CN103120953B - Disproportionation and alkyl transfer catalyst reducing method - Google Patents

Disproportionation and alkyl transfer catalyst reducing method Download PDF

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CN103120953B
CN103120953B CN201110366962.5A CN201110366962A CN103120953B CN 103120953 B CN103120953 B CN 103120953B CN 201110366962 A CN201110366962 A CN 201110366962A CN 103120953 B CN103120953 B CN 103120953B
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catalyst
hydrogen
gas
disproportionation
reducing
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CN103120953A (en
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邹薇
孔德金
李华英
李经球
郭宏利
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
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Abstract

The invention relates to a disproportionation and alkyl transfer catalyst reducing method which mainly solves the problems of low metal dispersity and high hydrogenation activity in the prior art. The reducing method of a catalyst for disproportionation and alkyl transfer reaction includes the steps: drying and dehydrating the catalyst by inert gas containing oxygen to obtain a catalyst I, and using reducing gas to reduce the catalyst I to obtain a catalyst II; and purging the catalyst II for 1-8 hours under the reducing gas and at the temperature of 300-700 DEG C to obtain a needed catalyst. By the technical scheme, the problems are well solved, and the method can be used in disproportionation and alkyl transfer industrial production of toluene and heavy aromatics.

Description

The method of reducing of disproportionation and transalkylation catalyst
Technical field
The present invention relates to the method for reducing of a kind of disproportionation and transalkylation catalyst.
Background technology
Paraxylene in C8 aronmatic is one of main basic organic of petrochemical industry, in numerous chemical production field such as chemical fibre, synthetic resin, agricultural chemicals, medicine, has purposes widely.For increasing production of xylol, utilize toluene disproportionation or toluene and carbon nine and above heavy aromatics (C thereof 9 +a) disproportionation and transalkylation reaction generate benzene and C8 aronmatic, are the effective ways of increasing yield of p-xylene.
Along with day by day becoming heavily of upstream reforming material, the comprehensive utilization of heavy arene becomes the problem that people are concerned about.C9 aromatic (C 9a) have the more ripe technology of utilizing, by the transalkylation reaction increasing production of xylol with toluene.And carbon ten and above heavy aromatics (C thereof 10 +a) can only partly be utilized at present, fused ring compound wherein easily aggravates the coking deactivation of catalyst, therefore, in traditional disproportionation and alkyl transfering process to the C in reaction raw materials 10 +a has strict restriction.For improving the stability of catalyst, can on molecular sieve catalyst, introduce hydrogenation metal component.But then, because metal has compared with strong hydrogenation performance, can promote the saturated and cracking side-reaction of the hydrogenation of aromatic hydrocarbons, production non-aromatics and light component, thus reduced dimethylbenzene yield.
The molecular sieve catalyst of carried metal generally need to carry out reduction activation before use, so that metal is converted into reduction-state by oxidation state.In commercial plant, the good no quality that is directly connected to catalyst performance of the reduction of metallic catalyst, and reduction process is also subject to the impact of factors, as water content, reduction temperature and reduction pressure etc. in reducing atmosphere.
WO2006039316 discloses a kind of method of ex-situ reduction of noble metal catalyst, and the method comprises and catalyst completed under the existence of hydrogen and noble gas mixtures in single step to dry and reduction.Secondly, the catalyst after reduction is carried out to passivation with mineral oil catalyst filling hole.
CN100357025 discloses a kind of method of reducing containing molecular sieve, noble metal catalyst, and the method contacts catalyst with ammonia with hydrogen with gaseous mixture, and in reducing metal, ammonia adsorbs shielding to strong acidic site, to suppress the high activity of crossing at the initial stage of driving.This patent is mainly concerned with the passivation completing in reduction process acid position.
The problems such as above-mentioned document, when metallic catalyst is carried out to reduction activation, exists metal dispersion low, the active height of metal hydrogenation.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to have that metal dispersion is low, the problem of metal hydrogenation hyperactivity, and the method for reducing of a kind of new disproportionation and transalkylation catalyst is provided.The method is for the activation of disproportionation and transalkylation catalyst, and activating catalyst has higher metal dispersion and suitable metal hydrogenation performance, can effectively reduce aromatic hydrocarbon ring loss.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for reducing of a kind of disproportionation and transalkylation reaction catalyst, comprises the following steps:
A) with the inert gas that contains oxygen, catalyst is carried out obtaining catalyst I after drying and dehydrating;
B) catalyst I is reduced to obtain to catalyst I I with reducibility gas;
C) under reducibility gas and at 300～700 ℃ of temperature, catalyst I I is purged to 1～8 hour, obtain required catalyst.
In technique scheme, inert gas is at least one in nitrogen, carbon dioxide, and in inert gas, oxygen content is 0.5～20vol%, preferred 1～6vol%, the final baking temperature of inert gas is 300～600 ℃, and during dry end, the water content in the dry gas of outflow is less than 200ppm.Reducibility gas is at least one in hydrogen, hydrogen～ammonia gas mixture, hydrogen～nitrogen mixed air, the Contact Temperature of reducibility gas and catalyst I is 300～500 ℃, be 1～15 hour time of contact, reducibility gas pressure is 0.05～5.0MPa, and the water content in reduction process in eluting gas is lower than 200ppm.Catalyst I I contacts with hydrogen and carries out passivation, and Contact Temperature is 400～650 ℃, and be 2～6 hours time of contact.By weight percentage, at least one in modenite, β zeolite, ZSM-12 molecular sieve that be selected from that catalyst contains 0.01%～0.2% the metal that is selected from VIIIB family and 50%～80%.
In the present invention, with the inert gas that contains certain oxygen, catalyst is dried, to remove the adsorbed water on catalyst, the existence of oxygen simultaneously can be avoided the agglomeration of metal oxide.Dried catalyst has contacted the reduction of metal oxide with reducibility gas, by control, optimize the condition such as moisture, reduction temperature in reducing gas, avoids reduction process to cause metallic agglomeration.Catalyst after reduction carries out suitable Passivation Treatment again, and the strong hydrogenation that has suppressed metal is active.
Use method of reducing of the present invention, can improve carried metal dispersiveness and optimize metal hydrogenation activity.Reducing catalyst, for disproportionation and the transalkylation reaction of toluene and heavy aromatics, has the advantages that reactivity is high, aromatic hydrocarbons loss late is low, has good industrial application value.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
By Na 20 content is less than 0.1% (weight), SiO 2/ Al 2o 3molecular proportion is 40 60 grams, β zeolite and Na 2o content is less than the γ-Al of 0.1% (weight) 2o 3h 257.1 grams of evenly mixing of O, then add a certain amount of rare nitric acid, field mountain valley with clumps of trees and bamboo powder to mediate evenly, and carrier is made in extruded moulding, roasting, and pelletizing is placed in steeper.A certain amount of chloroplatinic acid be impregnated in to carrier surface, and 120 ℃ of dry 4 hours, 500 ℃ roastings make catalyst A (0.05wt%Pt/ β) for 3 hours.Get 100ml catalyst A, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 400 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 500mL/min, reduce 1 hour at 200 ℃, be warming up to 400 ℃ of reduction 3 hours.Lift temperature to 500 ℃, hydrogen treat completes metal passivation for 3 hours.
Catalyst carries out reactivity investigation on fixed bed reaction evaluating apparatus.20 grams of Catalyst packings, liquid total feed weight air speed is 3.0 hours -1, 375 ℃ of reaction temperatures, reaction pressure 3.0MPa, hydrogen hydrocarbon molecule is than 3.0, and raw material is toluene: C 9 +a=30: 70 (weight), wherein C 9 +in A, contain 15% (weight) C 10 +a.C 9a raw material weight consists of: propyl benzene 4.2%, the first and second benzene 29.04%, trimethylbenzene 59.6%, C 10 +a weight consists of: diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49, dimethylnaphthalene 11.16%, other 12.90%, evaluation result is as shown in table 1.
[embodiment 2]
By Na 2o content is less than 0.1% (weight), SiO 2/ Al 2o 3molecular proportion is 40 60 grams of modenites and Na 2o content is less than the γ-Al of 0.1% (weight) 2o 3h 257.1 grams of evenly mixing of O, then add a certain amount of rare nitric acid, field mountain valley with clumps of trees and bamboo powder to mediate evenly, and carrier is made in extruded moulding, roasting, and pelletizing is placed in steeper.A certain amount of palladium bichloride be impregnated in to carrier surface, and 120 ℃ of dry 4 hours, 500 ℃ roastings make catalyst B (0.2wt%Pd/Mor) for 3 hours.Catalyst reduction condition and active examination condition are as described in Example 1.
[embodiment 3]
Get 100ml catalyst A, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 300 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 500mL/min, reduce 1 hour at 200 ℃, be warming up to 350 ℃ of reduction 4 hours.Lift temperature to 500 ℃, hydrogen treat completes metal passivation for 1 hour.Catalyst activity examination condition as described in Example 1.
[embodiment 4]
Get 100ml catalyst A, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 500 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 500mL/min, reduce 1 hour at 200 ℃, be warming up to 400 ℃ of reduction 4 hours.Lift temperature to 450 ℃, hydrogen treat completes metal passivation for 3 hours.Catalyst activity examination condition as described in Example 1.
[embodiment 5]
Get 100ml catalyst A, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 5vol.%, be warming up at 400 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 1000mL/min, reduce 1 hour at 200 ℃, be warming up to 400 ℃ of reduction 3 hours.Lift temperature to 450 ℃, hydrogen treat completes metal passivation for 5 hours.Catalyst activity examination condition as described in Example 1.
[embodiment 6]
Get 100ml catalyst A, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 400 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 500mL/min, reduce 1 hour at 200 ℃, be warming up to 450 ℃ of reduction 3 hours.Lift temperature to 550 ℃, hydrogen treat passivation 2 hours.Catalyst activity examination condition as described in Example 1.
[embodiment 7]
Get 100ml catalyst A, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 400 ℃ and be dried 3 hours, carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 500mL/min, reduce 5 hours at 450 ℃.Lift temperature to 550 ℃, hydrogen Passivation Treatment 5 hours.Catalyst activity examination condition as described in Example 1.
[embodiment 8]
Get 100ml catalyst B, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 400 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into flow and be the hydrogen-nitrogen mixture containing 60vol.% hydrogen of 500mL/min, reduce 1 hour at 200 ℃, be warming up to 400 ℃ of reduction 3 hours.Lift temperature to 500 ℃, hydrogen Passivation Treatment 2 hours.Catalyst activity examination condition as described in Example 1.
[embodiment 9]
Get 100ml catalyst B, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 400 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into flow and be the hydrogen-ammonia gas mixture containing 90vol.% hydrogen of 500mL/min, reduce 1 hour at 200 ℃, be warming up to 400 ℃ of reduction 3 hours.Lift temperature to 500 ℃, hydrogen Passivation Treatment 2 hours.Catalyst activity examination condition as described in Example 1.
[embodiment 10]
Get 100ml catalyst B, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 400 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 500mL/min, reduce 1 hour at 200 ℃, be warming up to 400 ℃ of reduction 3 hours.Catalyst activity examination condition as described in Example 1.
[embodiment 11]
Get 100ml catalyst B, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 400 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 500mL/min, reduce 1 hour at 200 ℃, be warming up to 400 ℃ of reduction 3 hours.Lift temperature to 600 ℃, hydrogen Passivation Treatment 2 hours.Catalyst activity examination condition as described in Example 1.
[embodiment 12]
Get 100ml catalyst B, be placed in tubular reactor, pass into nitrogen-air Mixture that oxygenous amount is 3vol.%, be warming up at 400 ℃ and be dried 3 hours, be cooled to 200 ℃, and carry out abundant nitrogen replacement.Pass into the hydrogen that flow is 500mL/min, reduce 1 hour at 200 ℃, be warming up to 400 ℃ of reduction 3 hours.Lift temperature to 600 ℃, hydrogen Passivation Treatment 5 hours.Catalyst activity examination condition as described in Example 1.
The Evaluation results of catalyst is as shown in table 1.Method of reducing of the present invention can obtain higher metal dispersity and applicable metal hydrogenation activity.Under more excellent condition, conversion ratio is higher than 46wt%, and aromatic ring loss late is less than 2wt%.
Table 1 evaluating catalyst result

Claims (5)

1. a method of reducing for disproportionation and transalkylation reaction catalyst, comprises the following steps:
A) with the inert gas that contains oxygen, catalyst is carried out obtaining catalyst I after drying and dehydrating;
B) catalyst I is reduced to obtain to catalyst II with reducibility gas;
C) under reducibility gas and at 300～700 ℃ of temperature, catalyst II is purged to 1～8 hour, obtain required catalyst;
Wherein, inert gas is selected from least one in nitrogen, carbon dioxide; In inert gas, oxygen volume content is 0.5～20%; The final baking temperature of inert gas is 300～600 ℃; During dry end, the water content in the dry gas of outflow is less than 200ppm;
Reducibility gas is at least one in hydrogen, hydrogen～ammonia gas mixture or hydrogen～nitrogen mixed air;
The Contact Temperature of reducibility gas and catalyst I is 300～600 ℃; Be 1～15 hour the time of contact of reducibility gas and catalyst I; Reducibility gas pressure is 0.05～5.0MPa; Water content in reduction process in eluting gas is lower than 200ppm.
2. the method for reducing of disproportionation according to claim 1 and transalkylation catalyst, is characterized in that in inert gas, oxygen volume content is 1～6%.
3. the method for reducing of disproportionation according to claim 1 and transalkylation catalyst, is characterized in that catalyst II continues to contact with hydrogen to carry out passivation.
4. the method for reducing of disproportionation according to claim 1 and transalkylation catalyst, is characterized in that catalyst II and hydrogen Contact Temperature are 400～650 ℃, and be 2～6 hours time of contact.
5. the method for reducing of disproportionation according to claim 1 and transalkylation catalyst, is characterized in that catalyst contains by weight percentage:
A) 0.01%～0.2% the metal that is selected from VIII B family;
B) 50%～80% be selected from least one in modenite, β zeolite, ZSM-12 molecular sieve.
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CN107866265B (en) * 2016-09-23 2020-07-03 中国石油化工股份有限公司 Selective deactivation of transalkylation catalyst

Citations (5)

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Publication number Priority date Publication date Assignee Title
CN101121144A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Catalyst for aromatics alkyl transferring and dealkylation to synthesis benzene and xylene
CN101688124A (en) * 2007-05-04 2010-03-31 沙索技术有限公司 catalysts
CN101703937A (en) * 2009-09-29 2010-05-12 武汉凯迪科技发展研究院有限公司 Method for regenerating cobalt-base catalyst for slurry-phase Fischer-Tropsch synthesis
CN101822985A (en) * 2009-03-04 2010-09-08 中国石油天然气股份有限公司 Pretreatment method of nickel-based hydrogenation catalyst
CN102145286A (en) * 2011-01-11 2011-08-10 山西大学 Preparation method of Ni-SiO2/Al2O3 catalyst

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US7592289B2 (en) * 2001-10-25 2009-09-22 Sasol Technology (Proprietary) Limited Process for activating cobalt catalysts

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121144A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Catalyst for aromatics alkyl transferring and dealkylation to synthesis benzene and xylene
CN101688124A (en) * 2007-05-04 2010-03-31 沙索技术有限公司 catalysts
CN101822985A (en) * 2009-03-04 2010-09-08 中国石油天然气股份有限公司 Pretreatment method of nickel-based hydrogenation catalyst
CN101703937A (en) * 2009-09-29 2010-05-12 武汉凯迪科技发展研究院有限公司 Method for regenerating cobalt-base catalyst for slurry-phase Fischer-Tropsch synthesis
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