CN1062100A - Be used for the light dydrocarbon aromatization reaction modified zeolite catalyst - Google Patents
Be used for the light dydrocarbon aromatization reaction modified zeolite catalyst Download PDFInfo
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- CN1062100A CN1062100A CN 90106456 CN90106456A CN1062100A CN 1062100 A CN1062100 A CN 1062100A CN 90106456 CN90106456 CN 90106456 CN 90106456 A CN90106456 A CN 90106456A CN 1062100 A CN1062100 A CN 1062100A
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Abstract
A kind of light dydrocarbon aromatization reaction modified ZSM-5 zeolite catalyzer that is used for is through zeolite and SiO
2, Si-Al, Al
2O
3Make carrier after the gel mixing moulding drying, carrier carries out ion-exchange with zinc or gallium salt again after ammonium ion exchange, carries out ion-exchange with platinum chloric acid at last and makes with dipping drying, roasting.This catalyzer is used for the lighter hydrocarbons (C of Sweet natural gas or oil field recovery
4～C
8) for raw material carries out aromatization can be at normal pressure, carry out under 500 ℃, catalyzer has higher activity and selectivity, aromatics yield can reach 50% (wt).Catalyzer has the very high life simultaneously, amounts to reaction 1000 hours, the basic no change of its catalytic performance through repeated regeneration.
Description
The present invention relates to a kind of at lighter hydrocarbons (C
4～C
8Alkane) be converted into modified ZSM-5 catalyst of using in the aromatization of aromatic hydrocarbons and preparation method thereof.
In Sweet natural gas or field produces, often can reclaim a large amount of C
4～C
8Light alkane utilizes these light alkane can be converted into aromatic hydrocarbons for raw material by catalyzed reaction.Have than the large economy benefit because these aromatic hydrocarbons mixtures can be used as petrochemical materials such as gasoline dope, therefore this aromatization is caused that people pay attention to.In the technology of being reported, mostly adopt Zn or Ga modified ZSM-5 zeolite catalyzer, Japanese Patent for example, Jp62,232,487 European patent Ep0299,392A1, European patent 0325,859A1 waits the technology of employing.In the Jp62.232.487 patented technology, can improve aromatics yield in order to make in the reaction of lighter hydrocarbons aromatization, the generated reactive gas by product is delivered to reaction system once more circulate, utilize film to divide membrane technique to make active relatively poor H in the reactant gases simultaneously
2, CH
4Air penetrating film is removed, and makes C
2H
6Above gas is sent back to reaction system.The GaZSM-5 zeolite catalyst is adopted in reaction, when with containing C
5～C
6When alkane is unstripped gas, be reflected at 560 ℃, pressure 3Kg/Cm
2Under the condition, get liquid yield 64.3Wt%, aromatic hydrocarbons is 63%, reacts liquid yield decline 3% after 8 days.As use C
3Make circulation gas, then liquid yield drops to 40% by 55.0Wt% after 8 days.Though this technology aromatics yield height will adopt membrane separation technique, complex process, investment is high, at Ep0299, same employing GaZSM-5 zeolite catalyst among the 392A1, but through roasting, modifications such as alkali are handled, to C
5～C
6Alkanes is that raw material production aromatic hydrocarbons reaction conditions is: catalyzer is at fixed bed reaction, air speed 2.0h
-1, use N
2Dilution is reflected at 500 ℃, carry out under the normal pressure, but aromatics yield only can keep 57 hours greater than 60%, and life of catalyst is very short.In addition, at patent Ep0.325, propose at raw material (C among the 859A1
2～C
12Aliphatic hydrocarbon) adds CO in
2, H
2O, H
2Compounds such as S can prevent the loss of Zn in the ZnZSM-5 zeolite catalyst.For example at C
3Add 25mol%CO in the raw material
2, at 550 ℃, during air speed 0.2
-1Reaction is 3 hours under the condition, arenes selectivity 51%(Wt), transformation efficiency 46%(Wt), but catalyzer is stable undesirable, and aromatics yield is low.
The objective of the invention is for light alkane (C
4～C
8) catalyzer and the technology of preparing thereof of a kind of high reactivity, highly selective and good stability be provided for raw material production arenes catalytic reaction process.Use the above-mentioned light alkane aromatization reaction of this catalyzer can be at normal pressure, than carrying out under the simple process condition, the yield height and the catalyst life of aromatic hydrocarbons be long about 500 ℃.
Catalyzer mesolite of the present invention is selected ZSM-5 and/or ZSM-11 and SiO for use
2And/or Al
2O
3Mixing is as carrier, is the catalyzer that metal active constituent constitutes with platinum and zinc or gallium dual element.Specifically, this catalyzer mesolite can adopt synthetic ZSM-5 of commodity or ZSM-11 zeolite, becomes platiniferous and zinc or gallium bimetal element through ion-exchange, and its composition can be represented by the formula:
1, when zeolite is selected ZSM-5 or ZSM-11 for use:
XNa
2O·（1-X）M
2/nO·Al
2O
3·（40～250）·SiO
2
In the formula: M is Pt and Ga or Zn,
n＝2，3;
X is 0.001～0.01.
2, when zeolite is selected ZSM-5 and ZSM-11 mixed crystal for use,
ZSM-5∶ZSM-11＝（0.3～0.5）∶（0.7～0.5）
X·Na
2O·（1-X）M
2/nO·Al
2O
3·（50～70）SiO
2
In the formula: M is Pt and Ga or Zn
n＝2，3;
X is 0.001～0.01.
Simultaneously press column weight amount per-cent as carrier zeolite and silicon, aluminum oxide:
Zeolite: 75～55%;
Silicon, aluminum oxide: 25～45%.
Metal element content in the catalyzer (Wt) is: Pt0.001～1%; Zn or Ga0.4～2%.
This Preparation of catalysts method mainly comprises the following steps:
1, with synthetic zeolite (ASM-5 and/or ASM-11) with contain SiO
2, Si-Al or Al
2O
3Gel is mixed in proportion moulding, and silicon (aluminium) gel promptly is the burl agent of zeolite moulding, also is one of the composition that constitutes the carrier of catalyzer, and sample carries out drying and roasting after the moulding.
2, above-mentioned 1 finished product are carried out ion-exchange with ammonium salt, ammonium salt can adopt ammonium nitrate or ammonium chloride to make ammonium type zeolite.Again ammonium type zeolite is carried out the exchange of zine ion or gallium ion with zinc salt or gallium salt, make and contain zine ion or gallium ion zeolite, zinc salt or gallium salt can be with nitrate or hydrochlorides.2 processes of also can finishing are earlier finished 1 process again, promptly zeolite carry out earlier ion-exchange again with contain SiO
2, Si-Al or Al
2O
3Gel is mixed in proportion moulding.
3, utilize the platiniferous solion that zinc or gallium zeolite (comprising silicon and/or aluminum oxide carrier) are carried out ion-exchange and dipping at last, the platinum element is downloaded in the carrier, the most frequently used platiniferous solion is a Platinic chloride.
In above-mentioned Preparation of catalysts process, when containing SiO
2, Si-Al or Al
2O
3After gel and the zeolite mixing moulding drying, carry out roasting at 200～500 ℃, roasting time was advisable in 8～48 hours.Carrying out ion-exchange can carry out under 80～95 ℃ of temperature, and sample after the ion-exchange is carried out drying, and drying temperature is advisable with 100～120 ℃.In addition, utilize platinum acid chloride solution to carry out carrying out drying behind ion-exchange and the dipping, carry out roasting in 300～540 ℃ then, roasting time was advisable with 3～8 hours.
To the invention provides Preparation of catalysts method and catalytic performance, further describe by following example.
Example 1, the catalytic carrier preparation
Get synthetic ZSM-5(56) zeolite 14 grams, add silicon sol and (press SiO
2Content is 5 grams), use 10%HNO
3Transfer PH～7 1.5ml mix, place 2 hours aftershapings,, got mixed carrier in 4～8 hours 500 ℃ of roastings then in 100～120 ℃ of dryings.
Example 2 Preparation of Catalyst 1
Example 1 is made mixed carrier 20 grams, add 150ml 1N NH
4NO
3In the solution, and add 130ml water, carried out ion-exchange 2 hours, filter, be washed till no NO with deionized water in 80～95 ℃ of water-soluble stirrings down
3Filter cake got NH in 3 hours in 100～120 ℃ of dryings
4The ZSM-5 zeolite.Get and make ammonium zeolite 10 gram, add (0.05M), zinc nitrate solution 40ml adds water 130ml and refluxes to stir under 80～85 ℃ of conditions and carried out ion-exchange 4 hours, and filtration is washed till no NO with deionized water
3, filter cake is in 100～120 ℃ of dryings 3 hours, in 540 ℃ of roastings 4 hours, the ZnZSM-5 zeolite.The zinc zeolite that makes added contain 0.0045 gram/ml platinum acid chloride solution 120ml and under 80 ℃, carried out ion-exchange and dipping 4～8 hours, filter, be washed till no Cl with deionized water
-Ion in 100～120 ℃ of dryings 3 hours, in 300～540 ℃ of roastings 4 hours, makes finished catalyst 1 again.
Example 3 Preparation of catalysts 2
Repeat example 2 preparation process, just replace zinc nitrate solution, make finished catalyst 2 with (0.05M) gallium nitrate solution 40ml.
Example 4 Preparation of Catalyst 3,4
Get synthetic ZSM-11(50) zeolite 14 grams replace the ZSM-5 zeolite to repeat example 1 and example 2 makes finished catalyst 3.Get synthetic ZSM-5(56) and ZSM-11(50) zeolite replace by 3: 7 mixed thing 14 grams that ZSM-5 zeolite repetition example 1 and example 2 make finished catalyst 4 in the examples 1.
Example 5 contains the zeolite catalyst of different Si/Al
SiO
2/ Al
2O
3Be 100 or 210 get ZSM-5 zeolite and SiO
2/ Al
2O
3Be 70 ZSM-5 and the ZSM-11 mixed crystal carries out example 1 and example 2 preparation process make finished catalyst 5,6,7.
Example 6 catalyzer are used for the experiment of light dydrocarbon aromatization reaction catalytic performance
Utilize the catalyzer 1～4 of example 2～4 preparations to carry out the light dydrocarbon aromatization reaction experiment, reaction conditions is: adopt quartz reactor, and internal diameter 8 * 300mm, interior filling 3ml diameter is 2.0 * 4 strip catalysts, is reflected at 500 ℃ of normal pressures, during air speed 2.0
-1Carry out under the condition, product separates to separator through condenser, quantitative collection gas, liquid product, each relevant component of chromatograph.Light hydrocarbon feedstocks consists of (Wt): C
0 30.38%; C
0 45.8%; C
0 522.22%; C
0 634.58%; C
724.52%; C
89.86%; C
92.63%.React after 30 hours the reaction result of sampling analysis and list in table 1.The catalyzer 5,6,7 that utilizes example 5 to prepare reacts it by above-mentioned condition and the results are shown in table 2.
Table 1 catalyzer is used for light dydrocarbon aromatization reaction experimental result 1
Reaction product (Wt%) catalyzer 1 catalyzer 2 catalyzer 3 catalyzer 4
H
21.96 1.78 2.13 1.61
C
1～C
443.33 53.94 50.08 44.30
C
5～C
88.11 1.45 1.63 5.60
Aromatic hydrocarbons 46.60 42.83 46.16 48.49
Table 2 catalyzer is used for light dydrocarbon aromatization reaction experimental result 2
Reaction product catalyzer 5 catalyzer 6 catalyzer 7
Liquid yield (Wt%) 50.02 63.52 55.33
Aromatic hydrocarbons in the product liquid (Wt%) 74.12 39.36 92.72
Aromatics yield (gram/100 gram raw materials) 37.10 25.44 51.32
The experiment of example 7 catalyst stabilities
React by example 6 described reaction conditionss with example 2 prepared catalyzer 1, respectively at reaction 30 hours, 100 hours, sampling is analyzed after 200 hours, every reaction was regenerated catalyzer in 3 hours in 500～550 ℃ of roastings in air after 200 hours, through amount to once more for 5 times reaction got in 1000 hours 5 times as a result mean value be 1000 hours reaction results, its reaction should the results are shown in table 3.
The experiment of table 3 catalyst stability
Reaction times (hour) virtue in liquid yield (Wt%) the aromatics yield product liquid
(gram/100 gram raw materials) hydrocarbon content (Wt%)
30 55.58 51.31 92.32
100 53.04 50.11 94.46
1000 60.91 50.47 82.86
By above-mentioned example as can be seen, utilize Pt of containing provided by the invention and metal zeolite catalysts such as Zn or Ga to lighter hydrocarbons (C
4～C
8) aromatization has higher selectivity and activity, aromatics yield can reach 50%(Wt).Simultaneously, this catalyzer has the very high life, behind the repeated regeneration of catalyzer footpath, amounts to 1000 hours basic no changes of its catalytic performance of reaction.
Claims (3)
1, a kind of light dydrocarbon aromatization reaction is characterized in that still containing platinum as metal active constituent with containing zinc or gallium ZSM-5 zeolite catalyst; As the carrier zeolite is ZSM-5 and/or ZSM-11 and SiO
2And/or Al
2O
3Mixture; And metal element content (Wt) is: Pt0.001～1%, Zn or Ga0.4～2%; Carrier mesolite 75～55%, silicon, aluminum oxide 25～45%;
Above-mentioned Preparation of catalysts method is:
1) with synthetic zeolite XSM-5 and/or ZSM-11 and contain SiO
2Si-Al, Al
2O
3Gel is mixed in proportion moulding, is shaped to sample and carries out drying and roasting;
2) with 1) carrier carries out ion-exchange with ammonium salt and makes ammonium type zeolite, and ammonium salt can adopt ammonium nitrate or ammonium chloride, again ammonium type zeolite is carried out zinc or gallium ion exchange with zinc salt or gallium salt, makes to contain zinc or gallium zeolite, and zinc salt or gallium salt can be with nitrate or hydrochlorides; Also can finish 2 earlier) process finishes 1 again) process, promptly zeolite carries out ion-exchange earlier, again with contain SiO
2, Si-Al, Al
2O
3Gel is mixed in proportion moulding;
3) utilize the platiniferous solion that zinc or gallium zeolite (comprising silicon and/or aluminum oxide as carrier part) are carried out ion-exchange and dipping, the platinum element is downloaded in the carrier, the most frequently used platiniferous solion is a Platinic chloride.
2,, it is characterized in that in the preparation process when containing SiO according to the described catalyzer of claim 1
2, Si-Al or Al
2O
3Carry out roasting at 200～500 ℃ after gel and the zeolite mixing moulding drying.
3, according to the described catalyzer of claim 1, it is characterized in that in the preparation process sample after the ion-exchange being carried out drying, drying temperature is advisable with 100～120 ℃, with platinum acid chloride solution carry out ion-exchange and soak after carry out drying, carry out roasting in 300～540 ℃ then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90106456A CN1046641C (en) | 1990-12-05 | 1990-12-05 | Modified zeolite catalyst for light hydrocardon aromatization reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90106456A CN1046641C (en) | 1990-12-05 | 1990-12-05 | Modified zeolite catalyst for light hydrocardon aromatization reaction |
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| Publication Number | Publication Date |
|---|---|
| CN1062100A true CN1062100A (en) | 1992-06-24 |
| CN1046641C CN1046641C (en) | 1999-11-24 |
Family
ID=4880095
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90106456A Expired - Fee Related CN1046641C (en) | 1990-12-05 | 1990-12-05 | Modified zeolite catalyst for light hydrocardon aromatization reaction |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048922C (en) * | 1994-10-20 | 2000-02-02 | 中国科学院山西煤炭化学研究所 | Method of preparing modified molecular sieve with metal surfactant |
| CN1058284C (en) * | 1998-04-10 | 2000-11-08 | 中国石油化工总公司 | Light hydrocarbon aromatization catalyst and its preparing process |
| CN1063103C (en) * | 1996-12-27 | 2001-03-14 | 中国科学院新疆化学研究所 | Catalyst with metal component for producing arenes from natural gasoline |
| CN100377783C (en) * | 2005-01-31 | 2008-04-02 | 中国石油化工股份有限公司 | Modifying catalyst for naphtha processed maferial and method therefor |
| CN100413586C (en) * | 2004-05-28 | 2008-08-27 | 中国石油化工股份有限公司 | Molecular screen microspherical catalyst |
| US7758847B2 (en) | 2003-10-31 | 2010-07-20 | China Petroleum & Chemical Corporation | Molecular sieve with MFI structure containing phosphorus and metal components, preparation process and use thereof |
| CN103752346A (en) * | 2013-12-09 | 2014-04-30 | 中国科学院山西煤炭化学研究所 | Catalyst for aromatization of low-carbon mixed hydrocarbons in Fischer-Tropsch synthesis tail gas and its preparation method and use |
| CN105498824A (en) * | 2014-09-23 | 2016-04-20 | 中国石油化工股份有限公司 | Hydrocarbon reforming catalyst containing mesoporous molecular sieve, and preparation method thereof |
| CN106423255A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Ethylbenzene catalyst and preparation method thereof |
| CN107930676A (en) * | 2016-10-12 | 2018-04-20 | 中国科学院大连化学物理研究所 | A kind of 11 catalyst of ZSM and preparation method for alkene aromatisation |
Families Citing this family (1)
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| CN1325378C (en) * | 2003-10-24 | 2007-07-11 | 中国石油化工股份有限公司 | Modified molecular sieve and its prepn process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55129232A (en) * | 1979-03-29 | 1980-10-06 | Teijin Yuka Kk | Isomerization of xylenes |
| US4886927A (en) * | 1987-10-16 | 1989-12-12 | Uop | Process for isomerization of alkylaromatics |
| US4957891A (en) * | 1987-10-16 | 1990-09-18 | Uop | Catalyst for isomerizing alkylaromatics |
-
1990
- 1990-12-05 CN CN90106456A patent/CN1046641C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048922C (en) * | 1994-10-20 | 2000-02-02 | 中国科学院山西煤炭化学研究所 | Method of preparing modified molecular sieve with metal surfactant |
| CN1063103C (en) * | 1996-12-27 | 2001-03-14 | 中国科学院新疆化学研究所 | Catalyst with metal component for producing arenes from natural gasoline |
| CN1058284C (en) * | 1998-04-10 | 2000-11-08 | 中国石油化工总公司 | Light hydrocarbon aromatization catalyst and its preparing process |
| US7758847B2 (en) | 2003-10-31 | 2010-07-20 | China Petroleum & Chemical Corporation | Molecular sieve with MFI structure containing phosphorus and metal components, preparation process and use thereof |
| CN100413586C (en) * | 2004-05-28 | 2008-08-27 | 中国石油化工股份有限公司 | Molecular screen microspherical catalyst |
| CN100377783C (en) * | 2005-01-31 | 2008-04-02 | 中国石油化工股份有限公司 | Modifying catalyst for naphtha processed maferial and method therefor |
| CN103752346A (en) * | 2013-12-09 | 2014-04-30 | 中国科学院山西煤炭化学研究所 | Catalyst for aromatization of low-carbon mixed hydrocarbons in Fischer-Tropsch synthesis tail gas and its preparation method and use |
| CN103752346B (en) * | 2013-12-09 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | For the catalyst of low carbon mixed hydrocarbon aromatisation in Fischer-Tropsch tail gas and method for making and application |
| CN105498824A (en) * | 2014-09-23 | 2016-04-20 | 中国石油化工股份有限公司 | Hydrocarbon reforming catalyst containing mesoporous molecular sieve, and preparation method thereof |
| CN105498824B (en) * | 2014-09-23 | 2018-06-19 | 中国石油化工股份有限公司 | Hydrocarbons reforming catalyst of containing mesopore molecular sieve and preparation method thereof |
| CN106423255A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Ethylbenzene catalyst and preparation method thereof |
| CN106423255B (en) * | 2015-08-12 | 2019-01-25 | 中国石油化工股份有限公司 | Ethylbenzene catalyst and preparation method thereof |
| CN107930676A (en) * | 2016-10-12 | 2018-04-20 | 中国科学院大连化学物理研究所 | A kind of 11 catalyst of ZSM and preparation method for alkene aromatisation |
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| Publication number | Publication date |
|---|---|
| CN1046641C (en) | 1999-11-24 |
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