
Example 2～15
When method provided by the invention is adopted in example 2～15 explanation, molecular sieve, the ammonium sulfate influence different with the ratio of water consumption.
In example 2～5, the Na of raw molecule sieve
2O content is 3.5 heavy %.
In example 6～15, the Na of raw molecule sieve
2O content is 8.9 heavy %.
Other raw material and preparation process are with example 1.
Molecular sieve size range rule is with example 1 sample.
The results are shown in Table 1.
Table 1
| Example number | Ammonium salt aqueous solution concentration (%) | The weight ratio of ammonium sulfate and molecular sieve | Temperature (℃) | Once exchange Na in the filter cake of back 2O content (heavy %) | Na in the filter cake of secondary exchange back 2O content (heavy %) | The lattice constant () of catalyst molecular sieve behind 800 ℃ of 4 hours hydrothermal agings | Light oil microactivity |
| ????2 | ????40.0 | ?2∶1 | ????104 | ????1.9 | ????1.0 | ????24.33 | ????85 |
| ????3 | ????50.0 | ?3∶1 | ????107 | ????1.8 | ????0.8 | ????24.32 | ????86 |
| ????4 | ????50.0 | ?6∶1 | ????107 | ????1.6 | ????0.8 | ????24.32 | ????88 |
| ????5 | ????50.0 | ?10∶1 | ????107 | ????1.1 | ????0.6 | ????24.32 | ????89 |
| ????6 | ????52.3 | ?11∶1 | ????110 | ????0.9 | ????0.5 | ????24.33 | ????86 |
| ????7 | ????44.4 | ?8∶1 | ????105 | ????2.2 | ????1.0 | ????24.33 | ????84 |
| ????8 | ????41.2 | ?7∶1 | ????104 | ????2.2 | ????1.1 | ????24.32 | ????84 |
| ????9 | ????37.5 | ?6∶1 | ????104 | ????2.3 | ????1.1 | ????24.35 | ????83 |
| ????10 | ????33.3 | ?5∶1 | ????103 | ????2.3 | ????1.1 | ????24.36 | ????83 |
| ????11 | ????28.6 | ?4∶1 | ????102 | ????2.5 | ????1.2 | ????24.35 | ????81 |
| ????12 | ????23.1 | ?0.27∶1 | ????102 | ????2.7 | ????1.3 | ????24.38 | ????81 |
| ????13 | ????10.2 | ?0.11∶1 | ????100 | ????2.8 | ????1.4 | ????24.36 | ????82 |
| ????14 | ????15.4 | ?0.17∶1 | ????101 | ????2.7 | ????1.3 | ????24.36 | ????80 |
| ????15 | ????23.3 | ?0.33∶1 | ????102 | ????3.1 | ????1.5 | ????24.34 | ????77 |
As can be seen from Table 1, the ammonium sulfate consumption is big more, and the residual sodium oxide content of molecular sieve is low more, and the molecular sieve structure cell is more little after the roasting; Water consumption is big more, and the residual sodium oxide content of molecular sieve is low more.
From table 1 result equally as can be seen, the catalyzer of the inventive method preparation at 24.32～24.38 , illustrates that the structural stability of molecular sieve in the catalyzer is good through the lattice constant of 800 ℃ of hydrothermal agings after 4 hours.
Example 16～28
NaY molecular sieve, the influence different of ammonium nitrate consumption when the explanation of this example is handled with the aqueous ammonium nitrate solution of different ammonium amounts with the ratio of water consumption.
Treatment temp is 110 ℃, and raw molecule sieves with example 6.Molecular sieve size range rule is with example 1 sample.The results are shown in Table 2.
Table 2
| Example number | Ammonium salt aqueous solution concentration % | The weight ratio of ammonium nitrate and molecular sieve | Once exchange Na in the filter cake of back 2O (heavy %) | Na in the filter cake of secondary exchange back 2O (heavy %) | The lattice constant () of catalyzer molecular sieve behind 800 ℃ of 4 hours hydrothermal agings | Light oil microactivity |
| ??16 | ????78.6 | ????22∶1 | ????0.74 | ????0.4 | ????24.33 | ????89 |
| ??17 | ????88.9 | ????24∶1 | ????0.65 | ????0.3 | ????24.32 | ????89 |
| ??18 | ????85.0 | ????17∶1 | ????1.4 | ????0.8 | ????24.32 | ????87 |
| ??19 | ????81.3 | ????13∶1 | ????1.4 | ????0.8 | ????24.32 | ????87 |
| ??20 | ????75.0 | ????9∶1 | ????2.0 | ????1.0 | ????24.33 | ????85 |
| ??21 | ????62.5 | ????5∶1 | ????2.5 | ????1.2 | ????24.33 | ????82 |
| ??22 | ????85.7 | ????6∶1 | ????2.3 | ????1.1 | ????24.32 | ????83 |
| ??23 | ????85.7 | ????12∶1 | ????1.5 | ????0.8 | ????24.35 | ????86 |
| ??24 | ????80.0 | ????4∶1 | ????2.5 | ????1.2 | ????24.36 | ????82 |
| ??25 | ????80.0 | ????8∶1 | ????1.7 | ????0.9 | ????24.35 | ????87 |
| ??26 | ????75.0 | ????18∶1 | ????1.9 | ????1.0 | ????24.38 | ????85 |
| ??27 | ????71.4 | ????15∶1 | ????1.2 | ????0.7 | ????24.36 | ????88 |
| ??28 | ????66.7 | ????12∶1 | ????1.7 | ????0.9 | ????24.36 | ????86 |
By identical with the table 1 as can be seen conclusion of table 2 result, can illustrate in addition when adopting aqueous ammonium nitrate solution fall that the sodium effect is better than adopting ammonium sulfate solution the sodium effect falls.
Example 29～32
Raw material is with example 1.The results are shown in Table 3
Table 3
| Example number | Temperature and treatment time | Ammonium salt kind and concentration of aqueous solution (%) | The ratio of ammonium salt and molecular sieve | Once exchange NaO in the filter cake of back 2Content (heavy %) | NaO in the filter cake of secondary exchange back 2Content (heavy %) | The lattice constant () of catalyst molecular sieve behind 800 ℃ of 4 hours hydrothermal agings | Light oil microactivity |
| ????29 | 95 ℃ 1 hour | Ammonium nitrate 15 | ????2∶1 | ????2.5 | ????1.9 | ????24.33 | ????81 |
| ????30 | 160 ℃ 1 hour | Ammonium nitrate 94 | ????2∶1 | ????1.6 | ????0.9 | ????24.32 | ????87 |
| ????31 | 115 ℃ 1 hour | Ammonium sulfate 55 | ????2∶1 | ????1.8 | ????1.0 | ????24.33 | ????86 |
| ????32 | 115 ℃ 1 hour | Ammonium chloride 48 | ????2∶1 | ????2.0 | ????1.1 | ????24.32 | ????85 |
Comparative Examples
This Comparative Examples explanation prior art adopts the ultra-steady Y molecular sieve of preparation after two hand over two roastings to prepare the process of catalyzer.
350 gram super-stable Y molecular sieves (Chang Ling catalyst plant products, the granularity V (0 of molecular sieve, 0.5)=4.2 μ m, V (0,0.9)=13.3 μ m), mix stirring 30 minutes with 200 gram pseudo-boehmites, 100 gram aluminium colloidal sols and 350 gram kaolin, filter back 120 ℃ of dryings, 550 ℃ of roastings make catalyzer again after washing and drying.This catalyzer through 800 ℃ 4 hours aging after the Y zeolite structure cell be 24.33 , light oil microactivity is 75.
Claims (17)
1, a kind of method for preparing cracking catalyst, it is characterized in that with NaY molecular sieve and concentration be 6～94 heavy % ammonium salt aqueous solution normal pressure, greater than 90 ℃ be that 0.1～24: 1 weight ratio contacts and mixes more than twice or twice to the condition that is not more than the ammonium salt aqueous solution boiling temperature according to ammonium salt and molecular sieve, make Na in the molecular sieve
2O content is reduced to below the 1.5 heavy %, mixes with carrier, drying again.
2, according to the method for claim 1, said NaY molecular sieve crystallinity greater than 80%, SiO
2/ Al
2O
3Be 3～6, Na
2O content is 8～12 heavy %.
3, according to the method for claim 1, the ammonium salt aqueous solution of said NaY molecular sieve elder generation and 2～5 heavy % makes its Na 70～90 ℃ of exchanges down
2O content is lower than 4.5 heavy %.
4, according to the method for claim 1, said ammonium salt is an ammonium nitrate, and the concentration of its aqueous solution is 15.0～90.0 heavy %.
5, according to the method for claim 4, the concentration of said aqueous ammonium nitrate solution is 60.0～90.0 heavy %.
6, according to the method for claim 1, said ammonium salt is an ammonium chloride, and the concentration of its aqueous solution is 10.0～36.0 heavy %.
7, according to the method for claim 6, the concentration of said aqueous ammonium chloride solution is 16.0～30.0 heavy %
8, according to the method for claim 1, said ammonium salt is an ammonium sulfate, and the concentration of its aqueous solution is 10.0～55.0 heavy %.
9, according to the method for claim 8, the concentration of said ammonium sulfate solution is 30.0～40.0 heavy %.
10, according to the method for claim 1, the weight ratio of ammonium salt and molecular sieve is more than or equal to 0.8.
11, according to the method for claim 1, the weight ratio of ammonium salt and molecular sieve is more than or equal to 1.
12, according to the method for claim 1, said treatment condition be 100 ℃ to being not more than the ammonium salt aqueous solution boiling temperature.
13, according to the process of claim 1 wherein that said cracking catalyst is made up of molecular sieve and carrier.
14, according to the method for claim 13, said carrier is binding agent and clay.
15, according to the method for claim 14, said binding agent is selected from a kind of in aluminium colloidal sol, pseudo-boehmite, silicon sol, the phosphorus aluminium glue or two or more mixture wherein.
16, according to the method for claim 13, said binding agent is the mixture of aluminium colloidal sol and pseudo-boehmite.
17, according to the method for claim 1, it is characterized in that the NaY molecular sieve is contacted twice with ammonium salt aqueous solution, make Na in the molecular sieve
2O content is reduced to below the 1.0 heavy %, mixes with carrier, drying again.
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|---|---|---|---|
| CNB2004100960017A CN100363105C (en) | 2003-11-28 | 2004-11-26 | Prepn process of cracking catalyst |
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|---|---|---|---|
| CN200310115509 | 2003-11-28 | ||
| CN200310115509.2 | 2003-11-28 | ||
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| Publication Number | Publication Date |
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| CN1636633A true CN1636633A (en) | 2005-07-13 |
| CN100363105C CN100363105C (en) | 2008-01-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106809854A (en) * | 2015-11-30 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of preparation method of porous material |
| CN106809855A (en) * | 2015-11-30 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of porous material and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085069A (en) * | 1976-08-27 | 1978-04-18 | Filtrol Corporation | Hydrothermally stable catalysts containing ammonium faujasite zeolites |
| US4058484A (en) * | 1976-09-09 | 1977-11-15 | Filtrol Corporation | Ammonium faujasite zeolites |
| US4415439A (en) * | 1980-10-28 | 1983-11-15 | W. R. Grace & Co. | Catalytic cracking catalyst |
| US4357265A (en) * | 1980-10-28 | 1982-11-02 | W. R. Grace & Co. | Catalytic cracking catalyst |
| NL8103069A (en) * | 1980-10-28 | 1982-05-17 | Grace W R & Co | METHOD FOR PREPARING CATALYTIC CRACKING CATALYSTS |
| US4699893A (en) * | 1985-04-29 | 1987-10-13 | Engelhard Corporation | Fluid cracking catalyst and method of making same from waste catalyst manufacture fines |
| US5013699A (en) * | 1988-04-07 | 1991-05-07 | Uop | Novel zeolite compositions derived from zeolite Y |
| CN1078819C (en) * | 1997-08-27 | 2002-02-06 | 中国石油化工集团公司 | Process for preparing overstable gamma zeolite |
| CN1104955C (en) * | 1998-01-19 | 2003-04-09 | 兰炼石化院高新石化开发公司 | Once-exchanging once-calcining phosphoreted Y-zeolite cracking catalyst and preparing method thereof |
| JP4833460B2 (en) * | 2001-09-26 | 2011-12-07 | Ｊｘ日鉱日石エネルギー株式会社 | Super stable Y-type zeolite |
-
2004
- 2004-11-26 CN CNB2004100960017A patent/CN100363105C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106809854A (en) * | 2015-11-30 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of preparation method of porous material |
| CN106809855A (en) * | 2015-11-30 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of porous material and preparation method thereof |
| CN106809855B (en) * | 2015-11-30 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of porous material and preparation method thereof |
| CN106809854B (en) * | 2015-11-30 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of preparation method of porous material |
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|---|---|
| CN100363105C (en) | 2008-01-23 |
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