CN1340487A - Noble metal modified selective disproportionation catalyst of toluene - Google Patents
Noble metal modified selective disproportionation catalyst of toluene Download PDFInfo
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- CN1340487A CN1340487A CN00119772A CN00119772A CN1340487A CN 1340487 A CN1340487 A CN 1340487A CN 00119772 A CN00119772 A CN 00119772A CN 00119772 A CN00119772 A CN 00119772A CN 1340487 A CN1340487 A CN 1340487A
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- catalyst
- toluene
- molecular sieve
- selective disproportionation
- noble metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A noble metal modified selective catalyst for the disproportionating reaction of toluene is prepared through using hydrogen-type ZSM-5 molecular sieve to carry noble metal and uniforcibly carry at least one of Cr, Ni, Mo, W, Sb and Bi. Its advantages are high activity and selectivity.
Description
The present invention relates to a kind of catalyst for selective disproportionation of toluene, particularly about the catalyst for selective disproportionation of toluene of modified with noble metals.
Toluene disproportionation process is one of industrial common reaction, and it can change into toluene higher benzene of using value and dimethylbenzene, and wherein the dimethylbenzene product is the equilibrium composition mixture of its three isomer, and the p-Xylol that has the call only accounts for about 24%.Therefore there is the people to propose the novel process of selective disproportionation, makes reaction system optionally generate p-Xylol.Conventional toluene disproportionation catalyst is main active ingredient with mordenite, because the mordenite channel diameter is bigger, three kinds of isomer of p-Xylol do not have the effect of selecting shapeization.After the beginning of the seventies, ZSM-5 was synthesized, because it is extensively paid attention to alkylation, isomerization, disproportionation, selective cracking process and the catalytic performance that has uniqueness by reactions such as methanol synthesized gasolines.The ZSM-5 zeolite constitutes pore canal system by 10 yuan of oxygen rings, has medium sized aperture and aperture.The aperture characteristics permission molecular diameter of ZSM-5 zeolite is that the p-Xylol of 0.63 nanometer spreads rapidly, can seriously hinder o-Xylol and m-xylene diffusion that molecular diameter is 0.69 nanometer simultaneously.In the toluene disproportionation process system, there is following relation in the spread coefficient of each species in the ZSM-5 duct: benzene 〉=toluene＞ethylbenzene ≈ p-Xylol＞o-Xylol ≈ m-xylene, this fact means carries out the possibility that shape is selected to toluene disproportionation process, can obtain to be higher than in the dimethylbenzene product p-Xylol content of isomer of thermodynamic(al)equilibrium concentration far away.Because the outer surface acidity position is to the isomerization of the rich contraposition product non-selectivity of coming out from the duct internal diffusion, so final product still is equilibrium composition.Though there are some researches show, under the condition of high-speed and low-conversion, adopt the ZSM-5 of big crystal grain also can obtain certain shape selectivity, there is not practical value.Therefore, expect catalyzer, the ZSM-5 molecular sieve be carried out modification be necessary with higher para-selectivity.
The early stage method of modifying that adopts mainly is phosphorus, magnesium elements modification, phosphorus, magnesium-modifiedly can play neutralization and promotor action to the molecular sieve surface acidity, phosphorus, molecular sieve surface strong acid center is reduced after magnesium-modified, and the weak acid center increases relatively.Strong acid center forms stable meta-isomer easily, and the weak acid center then helps forming para-isomeride.In addition, phosphorus can covering catalyst the strong acid center of outside surface, stop the quick isomerization of p-Xylol of coming out in the duct, phosphorus can also make the effective dimensions in duct infall or aperture reduce.Catalyzer through phosphorus, magnesium-modified after, also available halogenide, carbonic acid gas, nitrogenous compound, sulfocompound are further handled catalyzer to improve para-selectivity.But these treatment processs can obviously reduce activity of such catalysts, even reaction is carried out under very high temperature, transformation efficiency is still not high, and phosphoric easy loss under reaction conditions also is a defective of this technology.
Proposed modification in the document United States Patent (USP) 5367099 and 5607888, promptly reduced port size and shielding outer surface acidity active sites, the preparation catalyst for selective disproportionation of toluene the ZSM-5 molecular sieve structure.The method of modifying is to select the macromolecular cpd with thermolysis property for use, be deposited on molecular sieve outer surface by certain method, pass through pyroprocessing again, with these macromolecular cpd thermolysiss, be converted into inert coating, the acid sites of shielding molecular sieve outer surface has also dwindled port size simultaneously to a certain extent.Because the macromolecular cpd precursor does not enter in the duct, therefore do not change the acid matter of molecular sieve pore passage internal surface substantially, so just can too not seriously influence the activity of such catalysts generation.What these macromolecular cpds with thermolysis property were generally selected for use is silicane or (gathering) siloxane compound, and commonly used is polysiloxane-based.Thereby the meeting thermolysis under high temperature action of these silicon-containing compounds is converted into siliceous deposits and plays modifying function.The method that silicon-containing compound is deposited on molecular sieve outer surface has two kinds: a kind of is that silicon-containing compound is mixed in the methylbenzene raw material, under reaction conditions, make catalyzer original position (in situ) select shapeization, make catalyzer reach gratifying para-selectivity through pre-treatment after a while; Another kind is that dystopy (ex situ) is selected shapeization, is about to silicon-containing compound and impregnated in molecular sieve outer surface, and roasting obtains selecting the catalyzer of shapeization again.Patent points out that these two kinds of methods can combine use.Its catalyzer of report has higher activity and para-selectivity in these patents, but tests confirmation through the inventor, and it is active lower with para-selectivity.
To the objective of the invention is that catalyst for selective disproportionation of toluene exists activity and the lower defective of para-selectivity in the document in order overcoming in the past, a kind of catalyst for selective disproportionation of toluene of new modified with noble metals to be provided.This catalyzer has active high, the characteristics that para-selectivity is high.
The objective of the invention is to realize by following technical scheme: a kind of catalyst for selective disproportionation of toluene of modified with noble metals by weight percentage, contains Hydrogen ZSM-5 molecular sieve 20～90%, SiO
2/ Al
2O
3Molecular ratio is 10～100, and load is selected from least a precious metal element 0.005～5% in ruthenium, rhodium, palladium, rhenium, platinum or the gold on Hydrogen ZSM-5 molecular sieve, and binding agent silicon-dioxide or aluminum oxide are 9～75% in catalyzer.
In the technique scheme, the SiO of Hydrogen ZSM-5 molecular sieve
2/ Al
2O
3The molecular ratio preferable range is 15～80; Be selected from least a precious metal element in ruthenium, rhodium, palladium, rhenium, platinum or the gold by weight percentage, its charge capacity preferable range is 0.01～2%; The precious metal element preferred version is to be selected from least a in palladium or the platinum; On Hydrogen ZSM-5 molecular sieve also load be selected from least a in chromium, nickel, molybdenum, tungsten, antimony or the bismuth element, by weight percentage, charge capacity is 0.01～10%; For improving para-selectivity, behind shaping of catalyst, flood the phenyl methyl siloxane treated again, the consumption of phenyl methyl siloxanes is 5～40% of a catalyst weight, its preferable range is 10～30% of a catalyst weight.
Preparation of catalysts method of the present invention is as follows:
With the ZSM-5 molecular sieve is active main body, adopts the method that adds the binding agent extrusion to prepare moulding.The binding agent that adds can be SiO
2Or Al
2O
3, the add-on of binding agent is counted between 9% to 75% with its per-cent in preformed catalyst butt weight.In catalyst preparation process, introduce required metallic element and carry out modification.The existence form of metallic element can be oxide compound, oxyhydroxide or salt, and the method for introducing can adopt ion-exchange, dipping or mechanically mixing.The catalyzer of moulding adopts U.S. Pat 5367099 and the disclosed method of US5607888 again, selects the shape processing with the phenyl methyl polysiloxane, to obtain having the catalyzer of very high para-selectivity in toluene disproportionation process.
The present invention carried out modification by the element of introducing precious metal and be selected from chromium, nickel, molybdenum, tungsten, antimony or bismuth on Hydrogen ZSM-5 molecular sieve, weight space velocity 4.0 hours
-1Temperature of reaction is 425 ℃, reaction pressure is 2.1MPa, hydrogen hydrocarbon mol ratio is to carry out the toluene disproportionation process examination under 2.0 conditions, make toluene conversion the highlyest rise to 54.6% from 46.1%, increased by 18.4%, after handling with the phenyl methyl polysiloxane equally, para-selectivity the highlyest rises to 93.3% from 73.4%, has increased by 27.1%.These data declaration Hydrogens ZSM-5 molecular sieve is by precious metal with after being selected from the modification of chromium, nickel, molybdenum, tungsten, antimony or bismuth element, significantly improved activity of such catalysts, in addition by after handling with the phenyl methyl polysiloxane, can significantly improve the selectivity of the contraposition p-Xylol of catalyzer simultaneously, obtain effect preferably.
The invention will be further elaborated below by embodiment: [embodiment 1]
Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Mol ratio is ammonium type ZSM-5 molecular sieve powder 40.0 grams of 26,550 ℃ of calcination losses 10%, adds 30.0 gram silicon sol (SiO
2Weight percent content 40%) and 0.012 gram chemical pure Palladous nitrate [Pd (NO
3)
22H
2O], the solution that is made into of 0.2 milliliter of chemical pure nitric acid and 2 ml waters.Even this mixture thorough mixing, the kneading extruded moulding dries the back roasting, makes weight ratio and is: Pd/ Hydrogen ZSM-5 molecular sieve/SiO
2=0.01/75/25 catalyst A.[embodiment 2]
Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Mol ratio is 35, the ammonium type ZSM-5 molecular sieve powder of calcination loss 10% 40.0 grams, adds with chemical pure Palladous nitrate [Pd (NO
3)
22H
2O] mixing solutions that 7.51 grams, 4 milliliters in chemical pure nitric acid and 40 ml waters are made into, thorough mixing is even, and 110 ℃ of dryings are again with Na
2O content is less than the pseudo-boehmite (α-Al of 0.15%, 550 ℃ of calcination loss 30%
2O
3H
2O) 34.3 grams mix, and add 2 milliliters in chemical pure nitric acid and 30 ml waters again, mediate extruded moulding, dry the back roasting, make weight ratio and are: the catalyst B of Pd/ Hydrogen ZSM-5 molecular sieve/aluminum oxide=5.0/60/40.[embodiment 3]
Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Mol ratio is 38, the ammonium type ZSM-5 molecular sieve powder of calcination loss 10% 40.0 grams, and pseudo-boehmite 27.7 grams that add with embodiment 2 same sizes mix.With chemical pure Palladous nitrate [Pd (NO
3)
22H
2O] 0.693 the gram, analytical pure Platinic chloride [H
2PtCl
66H
2O] 0.735 the gram, chemical pure ammonium molybdate [(NH
4)
6Mo
7O
244H
2O] 1.0 grams, 3 milliliters in chemical pure nitric acid and 30 ml waters are made into mixing solutions.This mixing solutions is added in the mixture of ammonium type ZSM-5 molecular sieve and pseudo-boehmite, thorough mixing is even, the kneading extruded moulding dries the back roasting, makes weight ratio and is: the catalyzer C of Pd/Pt/Mo/ Hydrogen ZSM-5 molecular sieve/aluminum oxide=0.5/0.5/1.0/65/35.[embodiment 4]
Ammonium type ZSM-5 molecular sieve powder 40.0 grams of embodiment 1 add and pseudo-boehmite 22.0 grams of embodiment 2 same sizes mix.With chemical pure Palladous nitrate [Pd (NO
3)
22H
2O] 2.574 grams, 3 milliliters in chemical pure nitric acid and 30 ml waters are made into mixing solutions.This mixing solutions is added in the mixture of ammonium type ZSM-5 molecular sieve and pseudo-boehmite, mix, the kneading extruded moulding dries the back roasting, makes weight ratio and is: the catalyzer D of Pd/ Hydrogen ZSM-5 molecular sieve/aluminum oxide=2.0/70/30.[embodiment 5]
Ammonium type ZSM-5 molecular sieve powder 80.0 grams of embodiment 2, the silicon sol of adding 60.0 grams and embodiment 1 same size mixes, and mediates extruded moulding, dries the back roasting, makes weight ratio and is: Hydrogen ZSM-5 molecular sieve/SiO
2=75/25 catalyzer E.[embodiment 6～10]
Get 20 gram catalyst A～E respectively, join in the solution that phenyl methyl polysiloxane and 100 ml n-hexanes are made into, normal hexane is removed in distillation.Residuum behind the evaporate to dryness is warming up to 538 ℃ in muffle furnace, keep naturally cooling after 3 hours, by above-mentioned steps again re-treatment once obtain catalyzer F～J respectively, wherein handle successively with 2.0 gram phenyl methyl polysiloxane respectively must catalyzer F, G for catalyst A, B; Catalyzer C with 4.0 gram phenyl methyl polysiloxane handle catalyzer H; Catalyzer D, E respectively with 6.0 gram phenyl methyl polysiloxane handle catalyst I and J.[embodiment 11～20]
With catalyst A～J, on the fixed bed reaction evaluating apparatus, carry out the active and selectivity investigation of toluene disproportionation process.Loaded catalyst is 5.0 grams, and weight space velocity is 4.0 hours
-1, temperature of reaction is 425 ℃, and reaction pressure is 2.1MPa, and hydrogen hydrocarbon mol ratio is 2.Reaction result is listed in table 1.
The reaction result of table 1 catalyst A～L
[embodiment 21]
| Instance number | Catalyzer | Toluene conversion, % | The p-Xylol selectivity, % |
| ????11 ????12 ????13 ????14 ????15 ????16 ????17 ????18 ????19 ????20 | ????A ????B ????C ????D ????E ????F ????G ????H ????I ????J | ?????49.7 ?????52.4 ?????54.6 ?????53.1 ?????46.1 ?????23.3 ?????29.4 ?????32.8 ?????32.5 ?????15.8 | ?????23.9 ?????23.9 ?????24.2 ?????23.8 ?????23.7 ?????81.7 ?????92.1 ?????91.6 ?????93.3 ?????73.4 |
Ammonium type ZSM-5 molecular sieve powder 40.0 grams of embodiment 2, the silicon sol and 0.60 that adds 22.5 grams and embodiment 1 same size restrains analytical pure Platinic chloride [H
2PtCl
66H
2O], 0.83 gram chemical pure ammonium molybdate [(NH
4)
6Mo
7O
244H
2O], the solution that is made into of 0.5 milliliter in chemical pure nitric acid and 5 ml waters.Even this mixture thorough mixing, the kneading extruded moulding dries the back roasting, makes weight ratio and is: Pt/Mo/ Hydrogen ZSM-5 molecular sieve/SiO
2The catalyzer K of=0.5/1.0/80/20.
Getting 15 gram catalyzer K, place reactor, is reactant with the toluene that contains 2% (weight) phenyl methyl polysiloxane, carries out original position and selects the shape processing.Treatment condition are: weight space velocity 4.0 hours
-1, 446 ℃ of temperature of reaction, hydrogen hydrocarbon mol ratio is 2, reaction pressure 2.8MPa.The reaction result of different treatment time is listed in table 2.
Table 2 original position is selected the shape result
| Treatment time, hour | Toluene conversion, % | The p-Xylol selectivity, % |
| ????1 ????46 ????95 ????144 ????196 ????210 | ?????51.1 ?????46.3 ?????40.2 ?????37.8 ?????34.4 ?????31.3 | ?????24.6 ?????44.9 ?????66.4 ?????81.3 ?????86.7 ?????91.2 |
Claims (7)
1, a kind of catalyst for selective disproportionation of toluene of modified with noble metals by weight percentage, contains Hydrogen ZSM-5 molecular sieve 20～90%, SiO
2/ Al
2O
3Molecular ratio is 10～100, and load is selected from least a precious metal element 0.005～5% in ruthenium, rhodium, palladium, rhenium, platinum or the gold on Hydrogen ZSM-5 molecular sieve, and binding agent silicon-dioxide or aluminum oxide are 9～75% in catalyzer.
2,, it is characterized in that the SiO of Hydrogen ZSM-5 molecular sieve according to the catalyst for selective disproportionation of toluene of the described modified with noble metals of claim 1
2/ Al
2O
3Molecular ratio is 15～80.
3, according to the catalyst for selective disproportionation of toluene of the described modified with noble metals of claim 1, it is characterized in that being selected from by weight percentage at least a precious metal element in ruthenium, rhodium, palladium, rhenium, platinum or the gold, its charge capacity is 0.01～2%.
4,, it is characterized in that precious metal element is selected from least a in palladium or the platinum according to the catalyst for selective disproportionation of toluene of the described modified with noble metals of claim 3.
5, according to the catalyst for selective disproportionation of toluene of the described modified with noble metals of claim 1, it is characterized in that on the Hydrogen ZSM-5 molecular sieve also load and be selected from least a in chromium, nickel, molybdenum, tungsten, antimony or the bismuth element, by weight percentage, charge capacity is 0.01～10%.
6, according to the catalyst for selective disproportionation of toluene of the described modified with noble metals of claim 1, it is characterized in that flooding the phenyl methyl siloxane treated again behind the shaping of catalyst, the consumption of phenyl methyl siloxanes is 5～40% of a catalyst weight.
7, according to the catalyst for selective disproportionation of toluene of the described modified with noble metals of claim 6, the consumption that it is characterized in that the phenyl methyl siloxanes is 10～30% of a catalyst weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00119772XA CN1174803C (en) | 2000-08-29 | 2000-08-29 | Noble metal modified selective disproportionation catalyst of toluene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00119772XA CN1174803C (en) | 2000-08-29 | 2000-08-29 | Noble metal modified selective disproportionation catalyst of toluene |
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| CN1340487A true CN1340487A (en) | 2002-03-20 |
| CN1174803C CN1174803C (en) | 2004-11-10 |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008052445A1 (en) * | 2006-11-02 | 2008-05-08 | China Petroleum & Chemical Corporation | A toluene selective disproportionation catalyst |
| CN104275208A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of toluene shape-selective disproportionation catalyst |
| CN107952471A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation and application |
| CN108499596A (en) * | 2017-02-23 | 2018-09-07 | 中国石油化工股份有限公司 | Catalyst and preparation method thereof for toluene disproportionation and transalkylation |
| CN108499597A (en) * | 2017-02-23 | 2018-09-07 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and transalkylation and preparation method thereof |
| CN111068755A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Toluene methylation catalyst and preparation method and application thereof |
| CN112642467A (en) * | 2019-10-09 | 2021-04-13 | 中国石油化工股份有限公司 | Selective disproportionation catalyst and preparation method and application thereof |
-
2000
- 2000-08-29 CN CNB00119772XA patent/CN1174803C/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008052445A1 (en) * | 2006-11-02 | 2008-05-08 | China Petroleum & Chemical Corporation | A toluene selective disproportionation catalyst |
| JP2010508146A (en) * | 2006-11-02 | 2010-03-18 | 中国石油化工股▲ふん▼有限公司 | Catalyst for selectively disproportionating toluene |
| US8580702B2 (en) | 2006-11-02 | 2013-11-12 | China Petroleum & Chemical Corporation | Toluene selective disproportionation catalyst |
| CN104275208A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of toluene shape-selective disproportionation catalyst |
| CN104275208B (en) * | 2013-07-09 | 2017-09-15 | 中国石油化工股份有限公司 | The preparation method of toluene selective disproportionation catalyst |
| CN107952471A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation and application |
| CN108499596A (en) * | 2017-02-23 | 2018-09-07 | 中国石油化工股份有限公司 | Catalyst and preparation method thereof for toluene disproportionation and transalkylation |
| CN108499597A (en) * | 2017-02-23 | 2018-09-07 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and transalkylation and preparation method thereof |
| CN108499596B (en) * | 2017-02-23 | 2021-02-09 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and alkyl transfer and its preparation method |
| CN108499597B (en) * | 2017-02-23 | 2021-02-09 | 中国石油化工股份有限公司 | Toluene disproportionation and transalkylation catalyst and preparation method thereof |
| CN111068755A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Toluene methylation catalyst and preparation method and application thereof |
| CN112642467A (en) * | 2019-10-09 | 2021-04-13 | 中国石油化工股份有限公司 | Selective disproportionation catalyst and preparation method and application thereof |
| CN112642467B (en) * | 2019-10-09 | 2023-08-08 | 中国石油化工股份有限公司 | Selective disproportionation catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
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