CN1046641C - Modified zeolite catalyst for light hydrocardon aromatization reaction - Google Patents
Modified zeolite catalyst for light hydrocardon aromatization reaction Download PDFInfo
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- CN1046641C CN1046641C CN90106456A CN90106456A CN1046641C CN 1046641 C CN1046641 C CN 1046641C CN 90106456 A CN90106456 A CN 90106456A CN 90106456 A CN90106456 A CN 90106456A CN 1046641 C CN1046641 C CN 1046641C
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- zeolite
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Abstract
The present invention relates to a modified ZSM-5 zeolite catalyst used for the aromatization reaction of light hydrocarbons, which is prepared by the following steps: mixing zeolite with the gel of SiO2, Si-Al and Al2O3 to prepare carriers after drying and shaping; carrying out the ammonium ion exchange of the carriers; carrying out ion exchange by using zinc or galium salt; finally carrying out ion exchange by using chloroplatinic acid; carrying out soakage, drying and calcination. The catalyst can be used for the aromatization reaction using light hydrocarbons (C4-C8) recovered from natural gas or oil fields as raw materials at normal pressure and 500 DEG C. The catalyst has the advantages of high activity and selectivity and long service life. The yield of aromatic hydrocarbons can reach 50 wt%, total reaction time reaches 1000 hours by repeated regeneration, and catalytic performance is basically not changed.
Description
The present invention relates to a kind of at lighter hydrocarbons (C
4～C
8Alkane) be converted into the preparation method of the modified ZSM-5 catalyst that uses in the aromatization of aromatic hydrocarbons.
In natural gas or field produces, often can reclaim a large amount of C
4～C
5Light alkane utilizes these light alkane can be converted into aromatic hydrocarbons for raw material by catalytic reaction.Have than the large economy benefit because these aromatic hydrocarbons mixtures can be used as petrochemical materials such as gasoline additive, 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 catalyst, Japan Patent for example, JP62,232,487, European patent EP 0299,392A1, European patent 0325, the technology that 859A1 etc. adopt.At JP62, in 232,487 patented technologies, 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 technology to make active relatively poor H in the reacting gas simultaneously
2, CH
4Air penetrating film is removed, and makes C
2H
6Above gas is sent back to reaction system.Ga ZSM-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 making circulating air with Ca, 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 EP099, same employing Ga ZSM-5 zeolite catalyst among the 392A1, but through roasting, modifications such as alkali are handled, to C
5～C
6Alkanes is that raw material is produced the aromatic hydrocarbons reaction condition and is: catalyst 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 EP0325, 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), and conversion ratio 46% (Wt), but catalyst is stable undesirable, and aromatics yield is low.
The objective of the invention is for light alkane (C
4～C
8) produce catalyst and the technology of preparing thereof that the arenes catalytic course of reaction provides a kind of high activity, high selectivity and good stability for raw material.Use the above-mentioned light alkane aromatization reaction of this catalyst can be at normal pressure, about 500 ℃ than carrying out under the simple process condition, the yield height of aromatic hydrocarbons, and catalyst life is long.
Catalyst 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 catalyst that metal active constituent constitutes with platinum and zinc or gallium dual element.Specifically, this catalyst 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 percentage as carrier zeolite and silicon, aluminum oxide:
Zeolite: 75～55%;
Silicon, aluminum oxide: 25～45%.
Metal element content in the catalyst (Wt) is Pt0.001～1%:Zn or GaO.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-forming in proportion, and silicon (aluminium) gel promptly is the burl agent of zeolite moulding, also is one of the composition that constitutes the carrier of catalyst, and sample carries out drying and roasting after the moulding.
2. above-mentioned 1 manufactured goods 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 zinc ion or gallium ion with zinc salt or gallium salt, make and contain zinc 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-forming in proportion.
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 chloroplatinic acid.
In above-mentioned Preparation of catalysts process, when containing SiO
2, Si-Al or Al
2O
3After gel and the zeolite mixed-forming 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 baking 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 Ludox 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
Getting synthetic ZSM-11 (50) zeolite 14 grams replaces ZSM-5 zeolite repetition example 1 and example 2 to make finished catalyst 3.Get synthetic ZSM-5 (56) and ZSM-11 (50) zeolite and make finished catalyst 4 by ZSM-5 zeolite repetition example 1 in 3: 7 ratio mixture 14 gram replacement examples 1 and example 2.
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 catalyst are used for the experiment of light dydrocarbon aromatization reaction catalytic performance
Utilize the catalyst 1～4 of example 2～4 preparations to carry out the light dydrocarbon aromatization reaction experiment, reaction condition 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 quantitative collection gas, fluid product, each relevant component of chromatograph to separator through condenser.Light hydrocarbon feedstocks consists of (Wt); C
3° 0.38%; C
4° 5.8%; C
5° 22.22%; C
6° 34.58%; C
724.52%; C
89.86%; C
92.63%, react after 30 hours the reaction result of sample analysis and list in table 1.The catalyst 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 catalyst is used for light dydrocarbon aromatization reaction experimental result 1 product (Wt%) catalyst 1 catalyst 2 catalyst 3 catalyst 4 H
21.96 1.78 2.13 1.61C
1～C
443.33 53.94 50.08 44.30C
5～C
88.11 1.45 1.63 5.60 aromatic hydrocarbons 46.60 42.83 46.16 48.49
Table 2 catalyst is used for light dydrocarbon aromatization reaction experimental result 2 product catalyst 5 catalyst 6 catalyst, 7 liquid yields (Wt%) 50.02 63.52 55.33 product liquid aromatic hydrocarbons (Wt%) 74.12 39.36 92.72 aromatics yields (gram/100 gram raw materials) 37.10 25.44 51.32
The experiment of example 7 catalyst stabilities
React by example 6 described reaction conditions with example 2 prepared catalyst 1, respectively at reaction 30 hours, 100 hours, sampling is analyzed after 200 hours, every reaction was regenerated catalyst 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 time (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 catalyst has the very high life, behind the repeated regeneration of catalyst footpath, amounts to 1000 hours basic no changes of its catalytic performance of reaction.
Claims (2)
1. a light dydrocarbon aromatization reaction is in order to ZSM-5 and/or ZSM-11 and SiO
2Mixing is as carrier, and platinum and zinc or gallium dual element are the Preparation of catalysts method that metal active constituent constitutes, and it is characterized in that step is carried out in the following order:
(1) with synthetic zeolite ZSM-5 and/or ZSM-11 and SiO
2The routine by weight percentage zeolite 75～55% of gel, Si oxide 25～45% mixed-formings are shaped to sample and carry out drying and roasting;
(2) (1) carrier is carried out height exchange with ammonium salt and make ammonium type zeolite, 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; (2) process of also can finishing is earlier finished (1) process again, and promptly zeolite carries out ion-exchange earlier, again with SiO
2Gel, mixed-forming is shaped to sample and carries out drying and roasting in proportion, 200～500 ℃ of sintering temperatures, roasting time 8～48 hours;
(3) utilize the platiniferous solion that zinc or gallium zeolite are comprised that the silicon as carrier part carries out ion-exchange and dipping, the platinum element be downloaded in the carrier, behind the supported carrier platinum element, carry out again drying and roasting get final product catalyst of the present invention.
2. according to the described Preparation of catalysts method of claim 1, it is characterized in that doing quick-fried to sample after the ion-exchange in the preparation process, do quick-fried temperature and be 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062100A CN1062100A (en) | 1992-06-24 |
| CN1046641C true 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (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 |
| 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 |
| CN1257769C (en) | 2003-10-31 | 2006-05-31 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphor and metal component and its use |
| 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 |
| 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 |
| 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 |
| 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 |
| CN107930676B (en) * | 2016-10-12 | 2021-05-14 | 中国科学院大连化学物理研究所 | ZSM-11 catalyst for olefin aromatization and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4485185A (en) * | 1979-03-29 | 1984-11-27 | Teijin Petrochemical Industries, Ltd. | Catalyst composition |
| 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
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4485185A (en) * | 1979-03-29 | 1984-11-27 | Teijin Petrochemical Industries, Ltd. | Catalyst composition |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| Publication number | Publication date |
|---|---|
| CN1062100A (en) | 1992-06-24 |
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