CN101347742B - Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials - Google Patents
Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing light aromatic hydrocarbons and light paraffin hydrocarbons by using hydrocarbon raw materials, and the catalyst is mainly used for solving the technical problems that a binding agent in a bifunctional catalyst which is prepared by using a zeolite carrier containing the binding agent of the prior art can reduce the content of effective components, cause the decrease of the absorption capacity, reduce the effective surface area and further cause lower activity and poorer stability. The catalyst comprises the following components counted by the percentage by weight: a) 0.01 to 0.8 percent of at least one of Pt or Pd; b) larger than zero and less than or equal to 1 percent of one selected from Cu, Sn, Pb or Fe; c) the balance of at least one selected from binding agent-free mordenite, Beta zeolite, Y zeolite, ZSM-5 or ZSM-11, thereby preparing the bifunctional catalyst; therefore, the technical scheme can better solve the problems and can be used in the industrial production for the preparation of the light aromatic hydrocarbons and the light paraffin hydrocarbons by using the hydrocarbon raw materials.
Description
Technical field
The present invention relates to the catalyst that a kind of hydrocarbon raw material prepares light aromatics and light paraffins.
Background technology
Industrial generally is reforming process reformate of making and the drippolene that is obtained by the naphtha cracking to be carried out solvent extraction separate BTX aromatic hydrocarbons and non-aromatics, this process is according to aromatic hydrocarbons, the polarity difference of non-aromatics in using solvent, reaches the purpose of separate targets aromatic hydrocarbons.Though solvent extraction BTX can obtain the BTX aromatic hydrocarbons of higher degree, but need the complicated solvent extraction device of a cover, and extraction solvent needs to replenish into endlessly in the extraction procedure process, so the solvent extraction process has occupied the very big ratio of producing BTX aromatic hydrocarbons cost.U.S. Patent No. 4,058,454 have related to a kind of solvent extraction that separates and reclaim the polarity hydro carbons from the hydrocarbon mixture that comprises polarity hydro carbons and non-polar hydrocarbon.When the dissolving solvent of polar substances such as sulfolane contacted with hydrocarbon mixture, polar aromatics can optionally be dissolved, thereby separates from nonpolar non-aromatics.Described method is favourable from obtaining that highly purified aromatic hydrocarbon mixes, but from the extra solvent extraction equipment of needs with to drop into solvent continuously at equipment needs in service be disadvantageous.
U.S. Patent No. 3,729,409 non-aromatic hydrocarbons that propose to mix with aromatic hydrocarbons change into low-carbon alkanes by the hydrocracking reaction in the presence of catalyst, can isolate aromatic hydrocarbons by the vapour-liquid separator from non-aromatics.In addition, U.S. Patent No. 3,849,290 and 3,950,241 also proposed a kind of by making the straight-chain hydrocarbons component of mixing change into gaseous component to increase arene content in the liquid composition through the hydrocracking reaction in the presence of the ZSM-5 type zeolite to prepare the method for high-quality ethereal oil component with aromatic hydrocarbons.U.S. Patent No. 5,865,986 and No.6,001,241 has further disclosed a kind of naphtha cut upgrade method, by catalyst based at partial reaction device mesolite, to increase the output of aromatic hydrocarbons.Korea S SK patent CN1217892C can be prepared into liquefied petroleum gas and light aromatics with upgradings such as reformate and drippolenes by similar approach.
Acidic catalyst need overcome the rapid deactivation problem that the coking carbon distribution causes, can assign to be suppressed by the metal group that load has a highly hydrogenated activity.The hydrogenation activity of metal center is crossed and can be caused that by force another side reaction aromatic ring is saturated, United States Patent (USP) 5,865, and 986 propose to use sulphur compound to control metal active.In addition, at United States Patent (USP) 6,001, in 241, control degree of hydrogenation with lead or bismuth.Also can adjust by the decentralization that changes content of metal, carried metal.May contain the raw material that suppresses metal hydrogenation performance component for raw material is comparatively complicated, drippolene raw material such as sulfur compound, can consider two kinds of metal composite of Pt, Pd together, thereby this all can have good sulfur resistance than independent any one metal of use Pt, Pd and keeps good hydrogenation performance.Two kinds of metal composite of Pt, Pd can produce electro ultrafiltration or chemical action mutually, rather than separately exist in the catalyst, thereby good hydrogenation and sulfur resistance is provided.
Zeolite powder particularly nano zeolite powder can form dust in actual applications, inconvenient operation, there are weakness such as difficult recovery, easy inactivation and gathering, also can jeopardize operator's health, because too high pressure drop zeolite powder is not suitable for fixed bed reactors yet in catalytic reaction.Therefore the zeolite molecular sieve powder must be made particle with certain mechanical strength and shape, this process often needs to add binding agent, the binding agent that adopts considers that the influence in temperature, adhesion strength and use field also can be different, and often the binding agent that adopts comprises some oxides and some clay minerals such as aluminium oxide, silica, titanium dioxide.The body formed introducing binding agent of zeolite powder can reduce the content of active principle, causes adsorbance to descend, and effective surface area is reduced.Because binding agent may the part component can enter zeolite cavity or blocking portion zeolite aperture, therefore introduced diffusion-restricted, cause adsorption capacity to weaken, the adsorptive selectivity variation, absorption and desorption rate descend, then cause active the reduction in catalytic reaction, selectivity descends, and the binding agent composition may cause some and do not expect the side reaction that takes place.The binder free zeolite molecular sieve is meant and does not contain inert binder in the zeolite granular or only contain small amount of binder, higher zeolite content is arranged, therefore available effective surface area is bigger, have more performance aspect adsorbing separation and the ion-exchange, may in some reaction, have better catalytic performance.
Summary of the invention
Technical problem to be solved by this invention is the content that binding agent can reduce active principle in the bifunctional catalyst of the employing that exists in the prior art Zeolite support preparation that contains binding agent, cause adsorbance to descend, effective surface area is reduced, so the activity that causes is lower, the technical problem of less stable, provides a kind of new hydrocarbon raw material to prepare the catalyst of light aromatics and light paraffins.This catalyst is used for hydrocarbon raw material by the efficient bifunctional catalyst of binder free Zeolite support carried noble metal and is converted into light aromatics and light paraffins, generate the BTX light aromatics of high added value by the heavy aromatic hydrocarbon light in this process raw material, it is higher to have activity, and stability is advantage preferably.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of hydrocarbon raw material prepares the catalyst of light aromatics and light paraffins, and is composed of the following components by weight percentage: a) 0.01～0.8% be selected among Pt or the Pd at least a; B) greater than 0 and smaller or equal at least a among Cu, Sn, Pb or the Fe of being selected from of 1%; C) at least a in the modenite that is selected from binder free of surplus, zeolite beta, Y zeolite, ZSM-5 or the ZSM-11 type zeolite.
The load capacity of selecting Pt or at least a metal of Pd in the technique scheme for use preferable range by weight percentage is 0.01～0.5%, selected binder free zeolite preferred version is selected from least a in modenite, zeolite beta, ZSM-5 or the ZSM-11 type zeolite, and the silica/alumina mole ratio preferable range of binder free zeolite is 10～200.Also contain in the catalyst and be selected from least a among Cu, Sn, Pb or the Fe, its consumption is by weight percentage〉0～1%.
Preparation of catalysts method of the present invention is as follows: the binder free zeolite is synthetic with the preparation of sodium type, carry out ion-exchange with acid solutions such as ammonium salt solution or hydrochloric acid then, carry out roasting after the exchange and be converted into h-type zeolite, introduce at least a metal of Pt or Pd then by ion-exchange or dipping method, use palladium bichloride, palladium nitrate, ammonium chloropalladate, ammonium chloropalladite, platinum nitrate, chloroplatinic acid, ammonium chloroplatinate, ammonium chloroplatinite, dichloro four ammoniums close at least a aqueous solution of platinum as precursor, for the hydrogenation activity of regulating noble metal adds Cu, Sn, Pb, at least a among the Fe introduced as assistant metal, and its consumption is 0～1% by weight percentage.The binder free h-type zeolite is introduced after Pt or the Pd, carries out drying under less than 200 ℃, at 300～600 ℃ dried catalyst is calcined then.
Catalyst of the present invention is applicable to that hydrocarbon raw material prepares light aromatics and light paraffins, is preferably reformate, drippolene, contains C9
+The mixture of aromatic hydrocarbons, naphtha and their mixture are with preparation BTX aromatic hydrocarbons and liquefied petroleum gas LPG.
Catalyst of the present invention adopts the binder free zeolite as acidic components, and it is big to have sour density, and the characteristics that the aperture is unobstructed, metal hydrogenation component have the characteristics of hydrogenation moderate performance, are being used for reformate, drippolene, containing C
9 +The mixture of aromatic hydrocarbons, naphtha and their mixture prepare and have good actively and stable in the reaction of BTX aromatic hydrocarbons and liquefied petroleum gas LPG, have obtained better technical effect.Weight (hourly) space velocity (WHSV) at 250～600 ℃ of inlet temperatures, reaction pressure 0.5～5Mpa, hydrocarbon raw material is 0.5～10 hour
-1, hydrogen/hydrocarbon raw material counts 0.5～10 than with mole, to reformate, drippolene, contain C
9 +The mixture of aromatic hydrocarbons, naphtha and their mixture prepare in the reaction of BTX aromatic hydrocarbons and liquefied petroleum gas LPG the non-aromatics cracking and heavy arene takes off alkyl degree height, have improved the concentration of BTX in the product, have obtained better technical effect.
The present invention is further elaborated below by embodiment.But these embodiment limit scope of the present invention.
The specific embodiment
[embodiment 1]
With TPAOH (TPAOH) solution, positive tetraethyl orthosilicate (TEOS) and water according to (TPA)
2O: 5.5TEOS: 90H
2The mixed in molar ratio of O stirs, and obtains ZSM-5 crystal seed directed agents in three days 80 ℃ of aging down backflows.Take by weighing the white carbon black of 180 grams, 10 gram sesbania powder, the aqueous solution that contain 19.7 gram sodium aluminates and 40 gram ZSM-5 crystal seed directed agents add the Ludox (percentage by weight 40%) of 230 grams and suitable quantity of water again and mix to pinch and carry out drying after the shaping and obtain cylindric presoma.Add the ethylenediamine of 35 grams and the mixture of 5 gram distilled water in the reactor in advance, place sealing back, the online side of reactor porous stainless steel under 160 ℃, to carry out gas-solid the 150 cylindric presomas that restrain above-mentioned preparation and handled mutually 5 days.Product obtains the adhesiveless ZSM-5 zeolite in 550 ℃ of roastings after with the distilled water washing and drying in air atmosphere.Carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite.The infusion process load weight 400 ℃ of calcinings 4 hours, obtains catalyst a than the Pd of meter 0.15% and 0.15% Pt on Hydrogen adhesiveless ZSM-5 zeolite.
[embodiment 2]
Take by weighing the overstable gamma zeolite zeolite (SiO of 100 gram white carbons and 20 grams
2/ Al
2O
3Mol ratio is 16) the ZSM-5 crystal seed directed agents of 20 grams in the mix embodiment 1, add the Al that contain 26 grams
2(SO
4)
318H
2The aqueous solution of O is adjusted the silica alumina ratio of mixture, and the Ludox (mass percent 40 weight %) that add 150 grams again mix to pinch and carry out drying after the shaping and obtain cylindric presoma.Add the ethamine of 34 grams and the mixture of distilled water in the reactor in advance, place sealing back, the online side of reactor porous stainless steel under 180 ℃, to carry out gas-solid the 100 cylindric presomas that restrain above-mentioned preparation and handled mutually 5 days.Product takes out the back with the distilled water washing, dries the back and obtain adhesiveless ZSM-5/USY zeolite in 550 ℃ of roastings in air atmosphere.Carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite.The ion-exchange load weight 400 ℃ of calcinings 4 hours, obtains catalyst b than the Pd of meter 0.3% on Hydrogen adhesiveless ZSM-5/USY zeolite.
[embodiment 3]
Take by weighing the zeolite beta (SiO of 180 gram white carbons and 140 grams
2/ Al
2O
3Mol ratio is 20) the ZSM-5 crystal seed directed agents of 40 grams in the mix embodiment 1, add and contain 110 gram Al
2(SO
4)
318H
2The aqueous solution of O is adjusted the silica alumina ratio of mixture, and the Ludox (mass percent 40 weight %) that add 220 grams again mix to pinch and carry out drying after the shaping and obtain cylindric presoma.Add the ethamine of 40 grams and the mixture of distilled water in the reactor in advance, place sealing back, the online side of reactor porous stainless steel under 150 ℃, to carry out gas-solid the 100 cylindric presomas that restrain above-mentioned preparation and handled mutually 7 days.Product takes out the back with the distilled water washing, dries the back and obtain adhesiveless ZSM-5/zeolite beta in 550 ℃ of roastings in air atmosphere.Carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite.The ion-exchange load weight 400 ℃ of calcinings 4 hours, obtains catalyst c than the Pd of meter 0.10% and 0.10% Pt on Hydrogen adhesiveless ZSM-5/zeolite beta.
[embodiment 4]
The ion-exchange load weight 400 ℃ of calcinings 4 hours, obtains catalyst d than the Pt of meter 0.20% and 0.15% Cu on the Hydrogen adhesiveless ZSM-5 zeolite of example 1 preparation.
[embodiment 5]
Take by weighing the sodium aluminate (Al of 120 gram white carbons, 5 gram sesbania powder and 22.4 grams
2O
3Mass percent is 43%) mixing 200 gram zeolite beta (SiO
2/ Al
2O
3Mol ratio is 30), the Ludox (mass percent 40 weight %) that add 300 grams again mix to pinch and carry out drying after the shaping and obtain cylindric presoma.With cylindric presoma and the 83 gram mass percentage concentrations of the above-mentioned preparation of 60 grams is that 13% tetraethyl ammonium hydroxide (TEAOH) solution mixes and places crystallizing kettle to carry out hydrothermal treatment consists four days under 145 ℃.Product takes out the back with the distilled water washing, dries the back and obtain the binder free zeolite beta in 550 ℃ of roastings in air atmosphere.Carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite.The ion-exchange load weight 400 ℃ of calcinings 4 hours, obtains catalyst e than the Pd of meter 0.15% and 0.15% Pt on Hydrogen binder free zeolite beta.
[embodiment 6]
The siliceous alumina powder that takes by weighing 180 gram white carbons, 12 gram sesbania powder and 50 grams (contains SiO
2Mass percent is 26%) mix 21 gram NaOH, 60 gram modenite (SiO
2/ Al
2O
3Mol ratio is 20), the Ludox (mass percent 40 weight %) that mix 550 grams mix to pinch and carry out drying after the shaping and obtain cylindric presoma.With cylindric presoma and the 120 gram mass percentage concentrations of the above-mentioned preparation of 60 grams is that 2.5% sodium hydroxide solution mixes and places crystallizing kettle to carry out hydrothermal treatment consists three days under 160 ℃.Product takes out the back with the distilled water washing, dries the back and obtain the binder free modenite in 550 ℃ of roastings in air atmosphere.Carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite.The ion-exchange load weight 400 ℃ of calcinings 4 hours, obtains catalyst f than the Pd of meter 0.15% and 0.15% Pt on Hydrogen binder free modenite.
[embodiment 7]
With TBAH (TBAOH) solution, positive tetraethyl orthosilicate (TEOS) and water according to (TBA)
2O: 6.22TEOS: 163H
2The mixed in molar ratio of O stirs, and obtains ZSM-11 crystal seed directed agents in three days 95 ℃ of aging down backflows.Take by weighing the white carbon black of 200 grams, the siliceous alumina powder of 12.5 gram sesbania powder, 36 grams (contains SiO
2Mass percent is 26%) and 51 gram ZSM-11 crystal seed directed agents, add the aqueous solution that contains 20 gram NaOH, the Ludox (percentage by weight 40%) that add 475 grams again mix to pinch and carry out drying after the shaping and obtain cylindric presoma.
With cylindric presoma and the 80 gram mass percentage concentrations of the above-mentioned preparation of 40 grams is that 8% TBAH (TBAOH) solution mixes and places crystallizing kettle to carry out hydrothermal treatment consists three days under 160 ℃.Product obtains binderless ZSM-5-11 zeolite in 550 ℃ of roastings after with the distilled water washing and drying in air atmosphere.Carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite.The infusion process load weight 400 ℃ of calcinings 4 hours, obtains catalyst g than the Pd of meter 0.15% and 0.15% Pt on Hydrogen adhesiveless ZSM-5 zeolite.
[embodiment 8]
Take by weighing the NaZSM-5 Zeolites Zeolites (SiO of 200 gram white carbons and 80 grams
2/ Al
2O
3Mol ratio is 60) mix, add the sodium aluminate (Al that contains 26 grams
2O
3Mass percent is 43%) adjust the silica alumina ratio of mixture, the ZSM-5 crystal seed directed agents that add among the embodiment 1 45 grams again, the Ludox (mass percent 40 weight %) and 30 that add 410 grams again restrain water and mix to pinch and carry out drying after the shaping and obtain cylindric presoma.Adding the ethamine of 34 grams and distillation in the reactor in advance mixes to pinch and carries out drying after the shaping and obtain cylindric presoma.Add the ethamine of 34 grams and the mixture of distilled water in the reactor in advance, place sealing back, the online side of reactor porous stainless steel under 180 ℃, to carry out gas-solid the 100 cylindric presomas that restrain above-mentioned preparation and handled mutually 5 days.Product takes out the back with the distilled water washing, dries the back and obtain the adhesiveless ZSM-5 zeolite in 550 ℃ of roastings in air atmosphere.Carry out ion-exchange with ammonium nitrate solution then, carry out roasting after the exchange and be converted into h-type zeolite.The ion-exchange load weight 430 ℃ of calcinings 4 hours, obtains catalyst h than the Pd of meter 0.04% and 0.04% Pt on Hydrogen adhesiveless ZSM-5/USY zeolite.
Use is reacted examination by the above-mentioned a that makes～h catalyst, and reaction raw materials is formed (quality percentage composition) and is＜C
6Non-aromatic 3.99%, C
6～8Non-aromatic 3.563%, C
6～8Virtue: 71.662% (wherein ethylbenzene 5.14%, dimethylbenzene 9.142%), C
9: 15.471% (wherein indane 2.466%), tetrahydro-dicyclopentadiene 4.481%, catalyst in fixed bed reactors at Hydrogen Vapor Pressure 3.0MPa, H
2/ oil volume is than 400,400 ℃ of reaction inlet temperatures, weight (hourly) space velocity (WHSV) WHSV=2.0～4.0 hour
-1Situation under check and rate, reaction result is listed in table 1:
Table 1 catalyst performance result
From last table as seen, the non-aromatic component can be carried out the hydrocracking generation effectively less than C
6Non-aromatics mainly is LPG, therefore separates heavy end C easily from the aromatic hydrocarbons of liquid state
9 +Can most ofly transform, only need gas-liquid separator and destilling tower just can easily from hydrocarbon raw material, isolate the advantage of high-purity aromatic hydrocarbons and non-aromatic component so the present invention uses above-mentioned catalyst to have.
Claims (4)
1. a hydrocarbon raw material prepares the catalyst of light aromatics and light paraffins, and is composed of the following components by weight percentage:
A) 0.01～0.8% be selected among Pt or the Pd at least a;
B) greater than 0 and smaller or equal at least a among Cu, Sn, Pb or the Fe of being selected from of 1%;
C) at least a in the modenite that is selected from binder free of surplus, zeolite beta, Y zeolite, ZSM-5 or the ZSM-11 type zeolite.
2. the catalyst for preparing light aromatics and light paraffins according to the described hydrocarbon raw material of claim 1, it is characterized in that selecting for use by weight percentage consumption at least a among Pt or the Pd is 0.01～0.5%.
3. the catalyst for preparing light aromatics and light paraffins according to the described hydrocarbon raw material of claim 1 is characterized in that selected binder free zeolite is selected from least a in modenite, zeolite beta, ZSM-5 or the ZSM-11 type zeolite.
4. prepare the catalyst of light aromatics and light paraffins according to the described hydrocarbon raw material of claim 1, the silica/alumina mole ratio that it is characterized in that used binder free zeolite is 10～200.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100439409A CN101347742B (en) | 2007-07-18 | 2007-07-18 | Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials |
| TW097127136A TWI478768B (en) | 2007-07-18 | 2008-07-17 | Catalysts and methods for the production of light aromatics and light alkanes from hydrocarbon feedstocks |
| US12/175,835 US20090023968A1 (en) | 2007-07-18 | 2008-07-18 | Catalyst and process for producing light aromatic hydrocarbons and light alkanes from hydrocarbonaceous feedstock |
| KR1020080070320A KR101539613B1 (en) | 2007-07-18 | 2008-07-18 | Catalyst and process for preparing light aromatic hydrocarbons and light alkanes from hydrocarbonaceous feedstock using the catalyst |
| US13/290,596 US8309778B2 (en) | 2007-07-18 | 2011-11-07 | Catalyst and process for producing light aromatic hydrocarbons and light alkanes from hydrocarbonaceous feedstock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100439409A CN101347742B (en) | 2007-07-18 | 2007-07-18 | Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials |
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| CN101347742A CN101347742A (en) | 2009-01-21 |
| CN101347742B true CN101347742B (en) | 2011-07-20 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746091B (en) * | 2011-04-20 | 2015-04-08 | 中国石油化工股份有限公司 | Method for producing BTX (benzene, toluene and xylol) aromatic hydrocarbons and trimethylbenzene from heavy aromatic hydrocarbons |
| CN102746092B (en) * | 2011-04-20 | 2015-04-08 | 中国石油化工股份有限公司 | Method for separating and producing 1,3,5-trimethylbenzene through hydrocracking heavy aromatic hydrocarbons |
| CN102746093B (en) * | 2011-04-20 | 2016-01-13 | 中国石油化工股份有限公司 | Heavy aromatics hydrocracking is utilized to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene |
| CN102897788B (en) * | 2011-07-29 | 2015-05-20 | 中国石油化工股份有限公司 | Synthesis method for ZSM-11 molecular sieve |
| CN103374395B (en) * | 2012-04-26 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of take petroleum naphtha as the method for raw material production aromatic hydrocarbons and ethene |
| CN103418426B (en) * | 2012-05-16 | 2016-09-07 | 中国石油化工股份有限公司 | Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst and preparation method thereof |
| CN104549440A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Adhesive-free oxy-compound aromatization catalyst and preparation method thereof |
| CN109092351A (en) * | 2017-06-21 | 2018-12-28 | 江苏华伦化工有限公司 | A kind of preparation method and application of the support type composite molecular screen based on microwave technology |
| CN110180581B (en) * | 2018-02-22 | 2021-11-30 | 中国石油化工股份有限公司 | Catalysts and their use in C11+Application in reaction for converting heavy aromatics into light aromatics |
| CN110882721A (en) * | 2018-09-10 | 2020-03-17 | 国家能源投资集团有限责任公司 | Aromatization catalyst and preparation method and application thereof |
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| CN86106388A (en) * | 1986-09-23 | 1988-04-06 | 华东化工学院 | A kind of preparation method of alkane isomerization catalyst |
| CN1902145A (en) * | 2003-12-30 | 2007-01-24 | 沙地基本工业公司 | Process for alkane aromatization using platinum-zeolite catalyst |
| CN1927714A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Preparation method of ZSM-type molecular sieve without binding agent |
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2007
- 2007-07-18 CN CN2007100439409A patent/CN101347742B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106388A (en) * | 1986-09-23 | 1988-04-06 | 华东化工学院 | A kind of preparation method of alkane isomerization catalyst |
| CN1902145A (en) * | 2003-12-30 | 2007-01-24 | 沙地基本工业公司 | Process for alkane aromatization using platinum-zeolite catalyst |
| CN1927714A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Preparation method of ZSM-type molecular sieve without binding agent |
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