CN1362367A - Y-zeolite modifying method with RE ion and its product - Google Patents
Y-zeolite modifying method with RE ion and its product Download PDFInfo
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- CN1362367A CN1362367A CN 01106027 CN01106027A CN1362367A CN 1362367 A CN1362367 A CN 1362367A CN 01106027 CN01106027 CN 01106027 CN 01106027 A CN01106027 A CN 01106027A CN 1362367 A CN1362367 A CN 1362367A
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Abstract
The NaY zeolite can be used as raw material, undergone the processes of NH4(+) exchange, aqueous vapour treatment, treatment by using mixed solution containing H(+), NH4(+) and RE (3+), finally drying and roasting to obtain the invented modified gamma zeolite, containing rate earth. It can be used as catalyst acid component for production process of converting heavy distillate oil containig impurities of sulfur, nitrogen and oxygen, etc. into light and heavy naphtha, specially, it also can be used as catalyst acid component for hydrogenation cracking process.
Description
The present invention relates to method of Y zeolite modification and products thereof, especially contain modified Y zeolite preparation method of rare earth ion and products thereof.
The modified Y zeolite that contains rare earth ion is a most frequently used active principle in current hydrocracking and the catalytic cracking reaction catalyzer, but order, condition, the pH value of solution value of earth solution exchange have a significant impact the performance of rare earth ion exchanged and effect thereof.
United States Patent (USP) 4,584,287,4, in 429,053, the NaY zeolite is then carried out steam-treated with rare earth ion exchanged earlier, because the shielding effect and the support of rare earth ion make steam-treated process dealuminzation difficulty, its unit cell parameters before steam-treated increases to 2.465～2.475nm, and is 2.420～2.464nm after handling, and reduces unit cell parameters temperature required higher (593～733 ℃).
United States Patent (USP) 5,340, the SiO of raw material NaY zeolite in 957,5,206,194 methods that provide
2/ Al
2O
3Than being 6.0, cost is higher.And this patent also is after the NaY zeolite is carried out rare earth exchanged, to carry out hydrothermal treatment consists again, has aforesaid U.S. Patent 4,584 equally, 287 and 4,429, and the shortcoming of 053 patent.
The object of the present invention is to provide a kind of modified Y zeolite preparation method who contains rare earth and products thereof, be intended to reduce cost, simplify the operation, improve the distribution of rare earth on zeolite.
The method of Y zeolite modification of the present invention comprises: with the NaY zeolite is raw material, earlier through the ammonium exchange handle, carry out then hydro-thermal vapour handle, again with containing H
+, NH
4 +And RE
3+Solution-treated after the washing, drying, roasting obtains the modified zeolite product at last.
The relative crystallinity of described NaY zeolite raw material better is greater than 95%, preferably greater than 97%, and SiO
2/ Al
2O
3Than being 4.8～5.2, preferably 5.0～5.2, unit cell parameters is 2.464～2.470nm.Its X-ray diffractogram preferably meets United States Patent (USP) 3,130,007 diffraction result.
The concrete grammar of described ammonium exchange can carry out with reference to following steps: the NaY zeolite is contacted with ammonium salt solution, and used ammonium salt can be a mineral acid salt, as NH
4Cl, NH
4NO
3, (NH
4)
2CO
3, (NH
4)
2SO
4, can be organic acid salt also, as NH
4Ac etc.Ammonium salt exchange temperature is 40～120 ℃, and preferably 80～100 ℃, the time is 0.5～4 hour, and preferably 1～3 hour, zeolite was 1: 3～15 with the ratio of ammonium salt solution weight, preferably 1: 5～10.Exchange is under agitation carried out, the exchange after-filtration, and so operation repeats 1～5 time, until intermediate product NH
4Na in the NaY zeolite
2The O weight content reduces to 1.5%～3.5%, and preferably 1.8%～3.0%, so that zeolite migrates to zeolite surface with a part of aluminium from zeolite framework in the hydrothermal treatment consists process.
The detailed process of described hydrothermal treatment consists can be carried out with reference to following steps: the NH of above-mentioned ammonium salt exchange back gained
4The NaY zeolite places in the hydrothermal treatment consists stove, and is moisture with himself, contain NH
4 +The water vapor and the ammonia that produce are handled, temperature is 400～800 ℃, and preferably 550～750 ℃, system pressure is 0.05～0.5MPa, 0.1～0.3MPa preferably, the steam dividing potential drop is 0.5～3: 1 with the ratio of ammonia dividing potential drop, preferably 1～2: 1, and the time of hydrothermal treatment consists is 1～8 hour, preferably 2～4 hours, hydrothermal treatment consists finishes, and pressure release feeds N
2The zeolite temperature is reduced to room temperature, take out intermediates.Structure cell is contracted to 2.435～2.455nm in this process, 2.440～2.448nm preferably, skeleton SiO
2/ Al
2O
3Than being increased to 5.2～10.5, more suitable scope is 5.5～8.5.
Zeolite after the above-mentioned hydrothermal treatment consists also needs with containing H
+, NH
4 +And RE
3+Solution-treated, purpose is further to reduce Na in the zeolite
2The content of O is removed the non-framework aluminum that migrates to zeolite surface in the hydrothermal treatment consists process, with the acidity and the acid distribution of modulation zeolite.
The intermediates that obtain after the hydrothermal treatment consists are with containing H
+, NH
4 +, RE
3+Mixing solutions handle, actual conditions is: various ionic concns are respectively in the solution: H
+Concentration be 0.01～0.15mol/L, preferably equal 0.05～0.10mol/L, NH
4 +Concentration is 0.3～2.0mol/L, 0.5～1.0mol/L preferably, RE
3+Concentration expressed in percentage by weight in solution is 0.01～5.0%, preferably 0.05～3.0%, and RE
3+Can be independent rare earth ion, as lanthanum, cerium, praseodymium, rubidium etc., also can be mixed rare earth ions, and the negatively charged ion in the solution can be Cl
-, NO
3 -, SO
4 =, CO
3 =Deng, treatment condition are: system temperature is at 40～120 ℃, be preferably in 80～100 ℃, zeolite is 1: 3～15 with the ratio of solution weight, preferably 1: 5～10, the solution-treated time is 0.5～4 hour, preferably 1～2 hour, solution-treated is carried out 1～3 time repeatedly, preferably 1～2 time, all carry out mother liquor after each solution-treated and separate, the filter cake that the mother liquor of last solution-treated obtains after separating carried out drying 1～3 hour at 100～120 ℃, dried sample is at 400～750 ℃, and roasting promptly got modified Y zeolite product of the present invention in 2～6 hours in air atmosphere.
According to above method gained modified Y zeolite product characteristics be: the total weight percent with modified Y zeolite is a benchmark, RE
3+Content be 0.1%～5.0%, preferably 0.3%～3.0%, Na
2O content is 0.05%～0.5%, preferably 0.05%～0.3%; The silica alumina ratio of Y zeolite is 5.0～20.0, preferably 7.0～16.0, and lattice constant is 2.435～2.455nm, 2.438～2.445nm preferably, relative crystallinity is 85%～100%, preferably 90%～100%.
Modified Y zeolite product of the present invention can change into gently as heavy distillate, the acidic components in the heavy naphtha process catalyzer, is specially adapted to the catalyzer of hydrocracking process.
With products obtained therefrom of the present invention with SiO
2-Al
2O
3And/or Al
2O
3Be matrix, adopt hydrogenation metal commonly used such as Mo, Ni, W, Co etc., add Al as hydrogenation component
2O
3Tackiness agent adopts the kneading method moulding, carries out drying 4～12 hours at 100～120 ℃, and dried catalyst sample can be prepared into the catalyzer that contains modified Y zeolite of the present invention 400～550 ℃ of roastings 2～5 hours.
When modified Y zeolite product of the present invention is used for hydrocracking, heavy per-cent with catalyzer is benchmark, modified Y zeolite of the present invention accounts for 30%～80%, preferably 40%～70%, amorphous silicon aluminium accounts for 5%～25%, and preferably 5%～20%, binder constitutes 5%～25%, preferably 5%～15%, hydrogenation active metals ingredients constitute 10%～35%, preferably 20%～30%.
What described tackiness agent was the most frequently used is aluminum oxide, and what described hydrogenation active metals component was the most frequently used is to be selected from one or more among W, Mo, Ni, the Co in periodic table of elements VIB and the group VIII.
Compared with prior art, the present invention has following beneficial effect:
The NaY zeolite SiO that the present invention adopts
2/ Al
2O
3Than only is 4.8～5.2, cheap and easy to get, carries out the ammonium exchange before steam-treated, removes part Na
+, reduced cationic shielding effect, help removing of aluminium in the zeolite framework, therefore under lower temperature, carry out the scope that hydrothermal treatment consists can be reduced to unit cell parameters to be needed.Zeolite after the steam-treated is again with containing H
+, NH
4 +And RE
3+Mixing solutions handle, can lower the severity of steam-treated, avoid the hydrolysis of rare earth ion, make the specified location of rare earth ion exchanged to the zeolite, and can not cause rare earth to deposit at zeolite surface.Boil according to the prepared modification Y of the inventive method and to be particularly useful for as the heavy distillate hydrocracking changes into gently, heavy naphtha is main products acidity of catalyst component, in the one-stage serial flow process, demonstrate active height, the characteristics that the weight naphtha yield is high.
Example 1:
With 1000g Na
2The O weight content is 11.2%, SiO
2/ Al
2O
3Than being 5.1, degree of crystallinity is 97%, and unit cell parameters is that the NaY zeolite powder of 2.468nm is broken to less than 20 orders, is added to 10L and contains 800gNH
4NO
3The aqueous solution in, temperature is risen to 90～95 ℃, stir 1 hour after-filtration, filter cake is used above-mentioned solution again, repeat under the same conditions 3 times the exchange, the Na of products obtained therefrom
2The O weight content reduces to 2.2%.
Example 2:
The product of example 1 is placed the hydrothermal treatment consists stove of outer hot inner pressed, with 350 ℃/hour speed temperature is raised to 610 ℃, and keeps the system stagnation pressure, and to make the steam partial pressure and the ratio of ammonia dividing potential drop be 1.35: 1 at 0.10MPa, kept with this understanding 4 hours, and fed N then
2Gas makes sample be cooled to room temperature, takes out sample, and measuring its unit cell parameters is 2.442nm, and relative crystallinity is 81%, skeleton SiO
2/ Al
2O
3Than being 6.2.
Example 3:
With the sample break into portions of example 2, get 100g according to the form below condition with containing H for every part
+, NH
4 +And RE
3+Muriate or the solution of nitrate carry out solution-treated, zeolite is 1: 5 with the ratio of solution weight, temperature is 85～95 ℃, the time is 1 hour, suction filtration carries out 3 times repeatedly, drying was 400～550 ℃ of roastings 4 hours.Product property is listed in the table below:
| Sample | ????1 | ????2 | ????3 | ????4 | ????5 |
| Treatment soln is formed: H +，mol/L ??NH 4 +，mol/L ??RE 3+, heavy % | ??0.03 ??1.0 ??0.05 | ??0.05 ??1.0 ??0.05 | ??0.10 ??1.0 ??0.05 | ??0.15 ??1.0 ??0.05 | ??0.20 ??1.0 ??0.05 |
| The product property unit cell parameters, nm degree of crystallinity, % SiO 2/Al 2O 3??RE 3+, heavy % Na 2O, heavy % | ??2.442 ??90 ??8.79 ??2.7 ??0.075 | ??2.442 ??93 ??10.07 ??2.3 ??0.053 | ??2.441 ??95 ??13.58 ??2.1 ??0.047 | ??2.440 ??95 ??15.27 ??1.9 ??0.042 | ??2.439 ??98 ??17.82 ??1.8 ??0.039 |
Example 4:
Sample in the example 33 accordings to the form below are formed and SiO
2-Al
2O
3, tackiness agent, molybdenum oxide, nickelous nitrate mix and pinch, extrusion is made catalyzer, are finished catalyst after drying, the roasting, the catalyzer numbering is numbered identical with used zeolite.
| Catalyzer | ????1 | ????2 | ????3 | ????4 | ????5 |
| The heavy % of zeolite content | ????40 | ????45 | ????50 | ????55 | ????60 |
| Tackiness agent, heavy % | ????15 | ????12 | ????10 | ????8 | ????10 |
| ????SiO 2-Al 2O 3, heavy % | ????16.3 | ????18.1 | ????11.5 | ????9.2 | ????6.0 |
| ????MoO 3, heavy % | ????22.8 | ????23.1 | ????22.7 | ????22.1 | ????18.2 |
| ????NiO，w％ | ????5.9 | ????5.6 | ????5.8 | ????5.7 | ????5.8 |
Example 5:
Estimate on the 200ml hydroeracking unit with example 4 prepared catalyzer, raw materials used oil is Iranian VGO (subtract two/subtract three=3/2 (weights)), and stock oil character is listed in the table below:
One-stage serial is adopted in technical process, and an anti-dress catalyst for refining takes off the nitrogen in the stock oil to≤5 μ g/g, and two anti-dresses contain the catalyzer of this patent modified zeolite.Each catalyzer and the current up-to-date evaluation result of reference agent (commercial catalysts) on small-sized hydroeracking unit are listed in the table below:
| Density, g/cm3 | ????0.8988 |
| Boiling range, ℃ | ????237～547 |
| Sulphur, m% | ????1.54 |
| Nitrogen, m% | ????0.1652 |
| Catalyzer | ???1 | ???2 | ???3 | ???4 | ????5 | The reference agent |
| Temperature of reaction, ℃ | ???370 | ???370 | ???368 | ???366 | ????366 | ???372 |
| 65～177 ℃ of yields | ???48.0 | ???48.2 | ???50.1 | ???49.8 | ????51.3 | ???47.0 |
Claims (15)
1, a kind of Y zeolite method of modifying comprises: with the NaY zeolite is raw material, earlier through the ammonium exchange handle, carry out hydrothermal treatment consists then, again with containing H
+, NH
4 +And RE
3+Solution-treated after the washing, drying, roasting obtains the modified zeolite product at last.
2,, it is characterized in that the SiO of described NaY zeolite raw material according to the described Y zeolite method of modifying of claim 1
2/ Al
2O
3Than being 4.8～5.2, unit cell parameters is 2.464～2.470nm.
3,, it is characterized in that described NaY zeolite raw material relative crystallinity is greater than 95%, SiO according to the described Y zeolite method of modifying of claim 1
2/ Al
2O
3Than 5.0～5.2.
4, according to the described Y zeolite method of modifying of claim 1, the concrete grammar that it is characterized in that described ammonium exchange is: the NaY zeolite is contacted with ammonium salt solution, ammonium salt exchange temperature is 40～120 ℃, time is 0.5～4 hour, zeolite is 1: 3～15 with the ratio of ammonium salt solution weight, and exchange is under agitation carried out, the exchange after-filtration, so operation repeats 1～5 time, until intermediate product NH
4Na in the NaY zeolite
2The O weight content reduces to 1.5～3.5%.
5, according to the described Y zeolite method of modifying of claim 1, it is characterized in that the detailed process of described hydrothermal treatment consists is: the NH of described ammonium salt exchange back gained
4The NaY zeolite places in the hydrothermal treatment consists stove, and is moisture with himself, contain NH
4 +The water vapor and the ammonia that produce are handled, and temperature is 400～800 ℃, and system pressure is 0.05～0.5MPa, and the steam dividing potential drop is 0.5～3: 1 with the ratio of ammonia dividing potential drop, and the time of hydrothermal treatment consists is 1～8 hour, and hydrothermal treatment consists finishes, and pressure release feeds N
2The zeolite temperature is reduced to room temperature, take out intermediates, structure cell is contracted to 2.435～2.455nm in this process, skeleton SiO
2/ Al
2O
3Than being increased to 5.2～10.5.
6, according to the described Y zeolite method of modifying of claim 1, the intermediates that it is characterized in that obtaining after the described hydrothermal treatment consists are with containing H
+, NH
4 +And RE
3+Mixing solutions handle actual conditions and be: various ionic concns are respectively in the solution: H
+=0.01～0.15mol/L, NH
4 +Concentration is 0.3～2.0mol/L, RE
3+Concentration expressed in percentage by weight is 0.1%～10%, system temperature should be at 40～120 ℃, zeolite should be 1: 3 with the ratio of solution weight～and 15, the solution-treated time is 0.5～4 hour, and solution-treated is carried out 1～3 time repeatedly, all carries out mother liquor after each solution-treated and separates, the filter cake that the mother liquor of last solution-treated obtains after separating carried out drying 1～3 hour at 100～120 ℃, dried sample is at 400～750 ℃, and roasting is 2～6 hours in the air atmosphere, promptly gets described modified Y zeolite product.
7, according to the described Y zeolite method of modifying of claim 1, it is characterized in that described RE
3+Be to be selected from lanthanum, cerium, praseodymium, the rubidium one or more.
8, according to the described Y zeolite method of modifying of claim 1, it is characterized in that the described H of containing
+, NH
4 +And RE
3+Solution in negatively charged ion be to be selected from Cl
-, NO
3 -, SO
4 =, CO
3 =In one or more.
9, a kind of modified Y zeolite that contains rare earth is a benchmark with the total weight percent of modified Y zeolite, RE
3+Content be 0.1%～5.0%, Na
2O content is 0.05%～0.5%; The silica alumina ratio of Y zeolite is 5.0～20.0, and lattice constant is 2.435～2.455nm, and the preparation method who it is characterized in that described modified Y zeolite is to be raw material with the NaY zeolite, earlier through the ammonium exchange handle, carry out then hydro-thermal vapour handle, again with containing H
+, NH
4 +And RE
3+Solution-treated after the washing, drying, roasting obtains the modified Y zeolite product at last.
10,, it is characterized in that the RE of described modified Y zeolite according to the described modified Y zeolite that contains rare earth of claim 9
3+Weight content be 0.3%～3.0%, Na
2The weight content of O is 0.05%～0.3%; The silica alumina ratio of Y zeolite is 7.0～16.0, and lattice constant is 2.438～2.445nm, and relative crystallinity is 85%～100%.
11, a kind of application of claim 9 modified Y zeolite, it is characterized in that described modified Y zeolite product as heavy distillate change into gently, acidic components in the heavy naphtha process catalyzer.
12,, it is characterized in that described modified Y zeolite is used for the acidic components of hydrocracking process catalyzer according to the application of the described modified Y zeolite of claim 11.
13, a kind of hydrocracking catalyst that contains modified Y zeolite is a benchmark with the weight percent of catalyzer, and modified Y zeolite accounts for 30%～80%, and amorphous silicon aluminium accounts for 5%～25%, binder constitutes 5%～25%, hydrogenation active metals ingredients constitute 10%～35%; Described modified Y zeolite is a benchmark with the weight percent, comprises RE
3+Content be 0.1%～5.0%, Na
2O content is 0.05%～0.5%; The silica alumina ratio of Y zeolite is 5.0～20.0, and lattice constant is 2.435～2.455nm, and the preparation method of modified Y zeolite is to be raw material with the NaY zeolite, earlier through the ammonium exchange handle, carry out then hydro-thermal vapour handle, again with containing H
+, NH
4 +And RE
3+Solution-treated after the washing, drying, roasting obtains the modified Y zeolite product at last.
14, according to the described hydrocracking catalyst that contains modified Y zeolite of claim 13, weight percent with catalyzer is a benchmark, and modified Y zeolite accounts for 40%～70%, and amorphous silicon aluminium accounts for 5%～20%, binder constitutes 5%～15%, hydrogenation active metals ingredients constitute 20%～30%.
15, according to the described hydrocracking catalyst that contains modified Y zeolite of claim 13, it is characterized in that described tackiness agent is an aluminum oxide, described hydrogenation active metals component is to be selected from one or more among W, Mo, Ni, the Co in periodic table of elements VIB and the group VIII.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011060271A CN1169717C (en) | 2001-01-05 | 2001-01-05 | Y-zeolite modifying method with RE ion and its product |
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|---|---|---|---|
| CNB011060271A CN1169717C (en) | 2001-01-05 | 2001-01-05 | Y-zeolite modifying method with RE ion and its product |
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| Publication Number | Publication Date |
|---|---|
| CN1362367A true CN1362367A (en) | 2002-08-07 |
| CN1169717C CN1169717C (en) | 2004-10-06 |
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ID=4655085
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307098C (en) * | 2004-03-31 | 2007-03-28 | 中国石油化工股份有限公司 | Method for preparing rare-earth ultrastable Y-type zeolite |
| CN1319857C (en) * | 2005-06-23 | 2007-06-06 | 复旦大学 | High silicon super stabilizing natural foresite and it preparation process |
| CN100345632C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Alumina carrier containing compound zeolite and preparation method thereof |
| CN102847549A (en) * | 2012-08-27 | 2013-01-02 | 王小英 | Coal tar hydrocracking catalyst and preparation method thereof |
| CN103003202A (en) * | 2010-05-14 | 2013-03-27 | 墨西哥石油研究院 | Process for altering the physico-chemical properties of faujasite Y-type zeolites |
| CN103058217A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of rare-earth-containing Y molecular sieve |
| CN103055916A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
| CN110498424A (en) * | 2018-05-16 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of method that Y molecular sieve is modified |
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| CN116113679A (en) * | 2020-07-28 | 2023-05-12 | 沙特阿拉伯石油公司 | Hydrocracking catalyst comprising rare earth-containing post-modified USY zeolite, process for preparing the same, and process for hydrocracking hydrocarbon oils with the same |
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|---|---|---|---|---|
| CN1307098C (en) * | 2004-03-31 | 2007-03-28 | 中国石油化工股份有限公司 | Method for preparing rare-earth ultrastable Y-type zeolite |
| CN100345632C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Alumina carrier containing compound zeolite and preparation method thereof |
| CN1319857C (en) * | 2005-06-23 | 2007-06-06 | 复旦大学 | High silicon super stabilizing natural foresite and it preparation process |
| CN103003202B (en) * | 2010-05-14 | 2015-07-01 | 墨西哥石油研究院 | Process for altering the physico-chemical properties of faujasite Y-type zeolites |
| CN103003202A (en) * | 2010-05-14 | 2013-03-27 | 墨西哥石油研究院 | Process for altering the physico-chemical properties of faujasite Y-type zeolites |
| CN103055916A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN103058217A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of rare-earth-containing Y molecular sieve |
| CN103058217B (en) * | 2011-10-21 | 2015-04-01 | 中国石油化工股份有限公司 | Preparation method of rare-earth-containing Y molecular sieve |
| CN103055916B (en) * | 2011-10-21 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN102847549A (en) * | 2012-08-27 | 2013-01-02 | 王小英 | Coal tar hydrocracking catalyst and preparation method thereof |
| US11084024B2 (en) | 2015-08-05 | 2021-08-10 | Petrochina Company Limited | Method for modifying molecular sieve and a catalytic cracking catalyst containing the molecular sieve |
| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
| CN110498424A (en) * | 2018-05-16 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of method that Y molecular sieve is modified |
| CN110498424B (en) * | 2018-05-16 | 2021-10-08 | 中国石油化工股份有限公司 | Method for modifying Y molecular sieve |
| CN116113679A (en) * | 2020-07-28 | 2023-05-12 | 沙特阿拉伯石油公司 | Hydrocracking catalyst comprising rare earth-containing post-modified USY zeolite, process for preparing the same, and process for hydrocracking hydrocarbon oils with the same |
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|---|---|
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