CN1063103C - Catalyst with metal component for producing arenes from natural gasoline - Google Patents
Catalyst with metal component for producing arenes from natural gasoline Download PDFInfo
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- CN1063103C CN1063103C CN96123536A CN96123536A CN1063103C CN 1063103 C CN1063103 C CN 1063103C CN 96123536 A CN96123536 A CN 96123536A CN 96123536 A CN96123536 A CN 96123536A CN 1063103 C CN1063103 C CN 1063103C
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- gallium
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Abstract
The present invention relates to a metal component catalyst used for preparing arene from condensed oil of oil fields. The catalyst is prepared mainly by the following steps: mixing zeolite with Al2O3 gel; shaping and extruding the mixture into strips to prepare the carrier of the catalyst; introducing metal components of Zn, Ga and Pt into the carrier of the zeolite catalyst by using the methods of ion exchange, absorption and immersion; carrying out drying and calcination. The catalyst has the advantages of high activity and selectivity, long service life (1500 hours by repeated regeneration), slow carbon deposition, easy regeneration, high arene yield and low cost, and is a catalyst with industrial applications.
Description
The present invention relates to a kind of metal component molecular sieve catalyst that is used for producing arenes from natural gasoline
Rationally make full use of limited oil, natural gas resource is paid attention to by countries in the world.Aromatizing low-carbon paraffin can get oil gas, natural gas (moisture), lighter hydrocarbons through the directly synthetic aromatic hydrocarbons (benzene,toluene,xylene) of aromatisation (BTX) in field condensate, liquefied petroleum gas and the light naphthar, it not only provides new raw material sources for industrial chemicals aromatic hydrocarbons, has also opened up new approach for the comprehensive utilization of petroleum resources.Along with oil step up exploitation and condensate gas field large scale mining, will a large amount of condensate product (C of generation
3-C
9), but also only be emptying or point day lamp at present, a large amount of non-renewable fossil resources of waste.Therefore how rationally, making full use of the condensate resource has become the problem that presses for solution.According to the prior art report, the M-2 of Mabil oil company process uses the HZSM-5 molecular sieve zeolites to make lighter hydrocarbons be converted into aromatic hydrocarbons, but aromatics yield is not good.United States Patent (USP) 4157356 has been described C
3-C
8Alkane deoxidation cyclisation dimerization generates in the used catalyst of aromatic hydrocarbons and has used the component of calcic, but the application of calcium is confined in the catalyst that only contains silica supports.The Chinese patent 90106068 of Compagnie Francise des Petroles's application relates to a kind of zeolite catalyst of calcic at C
5-C
7Aromatization in the light fraction, but calcium content relates to the molecular sieve catalyst of platinum gallium (or zinc) bimetallic-modified up to 7% in the Chinese patent 90106456, platinum content is 0.001-1%, gallium or zinc content 0.4-2% (wt%) are used for light hydrocarbon feedstocks C
4-C
8Aromatisation, its catalyst life can reach 1000 hours.
The object of the invention is that the catalyst with metal component that is used for producing arenes from natural gasoline is with condensate (C
3-C
9) the catalyst reaction process of producing aromatic hydrocarbons for raw material provides a kind of high activity, high selectivity, good stability, cheap catalyst uses this catalyst to carry out the aromatization of condensate, can in atmospheric fixed bed reactor, carry out under 500 ℃ of better simply process conditions of reaction temperature, this catalyst is through repeated regeneration, and the life-span reaches 1500 hours, and carbon deposit is slow, regeneration is easy, the aromatics yield height.
The catalyst with metal component that is used for producing arenes from natural gasoline of the present invention, it is made up of three kinds of metals, it mainly is by making catalyst carrier after zeolite and the alundum (Al gel mixed-forming extrusion, method by ion-exchange, absorption, dipping then, metal component zinc, gallium, platinum are introduced the zeolite catalysis agent carrier, drying, roasting are made, metal component (percentage by weight) wherein: zinc 2.0-3.5%, gallium 0.2-0.8%, platinum 0.05-0.5%, zeolite 60-70%, alundum (Al 20-30%; Its preparation method is: prepare the alundum (Al gel at first according to a conventional method, with alundum (Al and zeolite mixed-forming drying, carry out roasting at 400 ℃, carry out ion-exchange with ammonium nitrate again, make ammonium type zeolite, the ammonium type zeolite of making is carried out ion-exchange with nitric acid pricker solution, make the molecular sieve catalyst that contains zinc, and then carry out ion-exchange with gallium nitrate solution, make the molecular sieve catalyst that contains zinc, gallium; Carry out ion-exchange and dipping with platinum acid chloride solution again, platinum is downloaded in the carrier, make the molecular sieve catalyst that contains zinc, gallium, platinum, carry out drying then, temperature places the muffle furnace roasting at 100-120 ℃ at 550 ℃.
The catalyst with metal component that is used for producing arenes from natural gasoline of the present invention, through adopting fixed-bed quartz reactor, each relevant component of chromatograph, carrying out data with chromatographic data processor handles, carbon number provides reaction result after returning-changing, and condensate is (wt%) C through GC-MS chromaticness on-line analysis component
3-C
5) 31.28%, C
629.41%, C
713.15%, C
84.7%, C
90.67%, C
100.12%C
5-C
9(cycloalkane) 20.53%, aromatic hydrocarbons 0.54%, material liquid density d=0.667g/ml
Referring to accompanying drawing
Fig. 1 is a life assessment experimental result of the present invention
Fig. 2 is the variation of product liquid yield in the single-pass reaction period of the present invention and arene content
Be to be figure take 50 hours as one-period among Fig. 1, as can be seen from Figure 1, the present invention is more activated After the life, the activation recovering rate is more than 97%, and its catalyst performance is more or less the same before and after the regeneration. From Fig. 2 Find out that catalytic performance of the present invention changes little within 100 hours.
Embodiment 1:
Prepare the alundum (Al gel at first according to a conventional method, get zeolite 60%, add alundum (Al gel 30%, splashing into rare nitric acid conciliation solution PH is 7, places 4 hours aftershapings, in 100-120 ℃ of drying, makes mixed carrier in 10 hours 400 ℃ of roastings then.
Get mixed carrier 30g then, add in the 210ml ammonium nitrate solution, and add 150ml water, carried out ion-exchange 3 hours, filter, be washed till no NO with deionized water in 80 ℃ of stirrings
3Make the ammonium nitrate zeolite in 100-120 ℃ of drying, in the ammonium nitrate zeolite, add 1N zinc nitrate solution 2.0% then, add water 100ml and carried out ion-exchange 10 hours, filter, be washed till no NO with deionized water in 80 ℃ of backwash stirrings
3In 100-120 ℃ of drying, in 550 ℃ of roastings 8 hours, make and contain the Zn molecular sieve catalyst, will contain the Zn molecular sieve catalyst again and carry out ion-exchange with gallium nitrate 0.8% solution, dry then, roasting makes and contains zinc, gallium molecular sieve catalyst, will contain zinc, gallium molecular sieve catalyst again and carry out ion-exchange and flooded 10 hours in 80 ℃ with chloroplatinic acid 0.05% solution, filters, be washed till no CL with deionized water, dry then, 550 ℃ of roastings made and contain zinc, gallium, platinum catalyst in 8 hours.
Embodiment 2:
Prepare the alundum (Al gel at first according to a conventional method, get zeolite 65%, add alundum (Al gel 25%, splashing into rare nitric acid conciliation solution PH is 7, places 42 hours aftershapings, in 100-120 ℃ of drying, makes mixed carrier in 10 hours 400 ℃ of roastings then.
Get mixed carrier 30g then, add in the 210ml ammonium nitrate solution, and add 150ml water, carried out ion-exchange 3 hours, filter, be washed till no NO with deionized water in 80 ℃ of stirrings
3Make the ammonium nitrate zeolite in 100-120 ℃ of drying, in the ammonium nitrate zeolite, add 1N zinc nitrate solution 3.0% then, add water 100ml and carried out ion-exchange 10 hours, filter, be washed till no NO with deionized water in 80 ℃ of backwash stirrings
3In 100-120 ℃ of drying, in 550 ℃ of roastings 8 hours, make and contain the Zn molecular sieve catalyst, will contain the Zn molecular sieve catalyst again and carry out ion-exchange with gallium nitrate 0.6% solution, dry then, roasting makes and contains zinc, gallium molecular sieve catalyst, to contain zinc, gallium molecular sieve catalyst again and carry out ion-exchange and flooded 10 hours in 80 ℃, filter, be washed till no CL with deionized water with chloroplatinic acid 0.25% solution, dry then, 550 ℃ of roastings made and contain zinc, gallium, platinum catalyst in 8 hours.
Embodiment 3:
Prepare the alundum (Al gel at first according to a conventional method, get zeolite 70%, add alundum (Al gel 20%, splashing into rare nitric acid conciliation solution PH is 7, places 42 hours aftershapings, in 100-120 ℃ of drying, makes mixed carrier in 10 hours 400 ℃ of roastings then.
Get mixed carrier 30g then, add in the 210ml ammonium nitrate solution, and add 150ml water, carried out ion-exchange 3 hours, filter, be washed till no NO with deionized water in 80 ℃ of stirrings
3Make the ammonium nitrate zeolite in 100-120 ℃ of drying, in the ammonium nitrate zeolite, add 1N zinc nitrate solution 3.5% then, add water 100ml and carried out ion-exchange 10 hours, filter, be washed till no NO with deionized water in 80 ℃ of backwash stirrings
3In 100-120 ℃ of drying, in 550 ℃ of roastings 8 hours, make and contain the Zn molecular sieve catalyst, will contain the Zn molecular sieve catalyst again and carry out ion-exchange with gallium nitrate 0.2% solution, dry then, roasting makes and contains zinc, gallium molecular sieve catalyst, to contain zinc, gallium molecular sieve catalyst again and carry out ion-exchange and flooded 10 hours in 80 ℃, filter, be washed till no CL with deionized water with chloroplatinic acid 0.5% solution, dry then, 550 ℃ of roastings made and contain zinc, gallium, platinum catalyst in 8 hours.
Claims (2)
1, a kind of catalyst with metal component that is used for producing arenes from natural gasoline, it is made up of three kinds of metals, it is characterized in that, by making catalyst carrier after zeolite and the alundum (Al gel mixed-forming extrusion, method by ion-exchange, absorption, dipping then, metal component zinc, gallium, platinum are introduced the zeolite catalysis agent carrier, and drying, roasting are made, wherein metal component (percentage by weight)
Zinc 2.0-3.5% gallium 0.2-0.8% platinum 0.05-0.5%
Zeolite 60-70% alundum (Al 20-30%
2, a kind of preparation method who is used for the catalyst with metal component of producing arenes from natural gasoline, it is characterized in that, prepare the alundum (Al gel at first according to a conventional method, with alundum (Al and zeolite mixed-forming drying, carry out roasting at 400 ℃, carry out ion-exchange with ammonium nitrate again, make ammonium type zeolite, the ammonium type zeolite of making is carried out ion-exchange with zinc nitrate solution, make the molecular sieve catalyst that contains zinc and then carry out ion-exchange, make the molecular sieve catalyst that contains zinc, gallium with gallium nitrate solution; Carry out ion-exchange and dipping with platinum acid chloride solution again, platinum is downloaded in the carrier, make the molecular sieve catalyst that contains zinc, gallium, platinum, carry out drying then, temperature places the muffle furnace roasting at 100-120 ℃ at 550 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96123536A CN1063103C (en) | 1996-12-27 | 1996-12-27 | Catalyst with metal component for producing arenes from natural gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96123536A CN1063103C (en) | 1996-12-27 | 1996-12-27 | Catalyst with metal component for producing arenes from natural gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1185997A CN1185997A (en) | 1998-07-01 |
| CN1063103C true CN1063103C (en) | 2001-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96123536A Expired - Fee Related CN1063103C (en) | 1996-12-27 | 1996-12-27 | Catalyst with metal component for producing arenes from natural gasoline |
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| CN (1) | CN1063103C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441412B (en) * | 2010-10-12 | 2015-02-18 | 中国石油化工股份有限公司 | Aromatization catalyst and application thereof in highly selective preparation of p-xylene |
| DE102012220810B3 (en) * | 2012-11-14 | 2014-02-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for increased phosphorus recovery from organic residues |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62232487A (en) * | 1986-04-03 | 1987-10-12 | Res Assoc Util Of Light Oil | Production of aromatic hydrocarbon |
| EP0299392A1 (en) * | 1987-07-15 | 1989-01-18 | Research Association For Utilization Of Light Oil | Process for production of crystalline galloalumino silicate and process for production of aromatic hydrocarbons |
| EP0325859A1 (en) * | 1987-12-31 | 1989-08-02 | Mobil Oil Corporation | Method for stabilization of zinc on aromatization catalysts |
| CN1062100A (en) * | 1990-12-05 | 1992-06-24 | 中国科学院大连化学物理研究所 | Be used for the light dydrocarbon aromatization reaction modified zeolite catalyst |
| CN1023633C (en) * | 1992-10-15 | 1994-02-02 | 大庆石油学院 | Gallium, zinc and platinum modified HZSM-5 catalyst for aromatization of low carbon chain hydrocarbon |
-
1996
- 1996-12-27 CN CN96123536A patent/CN1063103C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62232487A (en) * | 1986-04-03 | 1987-10-12 | Res Assoc Util Of Light Oil | Production of aromatic hydrocarbon |
| EP0299392A1 (en) * | 1987-07-15 | 1989-01-18 | Research Association For Utilization Of Light Oil | Process for production of crystalline galloalumino silicate and process for production of aromatic hydrocarbons |
| EP0325859A1 (en) * | 1987-12-31 | 1989-08-02 | Mobil Oil Corporation | Method for stabilization of zinc on aromatization catalysts |
| CN1062100A (en) * | 1990-12-05 | 1992-06-24 | 中国科学院大连化学物理研究所 | Be used for the light dydrocarbon aromatization reaction modified zeolite catalyst |
| CN1023633C (en) * | 1992-10-15 | 1994-02-02 | 大庆石油学院 | Gallium, zinc and platinum modified HZSM-5 catalyst for aromatization of low carbon chain hydrocarbon |
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| Publication number | Publication date |
|---|---|
| CN1185997A (en) | 1998-07-01 |
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